Sustainable Agriculture Reviews 26

Shivendu Ranjan
Nandita Dasgupta
Eric Lichtfouse Editors

Nanoscience
in Food and
Agriculture
5
Sustainable Agriculture Reviews

Volume 26

Series editor
Eric Lichtfouse
 Other Publications by Dr. Eric Lichtfouse

Books
Scientific Writing for Impact Factor Journals
Nova Publishers 2013
Sustainable Agriculture
Springer 2009
Sustainable Agriculture Volume 2
Springer 2011
Environmental Chemistry. Green Chemistry and Pollutants in Ecosystems
Springer 2005
Rédiger pour être publié ! Conseils pratiques pour les scientifiques
Springer 2012, 2e édition.
Journals and Series
Agronomy for Sustainable Development
www.springer.com/journal/13593
Sustainable Agriculture Reviews
www.springer.com/series/8380
Environmental Chemistry Letters
www.springer.com/journal/10311
Environmental Chemistry for a Sustainable World
www.springer.com/journal/11480
Blog
Agronomy blog
http://www1.montpellier.inra.fr/agronomy-blog
Magazine
Publier La Science
https://listes.inra.fr/sympa/d_read/veillecaps/

Sustainable agriculture is a rapidly growing field aiming at producing food and energy in a sustainable
way for humans and their children. Sustainable agriculture is a discipline that addresses current issues
such as climate change, increasing food and fuel prices, poor-nation starvation, rich-nation obesity, water
pollution, soil erosion, fertility loss, pest control, and biodiversity depletion.
Novel, environmentally-friendly solutions are proposed based on integrated knowledge from sci-
ences as diverse as agronomy, soil science, molecular biology, chemistry, toxicology, ecology, economy,
and social sciences. Indeed, sustainable agriculture decipher mechanisms of processes that occur from
the molecular level to the farming system to the global level at time scales ranging from seconds to
centuries. For that, scientists use the system approach that involves studying components and interactions
of a whole system to address scientific, economic and social issues. In that respect, sustainable agricul-
ture is not a classical, narrow science. Instead of solving problems using the classical painkiller approach
that treats only negative impacts, sustainable agriculture treats problem sources.
Because most actual society issues are now intertwined, global, and fast-developing, sustainable
agriculture will bring solutions to build a safer world. This book series gathers review articles that ana-
lyze current agricultural issues and knowledge, then propose alternative solutions. It will therefore help
all scientists, decision-makers, professors, farmers and politicians who wish to build a safe agriculture,
energy and food system for future generations.

More information about this series at http://www.springer.com/series/8380

Shivendu Ranjan  •  Nandita Dasgupta
Eric Lichtfouse
Editors

Nanoscience in Food
and Agriculture 5
Editors
Shivendu Ranjan Nandita Dasgupta
School of Biosciences and Technology School of Biosciences and Technology
VIT University VIT University
Vellore, Tamil Nadu, India Vellore, Tamil Nadu, India

Eric Lichtfouse
Europole Mediterraneen de l’Arbois
CEREGE INRA
Aix en Provence Cedex 04, France

ISSN 2210-4410     ISSN 2210-4429 (electronic)

Sustainable Agriculture Reviews
ISBN 978-3-319-58495-9    ISBN 978-3-319-58496-6 (eBook)
DOI 10.1007/978-3-319-58496-6

Library of Congress Control Number: 2016947716

1st edition: © Springer International Publishing Switzerland 2016

2nd edition: © Springer International Publishing Switzerland 2016
3rd edition: © Springer International Publishing Switzerland 2016
4th edition: © Springer International Publishing AG 2017
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We dedicate this book to our parents

Nano: a small prefix makes a big difference

Shivendu Ranjan
Nandita Dasgupta
Preface

Original concepts in food and agriculture have recently emerged following the dis-
covery of the new properties of nanomaterials. For instance, the hydrophobic
sheathing of leaves has been mimicked to coat food and agricultural materials at the
nanoscale. Research in nanoscience has produced materials with unique properties
such as nanotubes, nanofillers, nanoparticles, nanocomposites, nanoemulsions,
nanoliposomes, nanoclusters, and self-assembled nanoparticles. Nanoencapsulation
of functional molecules in food matrices is a new formulation technique that
enhances food quality and security. The hurdles previously observed during the
fabrication of encapsulating nanostructures have been addressed. Research is actu-
ally aiming at developing novel nanodelivery vehicles and evaluating their risks. In
particular, localized delivery and controlled release of nutrients is a current topic
(Fig. 1). Nanofertilizers and nanopesticides have the potential to enhance agricul-
tural productivity. However, the transfer of engineered nanoparticles in the food
chain may induce a toxic risk. This book reviews the formation, synthesis, function-
ality, applications, regulation, safety, and socioeconomic aspects of nanoparticles in
food and agriculture.
The first chapter by Yata et al. reviews patents and research trends. Sodano then
explains the actual issues of nanotechnologies in light of the social, economic, and
political aspects of the food chain, in Chap. 2. The principles and applications of
nanosensors are presented by Srivastava et al. in Chap. 3. In Chap. 4 Kumar and
Sarkar describe nanoemulsions for better nutrient delivery. Arora and Jaglan detail
a specific application of nanocarriers for therapeutic resveratrol in Chap. 5. Milk
proteins can be used for the encapsulation of active food ingredients, as explained
by Poonia in Chap. 6. In Chap. 7, Dev et al. review the uptake and toxicity of nano-
materials in plants. Nanoparticle toxicity and regulatory frameworks are discussed
in Chaps. 8 and 9 by Kaphle et al. and Kaundal et al. The concept of nanofertilizers
is explained in Chap. 10 by Sanivada et  al. The impact of nanomaterials on the

vii
viii Preface

Water Phase
Functional
Molecule
d (Steric
Thickness)

Emulsifier
Oil Phase
Core Bioactive Compound
Shell

Fig. 1  Left: shell-core model of an encapsulation matrix used for the protection of functional
molecules in food and agriculture. Copyright: H. Lohith, NIT Rourkela. Right: scheme of an oil
droplet dispersed in water, stabilized by an amphiphilic emulsifier. The bioactive compound
entrapped inside the oil droplet is a lipophilic molecule, which possesses health benefits and dis-
ease prevention properties (Sarkar et al. Chap. 4)

aquatic food chain is presented by Gupta et al in Chap. 11. Finally, nanoremediation
is presented by El-Ramady et al. in Chap. 12.
Thanks for reading.

Vellore, Tamil Nadu, India Shivendu Ranjan

Vellore, Tamil Nadu, India Nandita Dasgupta
Aix en Provence, France Eric Lichtfouse
Contents

1 Research Trends and Patents in Nano-food and Agriculture.............. 1

Vinod Kumar Yata, Bhupesh Chandra Tiwari,
and Irfan Ahmad
2 Politics of Nanotechnologies in Food and Agriculture.......................... 21
Valeria Sodano
3 Nanosensors for Food and Agriculture.................................................. 41
Anup K. Srivastava, Atul Dev, and Surajit Karmakar
4 Nanoemulsions for Nutrient Delivery in Food....................................... 81
DH Lohith Kumar and Preetam Sarkar
5 Nanocarriers for Resveratrol Delivery................................................... 123
Divya Arora and Sundeep Jaglan
6 Potential of Milk Proteins as Nanoencapsulation
Materials in Food Industry..................................................................... 139
Amrita Poonia
7 Uptake and Toxicity of Nanomaterials in Plants................................... 169
Atul Dev, Anup K. Srivastava, and Surajit Karmakar
8 Nanomaterial Impact, Toxicity and Regulation
in Agriculture, Food and Environment.................................................. 205
Anubhav Kaphle, Navya PN, Akhela Umapathi,
Maulick Chopra, and Hemant Kumar Daima
9 Nanomaterial Toxicity in Microbes, Plants and Animals..................... 243
Babita Kaundal, Swayamprava Dalai,
and Subhasree Roy Choudhury

ix
x Contents

10 Nanofertilizers for Sustainable Soil Management................................ 267

Santosh Kumar Sanivada, Venkata Smitha Pandurangi,
and Murali Mohan Challa
11 Impact of Nanomaterials on the Aquatic Food Chain.......................... 309
Govind Sharan Gupta, Rishi Shanker, Alok Dhawan,
and Ashutosh Kumar
12 Nanoremediation for Sustainable Crop Production............................. 335
Hassan El-Ramady, Tarek Alshaal, Mohamed Abowaly,
Neama Abdalla, Hussein S. Taha, Abdullah H. Al-Saeedi,
Tarek Shalaby, Megahed Amer, Miklós Fári,
Éva Domokos-Szabolcsy, Attila Sztrik, József Prokisch,
Dirk Selmar, Elizabeth A.H. Pilon Smits, and Marinus Pilon

Index.................................................................................................................. 365
About the Editors

Shivendu Ranjan has major expertise in Micro/

Nanotechnology and currently working in VIT
University, Vellore, Tamil Nadu, India. His area of
research is multidisciplinary which are as but not
limited to: Micro/Nanobiotechnology, Micro/Nano-­
toxicology, Micro/Nanoemulsions. He has published
many scientific articles in international peer-reviewed
journals. He has recently 5 edited books with Springer
and has contracted 3 books in Elsevier, 4 in CRC Press
and 1 in Wiley – all these books cover vast areas of
Applied Micro/Nanotechnology. He has vast editorial
experience. Briefly, he is serving as Associate Editor in Environmental Chemistry
Letters (Springer Journal with 2.91 Impact Factor); also serving as editorial panel in
Biotechnology and Biotechnological Equipment (Taylor and Francis, 0.3 Impact
Factor). He is also Executive Editor and expert board panel in several other journals.
He has been recently nominated as Elsevier Advisory Panel, Netherlands. He has
bagged several awards from different organizations e.g. Best poster award, special
achiever award, achiever award, research award, young researcher award etc.

Nandita Dasgupta has vast working experience on

Micro/Nanoscience and currently serving in VIT
University, Vellore, Tamil Nadu, India. She has been
exposed to verious research institutes and industries
including CSIR-­Central Food Technological Research
Institute, Mysore, India and Uttar Pradesh Drugs and
Pharmaceutical Co. Ltd., Lucknow, India. Her areas of
interest include Micro/Nanomaterials fabrication and
their applications in different fields majorly – medicine,
food, environment, agriculture, biomedical etc.
She has published many books with Springer and has
contracted few with Springer, Elsevier, CRC Press and
Wiley. She has also published many scientific articles in

xi
xii About the Editors

international peer-reviewed journals and also serving as editorial board member and
referee for reputed international peer-reviewed journals. She has received Elsevier
Certificate for “Outstanding Contribution” in Reviewing from Elsevier, The
Netherlands. She has also been nominated for Elsevier advisory panel for Elsevier,
The Netherlands. She is the Associated Editor in Environmental Chemistry Letters
– a Springer journal of 2.9 Impact Factor. She has received several awards from dif-
ferent organizations e.g. Best poster award, young researcher award, Special achiever
award, research award, etc.

Eric Lichtfouse, born in 1960, has PhD in organic

chemistry at Strasbourg University and is a geochemist
working on carbon sequestration and climate change at
the European Centre of Research and School in
Environmental Geosciences.1 He has invented the
13
C-dating method allowing to measure the dynamics of
soil organic molecules.2 He has published about 100
articles in organic synthesis, petroleum geochemistry,
environmental chemistry, food chemistry, soil science,
and phytoremediation.3 He is chief editor and founder
of the journal Environmental Chemistry Letters,4 the
book series Sustainable Agriculture Reviews5 and
Environmental Chemistry for a Sustainable World,6 and the magazine Publier La
Science.7 His book Scientific Writing for Impact Factor Journals8 contains the micro-
article,9 a new tool to identify the novelty of experimental results10,11,12,13,14. He is also
a triathlete who got the bronze medal in age groups at the World ITU Cross Triathlon
Championships. He has qualified for the Word Ironman, Ironman 70.3, and XTerra
Championships, finished 5 times in the top 3 of French Triathlon and Duathlon
Championships, and completed 17 ironman competitions. Further details are
available on LinkedIn and ResearchGate.

1
 www.cerege.fr
2
 http://dx.doi.org/10.1007/s10311-011-0334-2
3
 http://www.researcherid.com/rid/F-4759-2011,
https://scholar.google.fr/citations?user=MOKMNegAAAAJ
4
 http://www.springer.com/journal/10311
5
 http://www.springer.com/series/8380
6
 http://www.springer.com/series/11480
7
 http://www6.inra.fr/caps-publierlascience
8
 https://www.novapublishers.com/catalog/product_info.php?products_id=42211
9
 http://fr.slideshare.net/lichtfouse/micro-arten
10
 http://fr.slideshare.net/lichtfouse
11
 https://fr.linkedin.com/in/ericlichtfouse
12
 https://www.researchgate.net/profile/Eric_Lichtfouse
13
 http://www.researcherid.com/rid/F-4759-2011
14
 http://orcid.org/0000-0002-8535-8073
Chapter 1
Research Trends and Patents in Nano-food
and Agriculture

Vinod Kumar Yata, Bhupesh Chandra Tiwari, and Irfan Ahmad

Abstract  Today, with increasing population, food demand is on the rise and food
safety is a matter of concern. This has led to the development of innovative tech-
niques for better crop production and food preservation. In particular, publication
and patent analysis show a rise in nanoscience research for food and agriculture.
Food nanotechnology improves the shelf life and barrier properties, and prevents
food spoilage and nutrient loss. Nano-agri research work is aimed to solve issues of
stagnant crop yields, nutrient deficiencies, reduced delivery of plant growth regula-
tors, herbicides, shrinking arable land, and climate change.
Here we reviewed the active research, industrial development and global patent
trends of nanoscience in food and agriculture. The major points are: (1) work is
done to improve barrier properties of biopolymers, carbon nanotube sensors for
pathogen detection and antimicrobial packaging. (2) The year 2014 witnessed the
highest number of publications in nano food and agriculture. (3) The overall increase
in the number of patents in food and agriculture in 2011–2015 is 30.85%. (4) China
research has been on rise from 2012, having the highest score of 18 nano agriculture
patents in 2015, whereas Germany and Canada shows little activity in this field. (6)
There is actually research on nanosensors for soil quality detection, nanomagnets
for the removal of soil contaminants, nano-composites for the development of smart
delivery systems, nanoscale carriers for efficient delivery of fertilizers and
pesticides.

Keywords  Nano-food • Nano-agriculture • Patent trends • Nano industries

V.K. Yata (*) • B.C. Tiwari • I. Ahmad

Department of Biotechnology, Dr. B R Ambedkar National Institute of Technology Jalandhar,
Jalandhar 144 011, Punjab, India
e-mail: vinodyata@gmail.com; tiwaribhupesh25@gmail.com; irfanamu2007@gmail.com

© Springer International Publishing AG 2017 1

S. Ranjan et al. (eds.), Nanoscience in Food and Agriculture 5, Sustainable
Agriculture Reviews 26, DOI 10.1007/978-3-319-58496-6_1
2 V.K. Yata et al.

1.1  Introduction

Nanotechnology is playing a major role in the field of agriculture and food science
(Mousavi and Rezaei 2011). Research trends analysis of nanoscience publications
in food and agriculture has been carried out using the web of science. Web of sci-
ence is maintained by Thomson Reuters and provides us with tools by which in
depth exploration in any research discipline can be done. It covers full text articles,
reviews, technical papers, abstracts, proceedings, journals and chronologies. The
years 2014 has seen a sudden rise in the number of publications both in case of nano
food and nano agriculture. In case of nano food research is highly focused for
improving the food quality, preservation ensuring its safety, as evident from the
maximum number of publications in nano food packaging. Maximum number of
publications is seen in case of nano fertilizers implying that work is focused on
improving the crops productivity. Active research has been carried on in this field
and continuing due to wide scope for growth in this field (Scrinis and Lyons 2007).
Also, government funding and public awareness is acting like a catalyst to further
enhance the research and development in this field. We chose keyword based search
for the collection of research papers from the Thomson Reuters database, web of
science. Worldwide nanotechnology industries and business analysis data was col-
lected from Organisation for Economic Co-operation and Development (OECD).
Patent analysis is carried out using Google patent search tool for the past 5 years.
From 2011 to 2015 there has been a sudden rise in the patent applications of nano-
science in food and agriculture. It has been observed from the Google patent analy-
sis that China’s research has been progressing at a fast pace in the application of
nanoscience to agriculture whereas United States is active in the field of nanofood
compared to agriculture. Historically, agriculture preceded the industrial revolution
by around 90 centuries. However, while the seeds of research in nanotechnology
started growing for industrial applications nearly half a century ago, the momentum
for use of nanotechnology in agriculture came only recently with the reports pub-
lished by Roco (1999); Kuzma and Verhage (2006) along with similar publications.
These reports focused on identifying the research areas that should be funded, and
thus set the agenda for nanotechnology research in agricultural applications, which
became the principal guiding force for many nations, especially those where agri-
culture is the primary occupation of the majority of the population. However, the
conceptual framework, investigation pathways, and guidelines and safety protocols
were left aside for scientific laboratories to innovate (Mukhopadhyay and Sharma
2013). Nanobiotechnology may increase agriculture’s potential to harvest feed
stocks for industrial processes. Agro-Nano connects the dots in the industrial food
chain and goes one step further down. With new nano-scale techniques of mixing
and harnessing genes, genetically modified plants become atomically modified
plants. Pesticides may be more precisely packaged to knock-out unwanted pests,
and artificial flavorings and natural nutrients engineered to please the palate
(Dasgupta et  al. 2017; Shukla et  al. 2017; Walia et  al. 2017; Balaji et  al. 2017;
Maddinedi et al. 2017; Sai et al. 2017; Ranjan and Chidambaram 2016; Janardan
et al. 2016; Ranjan et al. 2016; Jain et al. 2016; Dasgupta et al. 2016). Visions of an
1  Research Trends and Patents in Nano-food and Agriculture 3

automated, centrally-controlled industrial agriculture can now be implemented

using molecular sensors, molecular delivery. The agricultural industry is no excep-
tion (Raliya et al. 2013). Nanotechnology can be used for combating the plant dis-
eases either by controlled delivery of functional molecules or as diagnostic tool for
disease detection (Tarafdar and Raliya 2012).

1.2  Research Trends of Nanoscience in Food and Agriculture

Analysis of the research trends of nanoscience in food and agriculture has been car-
ried out by using the tools of web of science. Thomson Reuters maintains this sci-
entific citation indexing service which provides a comprehensive citation search. It
provides access to multiple databases which allows for in-depth exploration using
cross-disciplinary research. Here we have used various field tags, boolean opera-
tors, parentheses, and query sets to create the query.
We have carried out the advanced search using search term TI = “nano food”
which finds records in which the exact phrase nano food appears in the title. Then
we carried out advanced search using search term TI = nano food which finds
records in which the terms nano and food appear in the title. Similarly, after carry-
ing out the topic search TS = “nano food” using advanced search option which
found records of articles containing the exact phrase nano food in a topic field and
TS = nano food advanced topic search provided us with records of articles contain-
ing the terms nano and food in any topic field. The terms do not have to appear
together in the same field.
We have carried out the search using the web of science advanced search box. We
have considered all years while carrying out the advanced search. The Table  1.1
shows the number of nano food publications in all years using different boolean
operators and tools available in web of science. As observed, minimum number of
publications i.e. 10 were found when we carried out the title TI=” nano food”
advanced search since it selects only those containing the exact phrase nano food in

Table 1.1  Number of publications in accordance to different search terms by carrying out
advanced search
SN Research areas Search terms Number of publications
1 Nano food TI = “nano food” 10
TI = nano food 385
TS = nano food 2871
TS = “nano food” 23
2 Nano agriculture TI = “nano agriculture” 1
TI = nano agriculture 22
TS = nano agriculture 351
TS = “nano agriculture” 1
TI title search and TS topic search for all years, under nano food and nano agriculture
4 V.K. Yata et al.

the title (Table 1.1). The title TI = nano food advanced search shown 385 number of
publications since the two terms nano and food don’t have to be together in the title
as in the previous case. When we carried out the topic TS = nano food advanced
search we obtained maximum publications because, it showed articles containing
the terms nano and food in any topic field. Second highest number of publications
were obtained when topic search TS = “nano food” is carried. Here we find out from
number of nano food publications that TI=” nano food” shows limited results since
it shows papers containing exact phrase nano food in the title whereas TS = nano
food shows maximum publications since it includes all publications with topic nano
and food. Hence, TI = nano food advanced search is better than TS = nano food
search.
We have carried out the advanced search in the web of science search box con-
sidering all years. The Table 1.1 shows the number of nano agriculture publications
in all years using different boolean operators and tools available in web of science.
As observed, the title TI = “nano agriculture” advanced search shows only one pub-
lication since it selects only those containing the exact phrase nano agriculture in
the topic (Table  1.1). The title TI = nano agriculture advanced search shown 22
number of publications since the two terms nano and agriculture do not have to be
together in the topic as in the previous case. When we carried out the topic TS =
nano agriculture advanced search we obtained maximum publications because, it
showed articles containing the terms nano and agriculture in any topic field.
We carried out advanced search using search term TI = nano agriculture since it
includes all papers in which title contains both nano and agriculture terms which is
more accurate then TS = nano agriculture since it includes all the publications under
topic nano and agriculture.
Here we carried out the title TI = Nano food advanced search using web of sci-
ence. It has been observed that the year 2014 shows highest number of publication
followed by 2015 and 2013 (Fig. 1.1). Hence, it can be concluded that during these
3 years active research was done in nano food field. The years 1996 and 2001 show
least number of publications. This may be due to the initial phase of the research
carried out in nano food field. The current year 2016 has seen a total of 13 publica-
tions till september month, implying that research work is carried actively.
Here we carried out the title TI = Nano agriculture advanced search using web of
science. The year 2014 shows the maximum number of publications whereas the
initial exploring year 1996 and 1994 shows very less publications (Fig. 1.2). Also,
years like 2011 and 2006 shows no publication at all. Moreover, we observe that as
compared to nano food, research publications in the field of nano agriculture are
very less. Hence, this field requires more research and funding (Table 1.2).
We observed from the number of publications in different research areas that the
publications are maximum in case of food packaging. Here we have carried out the
title search using the advanced search option of web of science. Title query TI =
Nano food sensors is entered into the advanced search box option. It showed second
highest number of publications. Title TI = Nano antimicrobial packaging advanced
search showed third highest number of publications. Hence, we observed that much
of the research work is focused on food packaging for increasing the shelf life of
1  Research Trends and Patents in Nano-food and Agriculture 5

70
NUMBER OF PUBLICATIONS

60

50

40

30

20

10

0
2016*

2015

2014

2013

2012

2011

2010

2009

2008

2007

2006

2005

2004

2003

2002

2001

2000

1998

1996
PUBLICATION YEAR

Fig. 1.1  Nano food publications from 1998–2016* (Title advanced search- terms nano and food
are not together). Constant upward trend is observed with downfall in the year 2010, 2012 and
2015 (*Data is till September 2016)

9
8
NUMBER OF PUBLICATIONS

7
6
5
4
3
2
1
0
2016*

2015

2014

2013

2012

2011

2010

2009

2008

2007

2006

1996

1994

PUBLICATION YEAR

Fig. 1.2  Nano agriculture publications from 1994–2016* (Title advanced search- terms nano and
agriculture are not together). Number of publications remained same over years with second high-
est number of publication in year 2012, 2009 and highest in 2014. (*Data is till January 2016)

food by protecting it from harmful micro-organisms and pathogens. Area of nano-

sensors development is also explored for early detection of contaminants in the
food, as to prevent any health problem. More research is needed to be done in the
field of natural polymers for development of biodegradable packaging (Table 1.3).
We observed from the number of publications in different research areas that the
publications are maximum in case of nano fertilizers. Here, we have carried out the
title search using the advanced search option of web of science. Research is highly
done in the field of nano fertilizers as evident from the maximum number of publi-
cations. Also, research is focused on development of nano agrochemicals for
improving the productivity. Further research work is needed to fully explore the
area of nano hydroponics and nano agriculture filtration.
6 V.K. Yata et al.

Table 1.2  Publication trends in different nano food research areas by title search- publications in
all years where searched terms appear in the title under nano food field
S. No. Topic Number of publications
1 Nano food sensors 13
2 Nano food packaging 73
3 Nano food natural polymers 1
4 Nano antimicrobial packaging 8

Table 1.3 Publication trends in different nano agriculture research areas by title search-
publications in all years where searched terms appear in the title under nano agriculture field
S. No. Topic Number of publications
1 Nano agrochemicals 10
2 Nano fertilizers 162
3 Nano hydroponics 1
4 Nano organic agriculture 2
5 Nano agriculture foods 4
6 Nano agriculture filtration 1

1.3  Industries in Nanotechnology

Global Nanotechnology industries and business data collected from OECD and it
indicates the significant scope of nanotechnology business in developed and devel-
oping countries. United States is leading in the development of nanotechnology in
industries and business with highest number of nanotechnology firms. Even though
it is the major contributor in the field of nanotechnology, it has only 1%of dedicated
nanotechnology firms. Germany, France, Korea, Italy, Czech Republic, Solvania
and Slovak republic have more than 20% of dedicated nanotechnology firms
(Table 1.4).

1.3.1  Scope of Nano-food Research in Industrial Development

There are wide opportunities for the developing countries and development is made
in the field of nanomaterials application for food packaging materials (Bradley et al.
2011; Chau et  al. 2007). Currently work is being carried on nanocomposites to
enhance the barrier properties of biopolymers for food packaging (Darder et  al.
2007; Lagaron et al. 2005). The advent of nanoscience has played an important role
in the field of food packaging and preservation (Silvestre et al. 2011; Ranjan et al.
2014; García et al. 2010). Food packaging is done to achieve various objectives like
physical protection, containment, barrier protection and marketing to increase the
shelf life by avoiding bacteria or preventing nutrient loss (Neethirajan and Jayas
2011; Paine and Paine 2012). Nanoscience and nanotechnology plays a crucial role
in achieving these food packaging objectives (Duncan 2011).
1  Research Trends and Patents in Nano-food and Agriculture 7

Table 1.4  Detailed data summary of the global nanotechnology firms and business analysis for 18
countries
Number of small Nanotechnology R&D in the
Number of nanotechnology firms, business enterprise sector as a
nanotechnology with fewer than 50 percentage of industry value
firms employees added
United States 10,341 7531 0.130
Germany 1110 800 0.080
France 649 435 0.065
Korea 504 312 0.697
Mexico 188 106 0.009
Switzerland 141 76 0.038
Italy 136 67 0.018
Belgium 125 66 0.061
Finland 98 58 0.016
Ireland 79 56 0.040
Poland 71 34 0.003
Norway 69 30 0.014
Czech 64 30 0.020
Republic
Denmark 54 40 0.015
Portugal 31 21 0.002
Slovenia 15 6 0.026
South Africa 10 2 0.009
Slovak 5 4 0.002
republic
Source: Data compiled from OECD

Apart from food packaging the preservation of food is highly important. In this
fast pace world, rapidly advancing in the field of technology there is an effort and
research is carried on to reduce the time required for the detection of these harmful
organisms in the food material (Bhattacharya et al. 2007). Since an early and rapid
detection would lead to lower health problems and money problems (Li and Sheng
2014). Nanosensors can be highly useful for the detection of pathogens causing
food spoilage and deterioration (Rashidi and Khosravi-Darani 2011; Sonkaria et al.
2012). Sensors play an important role in the detection and hence make an impact in
the routine life. There have been technological advances for the development of
miniatured sensors since they are cost-effective, consume less power and economi-
cal (Sanguansri and Augustin 2006).
The discovery of carbon-nanotubes has ignited the researchers for the develop-
ment of next generation of carbon-nanotube sensors (Sinha et al. 2006). In the food
industry they are used for the detection of a variety of chemicals the examples of
which include the measurement of levels of capsacionoids in chilli peppers (Sozer
and Kokini 2009; Pathak et al. 2012). Consumer awareness to the harm caused by
plastic based packaging to the environment has highly modified the research being
8 V.K. Yata et al.

carried on in the laboratories (Lusk et al. 2014; Frewer et al. 2014). Now, the major
thrust is on the development of entirely new class of packaging material whose
source of raw material is of biodegradable nature (Peelman et  al. 2013; Jiménez
et al. 2012). Consumer awareness and interest have further led companies to com-
mence new products and also focus on cost-performance basis.
Antimicrobial packaging offers a new way to deal with the problems associated
with food spoilage due to reduced shelf life, and microorganism attack etc.
(Quintavalla and Vicini 2002; Juneja et al. 2012). It is important for the consumers
and industries since it reduces the growth rate of micro-organisms. This concept of
antimicrobial packaging provides us with the potential of enhancing food safety and
security (Han 2003; Sung et al. 2013). In the initial stages of developing antimicro-
bial substances a wide range of antimicrobial substances have been tested in the
laboratory. These include the organic acids, antibiotics and silver compounds etc.
(Muriel-Galet et al. 2012). Different approaches and mechanisms are followed by
different substances for their action against the microorganisms (Appendini and
Hotchkiss 2002).
However, each method has some drawbacks which limits its commercial use and
also faces reduced marketing opportunities. Active research is carried on in the field
of antimicrobial packaging with work in the antimicrobial activity of chitosan,
organic acids for development of smart- antimicrobial packaging system. Results
have shown that the low and high molecular weight chitosan exhibits the highest
antimicrobial activity against all bacteria tested (Cruz-Romero et al. 2013).

1.3.2  S
 cope of Nano-agriculture Research in Industrial
Development

Agricultural scientists are facing a wide spectrum of challenges such as stagnation

in crop yields, low nutrient use efficiency, declining soil organic matter, multi-­
nutrient deficiencies, climate change, shrinking arable land and water availability
and shortage of labour besides exodus of people from farming. In spite of immense
constraints faced, we need to attain a sustainable growth in agriculture at the rate of
4% to meet the food security challenges. To address these problems, there is a need
to explore one of the frontier technologies such as ‘Nanotechnology’ to precisely
detect and deliver the correct quantity of nutrients and pesticides that promote pro-
ductivity while ensuring environmental safety and higher use efficiency.
The nanotechnology can be exploited in the value chain of entire agriculture
production system (Raliya et al. 2013; Subramanian and Tarafdar 2011; Roco 1999;
United States Department of Agriculture 2002; Nanoforum 2006; Kuzmo and
Verhage 2006). The nanotechnology aided applications have the potential to change
agricultural production by allowing better management and conservation of inputs
of plant and animal production. A survey by Salamanca–Buentella et al. (2005) pre-
dicted several nanotechnology applications for agricultural production for develop-
ing countries within next 10 years. These included – (i) Nanoforms zeolites for slow
1  Research Trends and Patents in Nano-food and Agriculture 9

release and efficient dosage of water and fertilizers for plants; drugs for livestock;
nanocapsules and herbicide delivery (ii) Nanosensors for soil quality and for plant
health monitoring; nanosensors for pest’s detection (iii) Nanomagnets for removal
of soil contaminants and (iv) Nanoparticles for new pesticides, insecticides, and
insect repellents.
Nanotechnology platform encompasses major themes such as synthesis of nano-­
particles for agricultural use, quick diagnostic kits for early detection of pests and
diseases, nano-pheromones for effective pest control, nanoagri inputs for enhanced
use efficiencies, precision water management, and stabilization of organic matter in
soil, nano food systems and bio safety besides establishing the policy frame work.
Green-synthesis and microbial synthesis of nanomaterials for their agricultural use
may be very important as they are naturally encapsulated with mother protein,
therefore, more stable and safer to biological system.
At present in India research is mainly concentrated on nano particle synthesis,
smart release of nutrients from nano-fertilizers, nano-induced polysaccharide pow-
der for moisture retention, soil aggregation and carbon build up, regulated release of
active ingredients from nano-encapsulated herbicides, nano-seed invigoration, and
slow and steady release of pesticides, nano-film for extended shelf-life of perish-
ables and nano-remediation of soil and aquatic pollutants. These are cutting-edge
researchable areas which are expected to expand in the years to come. However, if
the nanoproducts and the processes for creating them are not managed judiciously,
there could be serious health and environmental risks (Khot et  al. 2012; Sekhon
2010; Mousavi and Rezaei 2011; Sozer and Kokini 2009; Shrivastava and Dash
2009).
Nano-fertilizer technology is very innovative but scantily reported in the litera-
ture. However, some of the reports and patents strongly suggest that there is a vast
scope for the formulation of nano-fertilizers. Significant increase in yields has been
observed due to foliar application of nano particles as fertilizer (Tarafdar 2012;
Tarafdar et al. 2012a; Raliya 2012; Raliya and Tarafdar 2013, Tarafdar et al. 2012b).
It was shown that 640 mg ha-1 foliar application (40 ppm concentration) of nano-
phosphorus gave 80 kg ha-1 P equivalent yield of clusterbean and pearl millet under
arid environment. Currently, research is underway to develop nano-composites to
supply all the required essential nutrients in suitable proportion through smart deliv-
ery system. Preliminary results suggest that balanced fertilization may be achieved
through nanotechnology (Tarafdar et al. 2012c).
Indeed the metabolic assimilation within the plant biomass of the metals, e.g.,
micronutrients, applied as Nano-formulations through soil-borne and foliar applica-
tion or otherwise needs to be ascertained. Further, the Nano-composites being con-
templated to supply all the nutrients in right proportions through the “Smart”
delivery systems also needs to be examined closely. Currently, the nitrogen use
efficiency is low due to the loss of 50–70% of the nitrogen supplied in conventional
fertilizers. New nutrient delivery systems that exploit the porous nanoscale parts of
plants could reduce nitrogen loss by increasing plant uptake (Brock et al. 2011).
Fertilizers encapsulated in nanoparticles will increase the uptake of nutrients. In the
10 V.K. Yata et al.

next generation of nanofertilizers, the release of the nutrients can be triggered by an

environmental condition or simply released at desired specific time.
Herbicides available in the market are designed to control or kill the above
ground part of the weed plants. None of the herbicides inhibits activity of viable
belowground plant parts like rhizomes or tubers, which act as a source for new
weeds in the ensuing season. Soils infested with weeds and weed seeds are likely to
produce lower yields than soils where weeds are controlled. Improvements in the
efficacy of herbicides through the use of nanotechnology could result in greater
production of crops. The encapsulated nano-herbicides are relevant, keeping in
view the need to design and produce a nano-herbicide that is protected under natural
environment and acts only when there is a spell of rainfall, which truly mimics the
rain fed system. Developing a target specific herbicide molecule encapsulated with
nanoparticle is aimed for specific receptor in the roots of target weeds, which enter
into roots system and translocated to parts that inhibit glycolysis of food reserve in
the root system. This will make the specific weed plant to starve for food and gets
killed (Chinnamuthu and Kokiladevi 2007).
Adjuvants for herbicide application are currently available that claim to include
nanomaterials. One nanosurfactant based on soybean micelles has been reported to
make glyphosate-resistant crops susceptible to glyphosate when it is applied with
the ‘nanotechnology-derived surfactant. Persistence of pesticides in the initial stage
of crop growth helps in bringing down the pest population below the economic
threshold level and to have an effective control for a longer period. Hence, the use
of active ingredients in the applied surface remains one of the most cost-effective
and versatile means of controlling insect pests (Chen and Yada 2011; Rai and Ingle
2012). In order to protect the active ingredient from the adverse environmental con-
ditions and to promote persistence, a nanotechnology approach, namely “nano-­
encapsulation” can be used to improve the insecticidal value.
Nanoencapsulation comprises nano-sized particles of the active ingredients
being sealed by a thin-walled sac or shell (protective coating). Nano-encapsulation
of insecticides, fungicides (Raliya 2012) or nematicides will help in producing a
formulation which offers effective control of pests while preventing accumulation
of residues in soil. In order to protect the active ingredient from degradation and to
increase persistence, a nanotechnology approach of “controlled release of the active
ingredient” may be used to improve effectiveness of the formulation that may
greatly decrease amount of pesticide input and associated environmental hazards.
Nano-pesticides will reduce the rate of application because the quantity of prod-
uct actually being effective is at least 10–15 times smaller than that applied with
classical formulations, hence a much smaller than the normal amount could be
required to have much better and prolonged management. Several pesticide manu-
facturers are developing pesticides encapsulated in nanoparticles (OECD and Allianz
2008). These pesticides may be time released or released upon the ­occurrence of an
environmental trigger (for example temperature, humidity, light). Plant diseases are
major factors limiting crop yields. The problem with the disease management lies
with the detection of the exact stage of prevention. Most of the time appropriate plant
protection chemicals are applied to the crop as a precautionary measure leading to
1  Research Trends and Patents in Nano-food and Agriculture 11

avoidable environmental hazards, or else applications are made after the appearance
of the disease symptoms, thereby causing some amount of crop losses.
Among the different diseases, the viral diseases are the most difficult to control,
as one has to stop the spread of the disease by the vectors. But once it starts showing
its symptoms, pesticide application would not be of much use. Therefore, detection
of the exact stage such as stage of viral DNA replication or the production of initial
viral protein is the key to the success of control of viral diseases. Nano-based viral
diagnostics, including multiplexed diagnostics kits development, have taken
momentum in order to detect the exact strain of virus and the stage of application of
some therapeutic to stop the disease. Detection and utilization of biomarkers, that
accurately indicate disease stages, is also an emerging area of research in bio-­
nanotechnology. Measuring differential protein production in both healthy and dis-
eased states leads to the identification of the development of several proteins during
the infection cycle.
Clay nanotubes (halloysite) have been developed as carriers of pesticides at low
cost, for extended release and better contact with plants, and they will reduce the
amount of pesticides by 70–80%, thereby reducing the cost of pesticide with mini-
mum impact on water streams. Nanoscale carriers can be utilized for the efficient
delivery of fertilizers, pesticides, herbicides, plant growth regulators, etc. The
mechanisms involved in the efficient delivery, better storage and controlled release
include: encapsulation and entrapment, polymers and dendrimers, surface ionic and
weak bond attachments among others. These help to improve stability against deg-
radation in the environment and ultimately reduce the amount to be applied, which
reduces chemical runoff and alleviates environmental problems. These carriers can
be designed in such a way that they can anchor plant roots to the surrounding soil
constituents and organic matter. This can only be possible if we unravel the molecu-
lar and conformational mechanisms between the nanoscale delivery and targeted
structures, and soil fractions.
Such advances as and when they happen will help in slowing the uptake of active
ingredients, thereby reducing the amount of inputs to be used and also the waste
produced. It is worthwhile to recognize that a large number of nanomaterials have
existed since time immemorial in soils, plants, and the atmosphere (Li et al. 2012;
Wilson et al. 2008; Theng and Yuan 2008). Further opportunities for applying nano-
technology in agriculture lie in the areas of genetic improvement of plants (Eapen
and Souza 2005; Kuzma 2007) delivery of genes and drug molecules to specific
sites at the cellular level in plants and animals (Maysinger 2007) and nanoarray-­
based technologies for gene expression in plants to overcome stress and develop-
ment of sensors (Ahmed et  al. 2013; The Nanoscale Science, Engineering, and
Technology Subcommittee of the Committee on Technology of the National Science
and Technology Council 2009) and protocols for its application in precision farming
(Day 2005) management of natural resources, early detection of pathogens and con-
taminants in food products, smart delivery systems for agrochemicals like fertilizers
and pesticides, and integration of smart systems for food processing, packaging, and
monitoring of agricultural and food system security (Chau et al. 2007; Moraru et al.
2003).
12 V.K. Yata et al.

With nanofertilizers (DeRosa et  al. 2010) emerging as alternatives to conven-

tional fertilizers, buildup of nutrients in soils and thereby eutrophication and con-
tamination of drinking water may be eliminated (Bhalla and Mukhopadhyay 2010).
Overdependence on supplementary irrigation, vulnerability to climate, and poor
input and energy conversion are the three dominant issues in the current agricultural
production system, and nanotechnology could possibly reduce their impact. Also, it
has been observed that nanoremediation could be effective not only in reducing the
overall costs of cleaning up large contaminated sites, but also in decreasing clean-up
time by eliminating the need for treatment and disposal of contaminated soil and
reducing some contaminant concentrations to near zero, all in situ, although caution
is required, especially for full-scale ecosystem-wide studies, to prevent any poten-
tial adverse environmental impacts (Karn et al. 2009).

1.4  T
 rends of Intellectual Property Rights of Nanoscience
in Agriculture and Food Sector

There has been an exponential increase in the patent application worldwide with the
patent offices of the United States (United States Patent and Trademark Office
-USPTO), China (State Intellectual Property Office-SIPO), Japan (Japan patent
office-JPO), South Korea (Korean Intellectual Property Office-KIPO), Canada
(Canadian Intellectual Property Office-CIPO), Europe (European Patent Office
-EPO) and World Intellectual Property Organization (WIPO) being the front run-
ners. This study aims to lay emphasis on trends in the patent applications in nanosci-
ence in food and agriculture sector during the period (2011–2015) and have been
examined using The Google Patent search engine covering the patent offices of
USA, China, Canada, Germany and Europe.
Patent applications regarding the use of nanoscience in food and agriculture have
been examined for the offices of USA, Canada, Germany, Europe and China during
2011–2015 (Fig. 1.3). USA is most active internationally among all the patent office’s
followed by China. USPTO has published more nano food related patents during
2011–2015 while in China there has been more inclination towards nano agriculture
related patents. Germany has the least number of patents related to both nano food
and agriculture although there is a general rise in the trend recently. In case of nano
food patents, the increment has not been very significant with their number increas-
ing from 6 to 14 but for nano-Agriculture sector there has been a large gain in num-
ber of patents from 2 to 23 published in the years 2011 and 2015 respectively,
although the total number of nano food patents issued are greater (Fig. 1.4). By com-
paring the number of patent applications during this time period, a tremendous
increase in the applications in recent years can be comprehended and nanotechnol-
ogy derived food and agriculture advancements can be easily anticipated.
The annual rate increase in food and agriculture sector has been more pronounced
in the year 2014 and 2015 respectively. The corresponding annual increase is
29.16% and 50% respectively. Considering the nanotechnology patents on the
1  Research Trends and Patents in Nano-food and Agriculture 13

30 Nano-Food Patents
Nano-Agriculture Patents
25
NUMBER OF PATENTS

20

15

10

0
USA Canada Germany China Europe
COUNTRIES

Fig. 1.3  Distribution trends in total number of nano- food and agriculture patents during 2011–
2015. China has the highest number of agriculture patents whereas United States has the maximum
number of food patents

30
Nano-Food Patents
Nano-Agriculture Patents
25
NUMBER OF PATENTS

20

15

10

0
2011 2012 2013 2014 2015
PUBLICATION YEAR

Fig. 1.4  Nano- food and agriculture patents dispersion trend during 2011–2015(Based on data
from United States, Canada, Germany, China and Europe). The percent increase in nano food
patents during 2011–15 is 16.6% whereas for nano agriculture is 45.6%

whole, the annual rate increase has been more pronounced in the year 2015 with
39.36% (Fig. 1.4). China was most active internationally with the largest number of
nanotechnology patent applicants published. It is leading in the number of publica-
tions which is followed by United States. Canada, Germany and Europe have shown
a little contribution in this sector. China’s has shown the ability to understand and
control the matter at nanoscale leading to revolution in technology and in the indus-
try that benefits the society. Highest number of patents under ‘Nano in Agriculture’
was published by China with 18 patents in 2015. In 2011, both United States and
Canada were indulged with the slow pace in research and development under
­nanotechnology with number of patent One, whereas other country do not partici-
pate under this field. In 2012–13, United States continued its participation under
14 V.K. Yata et al.

20
2011 2012 2013 2014 2015
NUMBER OF PATENTS 18
16
14
12
10
8
6
4
2
0
USA Canada Germany China Europe
COUNTRIES

Fig. 1.5  Nano agriculture patent dispersion trend during individual years from 2011 to 2015.
China research has been on rise, with maximum patents and an increase of 60.7% during the year
2012–15

nanotechnology R&D. China and Germany contributed but with little involvement

under this area where as Canada and Europe were inactive during this 2 year.
The evolution of nanotechnological patent in every repository from the year
2011–2015 in the agriculture sector is shown in Fig. 1.5. China is emerging at an
exponential rate in the recent years and increasing steeply year after year. The varia-
tion in the USA’s contribution has remained consistent in the years 2011–15. China
contribution is Europe and Canada have shown some contributions which stands out
third and fourth respectively. Germany has remained a bit inactive in these years
with very less number of publications. Number of publications from US has shown
a growth about 28% (which is above average) in 2011–2015 in the agriculture sec-
tor. China’s share (60%) is rising at faster rate but it is starting from a smaller base.
Canada, Germany, Europe has shown the growth at a slower pace with 4%, 2%, 4%
respectively. The year 2015 remains excellent for nanotechnological development.
2011 has remained a dry year with least number of publications. Highest number of
patents under ‘Nano in Agriculture’ was published by China with 18 patents in
2015. In 2011, both USA and Canada were indulged with the slow pace in research
and development under nanotechnology with number of patent One, whereas other
country does not participate under this field. Significant number of patents are
issued pertaining to nano fertilizers and pesticides that are specific for certain crops
such as Spinach, Sugarcane, Eucalyptus etc., are environment friendly and required
in much less quantity than the conventional fertilizers. In the year 2015 highest
number of nanoscience agriculture patents were issued that might indicate the
increase in nanoagriculture science research in the coming years. Germany nano
agriculture research has not been taken up at an extensive scale yet.
The evolution of nanotechnological patent in every repository from the year
2011–2015 in the food sector (Fig. 1.6). USA has contributed to a greater extent.
China also remained at par with USA.Europe and Canada have shown some
­contributions which stands out third and fourth respectively. Germany has remained
1  Research Trends and Patents in Nano-food and Agriculture 15

10 2011 2012 2013 2014 2015

NUMBER OF PATENTS 9
8
7
6
5
4
3
2
1
0
USA Canada China Europe
COUNTRIES

Fig. 1.6  Nano food patents dispersion trends for five countries from 2011 to 2015. Both United
States and China has the maximum number of patents in the year 2015 amongst all countries.
Canada participation under nano-food is 20% whereas 33.3% for Europe during 2011–15. USA
shows the maximum patents with increase of 22.7% during 2011–14

inactive with no publications. The year 2014 and 2015 remains the excellent for
nanotechnological developments. In the food sector number of publications from
US has shown a growth about 45% in 2011–15. China’s being at second with its
contribution of 31%. Canada, Germany, Europe has shown the growth at a slower
pace with 10.4%, 12.5% respectively. It can be seen that nanotechnology has shown
its greater extent of applications in food sector than in agriculture sector. During
2011–2015, the number of patents for food nanotechnology is high in USA as com-
pared to other countries except in 2013. In 2013 and 2014; Canada, China and
Europe shows very little progress as compared to USA.  In 2015, China shows
­maximum patents as compared to other countries. USA loses its consistency in this
year with zero number of publications.
USPTO has issued maximum nano food patents since 2011 reaching its peak in
the year 2014. Greater emphasis is upon development of biodegradable and com-
postable high barrier food packaging material and nano structure based spectral
sensing for determination of food safety. In addition to food packaging, food pres-
ervation has also been given importance by using nanosensors that are designed to
fluoresce in different colours upon contact with food pathogens. These nanosensors
are placed directly into the packaging material where they function as an ‘electronic
tongue or nose’ by detecting chemicals released during food spoilage. In China
number of nano food patents has increased very significantly. Germany has not
issued any nano food related patent during this time. China is most active interna-
tionally among all the patent office’s followed by USA. In case of nano food pat-
ents, the increment has not been very significant with their number increasing from
6 to 14 but for nano-agriculture sector there has been a large gain in number of
patents from 2 to 23 published in the years 2011 and 2015 respectively, although the
total number of nano food patents issued are greater.
16 V.K. Yata et al.

1.5  Conclusions

In this chapter, we conducted an analysis of food and agriculture-nanosceince

research outcomes in the web of science database. The year 2014 has seen a rise in
number of publications both for nano food and nano agriculture. Research in needed
in the field of nano hydroponics as there is only one publication obtained on carry-
ing the title search. Also, biodegradable packaging needs to be fully explored due to
environmental pollution caused by existing non-biodegradable packaging materials
in the market. Industrial and business data of this field collected from OECD. USA
is the major contributor in the field of nanotechnology research and industrial devel-
opment with highest number of nanotechnology firms and business.USPTO has
published more nano food related patents during 2011–2015 while in China there
has been more inclination towards nano agriculture related patents. Germany has
the least number of patents related to both nano food and agriculture although there
is a general rise in the trend recently by comparing the number of patent applica-
tions during 2011–2015, a tremendous increase in the application in recent years
can be comprehended and nanotechnology derived food and agriculture advance-
ments can be easily anticipated. The opportunity for application of nanotechnology
in agriculture is prodigious. Research on the applications of nanotechnology in agri-
culture is less than a decade old. Nevertheless, as conventional farming practices
become increasingly inadequate, and needs have exceeded the carrying capacity of
the terrestrial ecosystem, we have little option but to explore nanotechnology in all
sectors of agriculture. It is well recognized that adoption of new technology is cru-
cial in accumulation of national wealth. Nanotechnology promises a breakthrough
in improving our presently abysmal nutrient use efficiency through nanoformula-
tion of fertilizers, breaking yield and nutritional quality barriers through bionano-
technology, surveillance and control of pests and diseases, understanding the
mechanism of host-parasite interactions at the molecular scale, development of
new-generation pesticides and safe carriers, preservation and packaging of food and
food additives, strengthening of natural fiber, removal of contaminants from soil
and water bodies, improving the shelf-life of vegetables and flowers, and use of clay
minerals as receptacles for nano resources involving nutrient ion receptors, preci-
sion water management, regenerating soil fertility, reclamation of salt-affected
soils, checking acidification of irrigated lands, and stabilization of erosion-prone
surfaces, to name a few. Revisiting our understanding of the theoretical foundations
of the agricultural production system along the geosphere (pedosphere)-biosphere-
atmosphere continuum coupled with application of advanced theories like the the-
ory of chaos and string theory may open up new avenues. Nanotechnology requires
a thorough understanding of science, as well as fabrication and material technology,
in conjunction with knowledge of the agricultural production system. The rigor of
this challenge might attract brilliant minds to choose agriculture as a career. To
achieve success in the field, human resources need sophisticated training, for which
new instruction programs, especially at the graduate level, are urgently needed.
Nanotechnology in agriculture might take a few decades to move from laboratory to
1  Research Trends and Patents in Nano-food and Agriculture 17

land, especially since it has to avoid the pitfalls experienced with biotechnology. For
this to happen, sustained funding and understanding on the part of policy planners
and science administrators, along with reasonable expectations, would be crucial
for this nascent field to blossom.

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Chapter 2
Politics of Nanotechnologies in Food
and Agriculture

Valeria Sodano

Abstract  The chapter discusses the reasons for the delay in the regulatory inter-
vention concerning nanotechnologies used in the agriculture and food sectors. The
main finding is that unregulated introduction of nanoinnovation into the food sys-
tem is due to the current neoliberal food policy and to the power struggles that
characterize the economic, social and political dynamics within the global supply
chain. Therefore, it is necessary to put the ‘question concerning technology’ at the
center of the regulatory debate in order to implement a regulatory system able to
face nanorisks. Which means looking at the way in which technology controls
power relationships within society. Attention should be shifted from efficiency to
power issues, and new technologies should be assessed from a political rather than
an economic or ethical perspective.

Keywords  Nanotechnology • Food • Agriculture • Power • Technological change •

Critical theory

2.1  Introduction

Over the last twenty years nanotechnology has silently entered the agrifood sector.
Currently, worldwide consumers buy a plethora of nanofoods, unaware of the
(incorporated) new technologies that have been used to produce and distribute them.
While in the late nineties scientists and businessmen engaged in nanoinnovation
praised the wonders and the benefits of nanotechnologies to the general public, at
the dawn of the new millennium a curtain of silence was slowly dropped over the
topic. Meanwhile, countless testimonies were collected of possible risks associated
with the new technologies (Nikodinovska et al. 2015) and a debate has grown, at

V. Sodano (*)
Dipartimento di Agraria, Università degli Studi di Napoli Federico II,
via Universitá 100, Portici 80055, Napoli, Italy
e-mail: valeria.sodano@unina.it

© Springer International Publishing AG 2017 21

S. Ranjan et al. (eds.), Nanoscience in Food and Agriculture 5, Sustainable
Agriculture Reviews 26, DOI 10.1007/978-3-319-58496-6_2
22 V. Sodano

food policy and regulatory bodies level, on the need for specific regulation as regards
nanofood (Ngarize et al. 2013; Mbengue and Charles 2013; Marrani 2013; Ehnert
2015; Sodano et  al. 2016). Notwithstanding the growing attention on the part of
academics and policymakers, though still ignored by the mass media and the gen-
eral public, almost no regulatory action has been taken so far. This paper investi-
gates the reasons for such a delay in the regulatory intervention with respect to a
technology that seems to pose serious risks to human health and the environment.
The main argument of the paper is that the unregulated introduction of nanoinnova-
tion into the food system is the result on the one hand of the current neoliberal food
policy and, on the other hand, of the power struggles that at various levels and
between various actors characterize the current economic, social and political
dynamics within the global supply chain. In particular, the paper discusses how
nanotechnologies represent a useful weapon for those corporations which are trying
to take over the control of the global food chain. An important objective of the paper
is to uncover the hidden socio-cultural and economic dynamics that prevent nano-
technologies from entering the food market in a safer and more democratic way, so
as to spur on changes that can put science and technology at the service of society
as a whole rather than at that of corporate power.
The paper is organized as follows. The first paragraph offers a brief picture of the
current state of application and regulation of nanotechnologies within the agri-food
sector. The presentation is very concise since a large body of literature (Bouwmeester
et al. 2007; Sozer and Kokini 2009; Neethirajan and Jayas 2011; Weir et al. 2012;
Cushen et al. 2012; Qureshi et al. 2012; Mura et al. 2013; Kumari and Yadav 2014;
Handford et al. 2014; Rossi et al. 2014; Mihindukulasuriya and Lim 2014; Sabourin
2015; Hannon et al. 2015; Dasgupta et al. 2015; Ranjan et al. 2014; Bhagat et al.
2015) now exists from which the reader can draw more detailed information. The
second paragraph describes how the weak regulatory effort can be explained as
stemming from the neoliberal attitudes that have been shaping food policy world-
wide for about thirty years. The third paragraph delves into the business practices
that function as drivers of nanoinnovation. The final paragraph shows how different
understandings of technical change can affect the perception and the assessment of
benefits and costs of innovations and how the embracement of the idea of techno-
logical determinism is a further factor explaining the lack of nanofood regulation.

2.2  Nanofoods, Risks and Regulatory Frameworks

In this paper the term nanofood is used to encompass all nanotechnology applica-
tions in agriculture, feed and food sector. Nanofood refers to “food that has been
cultivated, produced, processed or packaged using nanotechnology techniques or
tools, or to which manufactured nanomaterials have been added” (Joseph and
Morrison 2006). Throughout the paper when speaking of nanomaterial used in food
production it is implicitly meant that the reference is to engineered nanomaterials,
such as defined by Regulation EU N. 1169/2011 of 25 October 2011: “engineered
2  Politics of Nanotechnologies in Food and Agriculture 23

nanomaterial means any intentionally produced material that has one or more
dimensions of the order of 100 nm or less or that is composed of discrete functional
parts, either internally or at the surface, many of which have one or more dimen-
sions of the order of 100 nm or less, including structures, agglomerates or aggre-
gates, which may have a size above the order of 100 nm but retain properties that are
characteristic of the nanoscale”.1
There are several feasible nanotechnology applications along the food supply
chain (Handford et al. 2014), many of which are already on the market. In agricul-
ture some examples are: nanoformulation of agrochemicals; nanosensors for the
identification of plant diseases; nanodevices for genetic manipulation of plants;
nanobiocides for animal breeding (Sekhon 2014; Kumari and Yadav 2014). In the
food processing industry nanomaterials are used as: nanocapsules to improve dis-
persion, bioavailability and absorption of nutrients; nanomaterials as color and fla-
vor enhancers; nanotubes and nanoparticles as gelation and anticaking agents;
nanoparticles for selective binding and removal of chemicals and pathogens from
food; antimicrobic and nonstick cookware. In food packaging nanomaterials are
primarily used to impart antimicrobial function and to improve barrier and mechani-
cal properties; applications include: quantum dots for traceability, nanoclays as gas
barriers, carbon nanotubes to improve strengthening, ultraviolet light filters, nanosil-
ver as an antimicrobial (Hannon et al. 2015).
Since companies are not required to declare the presence of nanomaterials in
their products, it is difficult to estimate the actual use of nanotechnology in the food
chain. A publication (Peters et  al. 2014) of the European Food Safety Authority
(EFSA) provides an inventory of current and potential future applications of nano-
technology in the agri/feed/food sector based mainly on the review of the related
literature. The inventory reports the use of 55 types of nanomaterials and 14 types
of applications. The reported nanomaterials are: nano-encapsulates, silver, titanium
dioxide, nano- composite, zinc oxide, clay, synthetic amorphous silica, carbon
nanotubes, silicon dioxide, gold, iron, nanosilver, copper, quantum dot, chitosan,
fullerene, nisin, selenium. The applications include: pesticides, fertilizers, food
additives, food contact materials, novel foods, flavoring, enzymes, supplements,
food ingredients, feed additives  (Dasgupta et  al. 2017; Shukla et  al. 2017; Walia
et al. 2017; Balaji et al. 2017; Maddinedi et al. 2017; Sai et al. 2017; Ranjan and
Chidambaram 2016; Janardan et  al. 2016; Ranjan et  al. 2016; Jain et  al. 2016;
Dasgupta et al. 2016). Figure 2.1 synthetizes the data for the main nanomaterials
and field of application.

1
 This definition of engineered nanomaterial stems from the general definition of nanomaterial
previously in 2011 by the European Commission, with the Recommendation on Definition of
nanomaterial: «Nanomaterial means a natural, incidental or manufactured material containing par-
ticles, in an unbound state or as an aggregate or as an agglomerate and where, for 50% or more of
the particles in the number size distribution, one or more external dimensions is in the size range
1–100 nm. In specific cases and where warranted by concerns for the environment, health, safety
or competitiveness the number size distribution threshold of 50% may be replaced by a threshold
between 1 and 50%».
24 V. Sodano

120
110
100
90
80
70
60
50
40
30 APPLICATION TYPE not clear
20 OTHER Applications
FOOD Novel food
10
FOOD Component
0
FOOD Contact Material
ls

d
ia

FEED Sector
n
ol

r
Iro
er

n
G

lv

um
at

sa

in
Si

AGRICULTURE Sector
s
M

to

is

be
ni

y
o-

hi

la
N

e
le

e
tu

id
an

C
Se

id

a
ox
no

te
lic
N

ox

es
si
na

Si
nc
er

di

po

at
th

Zi
n

um

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Fig. 2.1  Nanomaterials in current and future applications by type of applications and sector.
Agriculture Sector include fertilizer and pesticide. Other Applications include biocide and veteri-
nary drugs Application type not clear includes all applications without specified type. (Source:
EFSA – Inventory of Nanomaterials: Current and future applications, 2014)

The EFSA inventory is rather inaccurate since it does not distinguish between
feasible and actual (that is products that are already commercialized) nano
­applications. Information explicitly targeted to commercialized nanofoods is con-
tained in the “interactive database of consumer food products containing nanomate-
rials” provided by the Center for Food Safety (CFS),2 on the basis of various,
rigorously quoted, sources of information. The CFS database includes: products
claiming to contain nano; products positively tested for nano; products previously
claiming to contain nano; Food and Drug Administration (FDA) approved additives
believed to contain nano. For each product the type of nanomaterial, the country of
origin, the product category, the commercial name and the producer/company are
specified. Figure 2.2 reports the commercialized products for category and country
of origin of the producer. Although the majority of the products belong to the cate-
gories of food supplements and food contact materials, it is worth noticing that
many everyday food products sold by some of the most powerful corporations in the
world (such as Nestlé, Kelloggs, Kraft food, Coca Cola, Unilever, General Mills)
contain nanomaterials, generally for taste and flavor enhancement.
Nanotechnology application in the agro-food sector may produce many negative
effects thus giving rise to various kinds of risks, such as health, environmental, eco-
nomic, social and political risks. Health risks mainly depend on the ability of
nanoparticles to bypass cellular membranes, to pass through biological barriers (as,
for instance, the blood-brain barrier) and to bio-accumulate with severe toxicological

 Center for Food Safety (CFS) http://www.centerforfoodsafety.org/

2
2  Politics of Nanotechnologies in Food and Agriculture 25

80

70

60

50

40

30

20
Previously Claimed To Contain Nano
10 Positively Tested For Nano
Packaging and Other Contact Devices Claiming to Contain Nano
Food Supplements and Additives Claiming to Contain Nano
0 Filtration and Bottle Products Claiming to Contain Nano
FDA Approved Additives Believed to Contain Nano
lia a Cooking and Eating Products Claiming to Contain Nano
ra in EU d
st Ch rs Baby and Infant Products Claiming to Contain Nano
Au lan he re
a d
Ze Ot Ko lan an A
Ne
w
th tz
er iw US
u Ta
So S wi

Fig. 2.2  Commercialized products for category and country of origin of the producer (Source:
Center for Food Safety)

effects (Elsaesser and Howard 2012; Hubbs et  al. 2013). Environmental risks are
associated with the limited biodegradation of nanoparticles and their interaction with
living organisms, soil and aquatic ecosystems. So far the following negative impacts
have been reported: phytotoxicity, damage to soil structure and fertility, reduction of
microbial biomass and diversity, toxicity for algae and daphnidis (Mueller and
Nowac 2008). Economic risks arise from (Scrinis and Lyons 2007; Invernizzi et al.
2008; Miller and Scrinis 2011): (1) the possible disruption of markets (for those tra-
ditional products which are replaced by new nanoproducts); (2) the displacement of
workers due to a more capital-intensive mode of production; (3) the further consoli-
dation of food systems, with the largest corporations more able to exploit the profit
streams from the patents on the new technologies. As regards socio-political risks, it
has been argued that the proliferation of nanotechnologies in the food systems might
exacerbate social injustice, deepen the North-South divide, and threaten the food
sovereignty of local communities (Lyons et al. 2012). Finally, because nanotechnol-
ogy is a dual-use technology (being developed for military as well as civilian pur-
poses) there may be military and security risks, as in the possible case of nanofood
being used to spread disease in scenarios such as war and terrorist attacks.
Despite the accelerated rate of innovation and the risks posed by new materials,
nanofoods are still entering the market in a regulatory vacuum, and this in disregard
of the many concerns raised by scientists and civil society (ETC Group 2010;
Savolainen et al. 2010; Shatkin 2013; Takeuchi et al. 2014) So far, the choice of regu-
latory bodies all over the world has been to consider nanomaterials equivalent to their
bulk form and as such not requiring specific provisions. The results of a 2015 over-
view (Amenta et al. 2015) of regulatory measures for nanomaterials in agri/feed/food
in EU countries showed that EU and Switzerland were the only world regions where
nano-specific provisions have been incorporated in legislation for agri/feed/food,
26 V. Sodano

which include specific information requirements for nanomaterials risk assessment

and/or legally binding definitions of the term “nanomaterial”. Nevertheless, under
closer scrutiny, apart from the effort to identify a standard definition of nanomateri-
als, even the EU has not yet set forth binding standards and regulations.
As regards the food sector, in the EU there are only a limited number of regula-
tions which provide specific provisions for nanomaterials.3 None of these interven-
tions, however, set stringent inspection rules for the entry of new products into the
market or for mandatory labeling. Overall, the choice of the European Commission
seems to be to leave the sector completely unregulated and deprive consumers of the
knowledge of the risks and the right to choose. In this regard, the story of Regulation
(EU) No 1169/2011 on the provision of food information to consumers is emblem-
atic. In its original form, this regulation contained an article (Article 18) stating that
all food containing manufactured nanomaterials should be labeled accordingly.
However, in 2013 the Commission submitted a proposal to amend this.
Regulation in order to eliminate the clause related to the mandatory labeling of
nanomaterials, to “avoid confusion” among consumers. On February 2014, the
Parliament approved a resolution rejecting the amendment, judging the Commission’s
justification to be “erroneous and irrelevant”, but the Commission reiterated the
amendment and the Regulation came into force in January 2015 without any provi-
sion on nano labeling.

2.3  U
 nregulated Nanofood: The Reasons of the Neoliberal
State

The main response that states have given to civil society organizations concerned
about the risks arising from nanofood is that there is still a lack of conclusive scien-
tific evidence of the dangers of new technologies. As a matter of fact, currently there
are many technical obstacles to carrying out a sound risk assessment for the novel
nanomaterials (Elsaesser and Howard 2012; Shatkin 2013), since toxicological risk
characterization is a challenging task. Nanomaterial characterization is difficult
because of the multitude of variables in the parameter space, such as particle size,
roughness, shape, charge, composition and surface coating. Exposure assessment,
that is the estimate of how much of a nanomaterial comes into contact with humans,
is also difficult to perform. The level of exposure depends on a variety of aspects
(such as substance concentration, likelihood of contact, bioavailability) that are
scarcely predictable in the case of nanomaterials, since there is still poor scientific
knowledge of the way these materials behave when dispersed in the environment.
Finally, estimation of nanoparticle “toxic dose” is complex, requiring a number of
direct and/or indirect technologies to determine how many particles are reaching

3
 Namely: Reg. 1333/2008 on food additives; Reg. 1332/2008 on food enzymes, Reg. 450/2009 on
active and intelligent materials and articles intended to come into contact with food; Reg. 10/2011
on food contact plastic materials; Reg. 1169/2011 on novel foods.
2  Politics of Nanotechnologies in Food and Agriculture 27

defined targets. Nevertheless, these difficulties, that somehow highlight the weak-
ness of the science, should elicit more cautious stances on the part of the policy
makers and should be an incentive for delaying the introduction of the new products
into the market. In other words, they should not be an excuse for not regulating, but
instead a strong incentive for higher standards, greater demands for toxicity tests on
the firms and even moratoria, appealing to the precautionary principle. Therefore it
is possible to argue that there is not an inability but rather an unwillingness to tackle
nanofood risks. Such an unwillingness is the result of the economic policy approach
embraced by many governments all over the world, which is neoliberalism (Sodano
2015; Sodano and Hingley 2016).
Neoliberalism is the new economic policy approach in liberal systems of modern
capitalist societies, which has spread all over the world over the last 30 years. On
theoretical grounds, neoliberalism is anchored in the political tradition of contracta-
rianism and in neoclassical economic theory. Contractarianism, associated with
Nozick’s libertarian approach, states that a free society is one in which the state
should have no power and duty other than that of securing private property rights
and guaranteeing the proper functioning of markets. Neoclassical economics
stresses that competitive markets are the best means to ensure an efficient resource
allocation. On practical grounds, neoliberalism is a project aimed at the restoration
of class power, where the capitalist class is eager to regain the economic and politi-
cal power lost, to the benefit of middle and working classes, as a consequence of the
welfare state policies carried out in three decades following the Second World War
(Harvey 2005). In general, state intervention in the economy is warranted with ref-
erence to three goals: restore market efficiency; redistribute wealth to ensure social
justice; protect citizens’ health, and human rights and the environment (when the
rights of future generations are taken into account based on sustainability princi-
ples). Given its theoretical stances, it is clear that a neoliberal state may pursue only
the first objective and that, given its blind faith in the allocative efficiency of the
market, only according to the Coase theorem (Coase 1960), that is tackling the inef-
ficiencies due to public goods by assuring clear property rights (i.e privatization).
No intervention instead is foreseen with respect to redistributive, health and sustain-
ability goals. Moreover, a new goal arises in the neoliberal state: foster capital accu-
mulation, i.e. a regressive wealth redistribution, transferring wealth from poor to
rich people.
Table 2.1 synthetizes the effects of the endorsement of a neoliberal economic
policy on the public management of the risks posed by nanofoods. The section a of
the table shows how the choice under neoliberalism is to give up public regulation
and promote private regulation instead, which gives corporations the power to set
the institutional stage that best fits their vested interests. The securing of public
research funds, the weakening of firms’ liability with regards to nanofood adverse
effects and the reinforcement of patent laws are the major consequences of such a
choice, resulting in what I have called in the table “progress without people” using
the title of a book which is a masterpiece in describing the role of state corporate
power in the processes of technological innovation (Noble 1995). I will discuss the
arguments developed by Noble with reference to nanofood innovation in the next
28 V. Sodano

Table 2.1a  How neoliberal policies affect nanofood regulation

Goals and related policy interventions in a neoliberal state
Policy Goals allowed by Restore market efficiency by establishing clear private
neoliberalism property rights.
Protect private property
Foster capital accumulation.
Interventions Deregulation.
Substituting public regulation with private regulation (soft
regulation).
Privatization
Tightening patent systems.
Enforce private property rights.
Promote innovation.
Public funds to private research.
Effects on Nano innovation Corporate lobbies setting regulatory rules.
Low level of risk management and consumer protection.
Science at the service of corporate profits.
Innovation used as a competitive weapon.
Abandonment of useful research patterns because not
consistent with vested interests.
In a nutshell: progress without people (Noble 1995).

Table 2.1b  How neoliberalism prevents from tackling nanofood risks

Goals and policy interventions, consistent with nanofood risk effective management, which are
not allowed in a neoliberal sates
Policy Goals not Fulfillment of Economic justice Global social justice
allowed by human rights and
neoliberalism sustainability
Entailed nanofood Human health. Monopoly. Corporate Market disruption.
risks Environment power Unemployment. North-­
South divide. Nanorisk
dumping. Food sovereignty
(Not allowed) Precautionary Strong antitrust Trade policy
Interventions principle policy. Mandatory
Standard setting monitoring and Welfare policies (social
reporting. Lobbying security). International
transparency cooperation

paragraph of the paper. The second section of Table 2.1 calls attention to the goals
excluded by neoliberal policies, showing how such excluded goals, and the related
policy instruments, are the ones that would help tackle nanofood risks. The current
regulatory framework in the EU, in the same way as in the United States and in most
other countries, clearly reflects the outline sketched in the table. As a matter of fact,
none of the regulatory interventions quoted among the “excluded interventions” in
Table 2.1b have been implemented. The choice has been to set a plethora of n­ on-­binding
suggestions and guidelines (that is soft regulation as quoted in Table 2.1a) and let the
2  Politics of Nanotechnologies in Food and Agriculture 29

agribusiness, by endorsing the stakeholder approach in the regulatory decision pro-

cesses, set the stage for future regulation. It has been pointed out (Bonnafous-
Boucher and Porcher 2010; Sodano and Hingley 2016) how the consequence of soft
regulation and the stakeholder approach has been the cooptation of the regulatory
bodies by the most powerful stakeholders (namely agribusiness corporations), with
the demission of democratic governmental regulatory institutions and the birth of a
sort of corporatist state.

2.4  Unregulated Nanofood: The Reasons of the Agribusiness

Starting from the late seventies the agrifood sector has been affected by growing
processes of consolidation and globalization. Currently, each stage of the food sup-
ply chain, from the agricultural input industry (seed, agrochemicals and agricultural
machinery industry) to the food processing industry and retailing, presents a high
rate of concentration, with huge corporations controlling large shares of the world
market. In order to further accrue their market share and their profits, these corpora-
tions have to continuously gain competitive advantages over their competitors both
at horizontal (i.e. towards firms operating in their same industry) and vertical level
(i.e. towards firms operating in the other stages along the food supply chain). For
example, a food manufacturer has to gain market share with respect to other food
manufacturers but also has to gain bargaining power over its suppliers (for example,
farmers supplying raw agricultural products) and its distributors (for example retail-
ers) in order to appropriate larger shares of the added value of the entire food supply
chain. The main source of competitive advantage is innovation, which allows the
pursuit of cost reduction as well as differentiation strategies (Porter 1985).
Nanotechnologies together with biotechnologies and information technologies are
certainly among the most important sources of innovation within the food supply
chain. Food nanoinnovations that have been introduced so far show how firms at any
stage of the supply chain can benefit from them as a source of competitive advan-
tage. Seed and agrochemical corporations are using nanoinnovations (nanoformula-
tion of agrochemicals; nanosensors, nanobiocides and nanodevices for genetic
manipulation) to complete the second green revolution initiated with seed bioengi-
neering, and to make traditional farming techniques obsolete, further undermining
peasant agriculture and agroecological practices. The processing industry is using
nanoinnovation to carry out differentiation strategies to outperform competitors and
exercise market power through price discrimination. Moreover, the focus on func-
tional food is part of the attempt to change the attitudes of consumers towards high-­
tech food, overcoming their neophobia and increasing their trust in agribusiness.
Modern retail can benefit from nanoinnovations in packaging and nanosensor, to
extend shelf life and improve their logistics, lowering their distribution costs and
snatching even more market share from traditional retailers.
A general outcome of nanoinnovation is to deepen the segmentation of the food
market, starting from the breakdown of the market into four basic segments, namely:
30 V. Sodano

low price/low quality industrialized products for the poor masses (a sort of huge
junk food market), medium price/high tech food to capture the new induced needs
of functional foods of low-medium income consumers; high quality “traditional/
natural” food for high income consumers (this segment would capture what will
remain of organic and/or local food and gourmet); high price/high tech/high quality
foods for rich consumers. Such a segmentation would be consistent with the ever
increasing polarization of wealth distribution produced by neoliberalism. As long as
new tech food products require the joint effort of different actors along the supply
chain (for example, new genetically engineered plants may be programmed to
‘coordinate’ with nanobiocides and/or the addition of supplements and/or better
(nano) packaging to support longer shelf life and long distance transportation)
besides horizontal consolidation, vertical consolidation processes may also occur,
with the emergence of large conglomerates. Overall, nanoinnovations support and
reinforce the techno-corporate agri-food paradigm (Scrinis and Lyons 2007) within
the current neoliberal food regime (McMichael 2009). They serve, interalia, to
change people’s understanding of food and nutrition, separating ever-further the
consumption from the production sphere (that is the notion of ‘food from nowhere’
introduced by: Bové and Dufour 2001, p. 55), severing the bond between nature and
food, and accustoming the consumer to the new diets and lifestyles imposed by
corporate marketing policies.
Given the many benefits corporations may have from nanoinnovation it is strik-
ingly clear that they want to avoid any obstacle to the fast commercialization of
nanofoods, and therefore oppose any form of intervention. Not only do they want to
repeat the experience of the introduction of genetically modified organisms in the
United States, where the dramatic diffusion of genetically modified crops has been
made possible by choosing to consider them equivalent to their conventional coun-
terparts, moreover they want people to remain completely unaware of the new tech-
nologies, in such a way as to avoid raising concerns and requests for regulation (as
it has been from the beginning in the case of genetically modified organisms in the
EU and successively of their diffusion in the US). It is not by chance that after the
triumphant announcements of the first nano-innovations, a deafening silence has
fallen over the nanofoods that have been rather constantly placed on the market. It
is also not by chance that in almost every article addressing the issue of nanofood
regulation, it is stressed that it is better (it is implicit on the part of governments and
scientists) not to make too much noise about nanorisks, in order to avoid any con-
troversy as to the social desirability of the new technology and prevent the request
for regulation and mandatory labeling from coming from citizens who want to
defend their right to know. A further motivation for firms to have nanofoods unregu-
lated might depend on the difficulties encountered in clearly defining the private
intellectual property rights (IPRs) of the new products. The patent regime for nano-
technologies faces some challenges. Notwithstanding the fact that a high number of
nano-patents already exist worldwide (with the primacy of the USA, followed by
Japan, Germany and China), there are some unsolved legal issues concerning the
consistency among the patent systems of different countries and the verifiability and
the acceptability of the claims contained in patent requests. Many nano-applications
2  Politics of Nanotechnologies in Food and Agriculture 31

rely on nanotechnologies already patented and which have a necessary enabling

function with respect to a wide array of nanoapplications. There are few nanotech-
nologies that are critical research tools for the development of further innovation
(Barpujari 2010). The majority of these key patents are owned by the public sector,
and in particular by the US universities which have benefited from the huge amount
of public funds devoted to nanotechnologies in the US. The choice of these universi-
ties so far has been to exclusively license their discoveries to the industry, so that a
handful of mostly USA companies currently have the control of large swathes of the
new technologies. Given the still blurred system of intellectual property rights for
nanotechnologies, it might be the case for firms selling nanofood to protect their
innovation through trademark and industrial secrets, and therefore have no incen-
tives to give clear information (including nano-labels) on their nanoproducts.
Meanwhile, they can work behind the scenes in such a way as to gain future control
(through patents of key enabling technologies and systems of licenses) of the most
profitable nanotechnologies. The strategy of open innovation (Huizingh 2010;
Duarte and Sarkar 2011) that has until now been embraced by many companies also
makes the use of trademarks and industrial secrets more appropriate ways to protect
their innovative products.

2.5  U
 nregulated Nanofood: Nano-innovation Backed by the
Techno-scientific Ideology

Neoliberal policies and firms’ strategies are strong drivers of the current unregu-
lated nanofood development. Nonetheless, there is another important factor which
is helping the relentless advance of the new technologies, namely the notion of
technological determinism, and the generally accepted idea of technological change
as an engine of progress.
The notion of technological determinism is grounded on the idea of autonomy
and neutrality of science and technology. Autonomy means that scientific knowl-
edge, and the subsequent technological innovations, proceed independently from
the other forces that shape societies, such as norms, beliefs, political and ethical
issues. They proceed as autonomous forces and intellectual enterprises, guided by
an innate unbounded and value-free human rationality. Science and technologies
shape society, triggering processes of modernization and progress, but are not them-
selves influenced by society.
Neutrality means that science and technology are not affected by any value
judgement concerning the goals of society; neutrality also means that science and
technology have no preferences as to the various possible uses to which they can be
put (Feenberg 2002). As such, social changes are deterministically caused by sci-
ence and technology, the latter viewed as autonomous forces of social progress. The
notion of technological determinism dates back to the European Enlightenment of
the eighteenth century when the traditional conception of society, where social
32 V. Sodano

i­ nstitutions and beliefs were justified by taking for granted myths and customs, was
substituted by the modern conception, where customs and institution were justified
on the basis of an instrumental human rationality. Later, in the nineteenth century, it
became commonplace to view modernity as an unending progress towards the ful-
fillment of human needs through technological advance. A consequence of the
endorsement of technological determinism is that technical change, even when it
entails high social and environmental costs, must never be delayed. At the dawn of
the early industrial revolution the notion fueled the faith in progress, which in turn
fueled the industrialization of western economies and capitalistic accumulation.
Precisely the negative consequences of the industrial revolution, despite the pro-
tests by the social classes adversely affected by industrialization, fed the rise of
critical theory of technological change in the first half of the twentieth century. One
of the manifestoes of the Frankfurt school of social theory, Adorno and Hokheimer’s
classic Dialectic of Enlightenment, explored the intertwining of the domination of
nature, psychological repression, and social power. This work opened new perspec-
tives in the study of the authority system of advanced society, on the technologies
that integrate it, and on the forms of social struggle that resist its hegemony
(Feenberg 2002, 2005). Central to the critical theory is the view that technical
change is the product of the pursuit of its own interest by some group in society
(generally the dominant class) who chooses, from among different feasible techno-
logical paths, the ones that better fit their personal goals. In this sense, science and
technological systems are neither autonomous nor neutral, rather they are spheres of
human activity embedded in the general social structure which shapes (and is shaped
by) them. In other words, technologies develop in predetermined directions and
determine social change (MacKenzie and Wajcman 1999). In the last thirty years of
the twentieth century, the critical theory paved the way for a large body of technol-
ogy studies that rejected the notion of technological determinism. Particularly suc-
cessful was the constructivist theory, with the adoption of Thomas Hughes’ notion
of sociotechnical (1986) and the actor network theory of Bruno Latour. The main
argument of the constructivist technology studies is that those who design technolo-
gies are by the same token ‘designing society’ (Latour 1988, 1992).
As regards economic science, the neoclassical theory embraced from its very
beginning a deterministic stance. In the neoclassical model, science and technology
are spheres separated from the economic activity; technology is an exogenous vari-
able which is not explained by the behaviors of economic actors. Only after the
work of Schumpeter has an economics of innovation been developed, embracing a
large array of research themes, such as the study of firms’ research and development
policies, the development of technological systems, the dynamics of innovation, the
study of public research policy and so on. However, it is important to stress that
most economic literature only partially overcomes the notion of economic deter-
minism. On the one hand, it acknowledges the embeddedness of the technoscience
in the larger socioeconomic system and the influence that firms’ strategies and pub-
lic policy may have on research and innovation patterns, thus questioning the
­autonomy of technology. On the other hand, it does dispute the principle of neutral-
ity, but from the point of view of substantivism, which argues that technology is a
2  Politics of Nanotechnologies in Food and Agriculture 33

Table 2.2  Alternative theories of technical change and economic and political thoughts
Technology is: Autonomous Not autonomous, human controlled
Neutral Technological determinism Instrumentalism (liberal faith in
(complete progress)
separation of Modernization theory; Liberal political thought; management
means and ends) neoclassical economics; studies; constructivism.Neoliberalism
traditional
Marxism.Neoliberalism
Not neutral. Substantivism (means and Critical theory (choice of alternative
Value laden ends linked in systems) means-ends systems)
(means for way Economic neo-institutionalism; Technological change is power driven
of life that evolutionary economics
includes ends)
Source adapted from Quan-Haasen (2013)

force of its own that determines what our society will be like, on the basis of its own
values (good or bad) which people cannot control. Therefore, technology itself
determines how it will be used and towards what ends, but it moves autonomously
along its own path and people have little influence on its socio-economic and politi-
cal impacts. In short, economics either assumes that technology is autonomous and
neutral, or it removes the two elements of the notion of technological determinism
one at a time.
Table 2.2 reassumes the different conceptions of technical change on the basis of
the endorsement of the two elements of technological determinism (i.e. autonomy
and neutrality); for each of the four identified approaches (technological determin-
ism, instrumentalism, substantivism and critical theory), some economic and politi-
cal theories embracing them are mentioned. It is worth noticing that none of the
most popular theories (within the orthodox, but also within the heterodox theories)
simultaneously dispute autonomy and neutrality of technology. Only the critical
theory fully challenges the notion of technological determinism; nevertheless, the
dominant schools of political, social and economic thought do not endorse critical
theory and, as a consequence, lose sight of power and class domination in the tech-
nological discourse. It is also worth noticing the position of neoliberalism which
never questions the neutrality of technology, but is more flexible on the autonomy
assumption, accepting that technological innovation can and ought to be financed
and supported by the public and the private sector, on the basis of faith in progress,
i.e. the assumption that technological change is always beneficial.
Technological determinism has been the best ally of the capitalist class since the
early phases of the industrial revolution. In his books, Noble (1995) has masterly
shown how the social negative impacts, in terms of labor displacement, unemploy-
ment and environmental and health effects, of the mechanical and chemical innova-
tions throughout the nineteenth and twentieth century have been dismissed as trivial
side effects by appealing to an almost religious commonly shared faith in progress.
As pointed out by Noble, since the time of the Enlightenment, “science had come to
be identified with transcendence, on the basis of the inheritance of the new medieval
34 V. Sodano

view of technology as a means of recovering mankind’s original perfection”44

(Noble 1997, p.26). The faith in technology and faith in progress ideology served
the dominant classes to create social consensus for the violent repression of riots
against those new technologies, as in the case of the Luddites, or in the case of the
Swing riots of the 1930s caused by the introduction of threshing machines. The true
fact is that workers opposing the new machineries “were not against technology,
rather they were against the efforts of capital, which was using technology as a
vehicle, to restructure social relations and the patterns of production at their
expense” (Noble 1995, p. 7).
Since the first industrial revolution until today, the notion of technological deter-
minism has allowed capital to impose any technological change functional to the
mere pursuit of profit. Nevertheless, in the first three decades after World War II,
thanks in part to the critical theory and in part to the advent of the welfare state, the
idea arose of the need for state intervention in order to direct scientific research
towards goals of social justice and to mitigate the socially undesirable effects of
new technologies. The victories achieved by labor unions and environmental move-
ments in those years bear witness to this momentary rift of the notion of technologi-
cal determinism. The raise of neoliberalism at the end of the seventies gave renewed
strength to the notion of technological determinism leading to the establishment of
the techno-scientific ideology (Levidow et al. 2012; Hess 2012), which preaches the
ability of scientific knowledge to solve any problem of human societies, and pledges
the ethical and political neutrality of science (and scientists). Such an ideology is
used by business to impose their technological choices and to capture state regula-
tory and public research institutions in order to shape the institutional framework in
such a way as to serve business interests.
The way in which the issue of nanotechnology regulation has been framed so far
is an outstanding example of how the notion of technological determinism has given
support to the new power relationships established by neoliberalism. Three ele-
ments in particular of the nanoregulation framing strategy, which is outlined in the
majority of public documents and academic literature dealing with the issue of
nanoregulation, help clarify this point.
The first element is the common stated presumption that scientific knowledge
and technology can definitively solve the most important social problems (this is the
myth of technological salvation, which is part of the faith in progress credence). The
following statement opening a Communication of the European Commission on the
Second Regulatory Review on Nanomaterials provides an insightful example; “the
benefits of nanomaterials range from saving lives, breakthroughs enabling new
applications or reducing the environmental impacts to improving the function of

4
 And Noble makes clear that the term mankind referred literally only to men, since the religion of
technology was part of the myth of a masculine millennium, which served to shape the hierarchical
organizational structures, in the economy and in society, and the mode of exploitation which
formed the backbone of the processes of capitalistic accumulation (Noble 1995, ch. 7).
2  Politics of Nanotechnologies in Food and Agriculture 35

everyday commodity products”.5 Another example is the following statement from

The OECD Working Party on Nanotechnology6: “Nanotechnologies are likely to
offer a wide range of benefits, including in helping address a range of societal and
environmental challenges, e.g. in providing renewable energy and clean water, and
in improving health and longevity, as well as the environment”.7 Similar statements
can be found in FAO documents: “nanotechnology offers considerable opportuni-
ties for the development of innovative products and applications for agriculture,
water treatment and food production, processing, preservation and packaging, and
its use may benefit farmers, the food industry and consumers alike” (FAO 2014).
Linked to the first is the second element which bears witness to the endorsement
of technological determinism in the nanoregulation issue: the emphasis on risks
when making judgments on the social desirability of the technology. The emphasis
on risk reinforces the assumption of the indisputable benefits; the clear message is
that we must not question ‘whether or not” or ‘for the benefit of whom’ the new
products have to enter the market, rather ‘how’ to deal with the associated risks. “For
critics (Felt and Wynne 2007), framing technoscience issues in terms of risk means
pre-empting any possible debate on the need and desirability of innovation, or its
distributional effects. The assumption is that the benefits of innovation are unques-
tionable and general” (Pellinzzoni 2012). Moreover, besides shifting the discourse
from assessing the benefits to dealing with risks, the issue of risk is understood in
terms of risk perception. In this view, the real social issue associated with nanotech-
nologies is the fear and anxiety that their unknown health and environmental effects
may raise, with people’s concerns framed as inability to rationally understand sci-
ence and technology. In such a way any skepticism about the new technologies is
delegitimized and risk management intervention ends up being directed towards
communication policies aimed at increasing consumers’ willingness to take risks
rather than protect them from hazardous products; the principal public intervention
is therefore directed at increasing their social acceptance (Vanclay et al. 2013).
The third element of the nanoregulatory strategy which is strictly linked to the
embracement of technological determinism is the shift from political to ethical dis-
course. Since the social benefits of the new technologies are certain and unquestion-
able, there may not be political conflicts about technology but only divergent ethical
stances. When any resistance is viewed as consequence of the possible diverse ethi-
cal instances present in society, the role of the state is to smooth these divergences
through various forms of governance under the guidance of experts in the field of
ethics. The centrality of ethics in state regulatory activities has been associated with
the spread of a flexible way of governing without law and have been indicated as

5
 Communication from the Commission to the European Parliament, the Council and the European
Economic and social Committee. Second Regulatory Review on Nanomaterials (2012)
{SWD(2012) 288 final}.
6
 https://www.oecd.org/sti/nano/oecdworkingpartyonnanotechnologywpnvisionstatement.htm.
7
 However, unlocking this potential will require a responsible and co-coordinated approach to
ensure that potential challenges are being addressed at the same time as the technology is develop-
ing. The OECD Working Party on Nanotechnology.
36 V. Sodano

‘ethical legislation’ in many EU policy documents (Felt and Wynne 2007). Ethical
councils and participatory discussion settings led by experts are outstanding exam-
ples of such forms of intervention. Ethical councils are made up of appointed
‘experts’, allegedly capable of representing relevant viewpoints and concerns, or, in
the case of public citizen dialogues, to interpret inputs from, and give proper guid-
ance to, the reflections of ‘lay’ people. For critics, ethical councils are used to mar-
ginalizing non-negotiable standpoints (i.e. political struggles) as regards new
technologies, by stigmatizing them as ignorance or prejudice. Ethics is presented as
a neutral technique capable of producing ‘a single, correct solution for each ethical
problem and therefore ethics councils may be depicted as ‘a “neutral” normative
tool. Ethics, in other words, is framed as the equivalent in the normative realm of the
function that ‘sound science’ performs in the realm of facts (Pellinzoni 2012,
pp. 262–263). As a consequence, the legislative activity is severed from its linkages
with politics and finds its new foundation in ethics, with the latter moreover assum-
ing the character of an exact science. Such an alliance between science and ethics
serves to further shrink the room for political and distributive questions about tech-
nological innovation and dramatically reinforce the ideology of technological
determinism.

2.6  Conclusion

The way in which the issue of nanotechnology regulation has been dealt with so far
by national and international regulatory bodies is at the same time grotesque and
deceitful. The unanimous agreement on the possible risks of new technologies and
on the need for their regulation, emerged in the countless reports and discussion
forum on the subject, has been accompanied by an almost complete legislative inac-
tion. With respect to the food and agricultural sectors, this state of affairs is well
portrayed in the FAO/WHO technical report (FAO 2014) on the ‘state of the art on
the initiatives and activities relevant to risk assessment and risk management of
nanotechnologies in the food and agriculture sectors’. Here the call for an interna-
tional coordinated effort to face food nanorisk is not supported by real action pro-
grams and strong request of commitment to governments.
The paper has investigated the causes of such a paradoxical situation, with a
focus on the political besides the technical reasons beyond the regulatory paralysis.
Three main reasons have been discussed. First, the attitudes of the neoliberal state,
which praises deregulation and the primacy of the economic over social and politi-
cal spheres. Second, the lobbying activities of the business sector which wants to be
free to use the new technologies, whatever their health and environmental negative
impacts, for its profit seeking strategies. Third, the dominance of a techno-scientific
ideology which, by praising the idea of technological determinism, helps to remove
the technology question from public debate, namely the problem of the social and
political effects of technological change. Together these three driving forces are
contributing not only to the regulatory delay, but also to a subtle communication
2  Politics of Nanotechnologies in Food and Agriculture 37

campaign directed at accommodating consumers’ attitudes in such a way as to

accept nanofoods and the related risks.
Nanotechnologies in the agri-food sector, also combined with biotechnologies,
may dramatically change the way we conceive food and nutrition and may have
unexpected negative effects on our lives. Main risks are associated with adverse
health and environmental effects, but also with the restructuring of the food system
in a way which, by further strengthening corporate power, weakens people’s control
over the food they grow and eat. Nanotechnologies are a core engine of the techno-­
corporate agri-food paradigm (Scrinis and Lyons 2007), leading to an increasingly
globalized, export-oriented and corporate-dominated food system; a system which
jeopardizes food sovereignty, local food diversity and democracy (Windfuhr and
Jonsen 2005). The findings of the paper show that in order to oppose such a system
it is necessary to put at the center of the regulatory debate the “question concerning
technology”, that is to look at the way in which technology affects power relation-
ships within society. What is needed is to shift attention from efficiency to power
issues and assess new technologies from a political rather than an economic or ethi-
cal perspective. The assumption of technology determinism should be avoided in
order to reassert the fact that technology is a means to an end and that it is a human
tool; as such, it is used to pursue the individual goals of those who control technol-
ogy. Nanofood regulation should be tailored with the aim, above all, to socialize and
democratize processes of technological changes, by ensuring that technology is not
mostly privately owned and that all those affected by technology have their voices
heard in the processes of technological change.

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Chapter 3
Nanosensors for Food and Agriculture

Anup K. Srivastava, Atul Dev, and Surajit Karmakar

Abstract  Food and Agriculture is a major sector impacting the economic growth of
a developing country. Food industry includes agriculture practices of growing crops,
raising livestock and sea foods, food processing and packaging, regulating produc-
tion and distribution. Agriculture comprises farming, forestry, dairy, fruit cultiva-
tion, poultry, beekeeping, and mushroom cultivation. According to the Food and
Agriculture Organisation (FAO) about 20–45% of plant, meat and fish products are
lost or wasted, amounting for instance to 286 million tons of cereals products in
industriallized countries. Therefore, at all stages of food production there is a need
to monitor the quality of products in order to ensure food safety and commercial
viability.
Here we review nanosensors and nanobiosensors used in food and agricultural
sectors. Nanomaterials comprise metal nanoparticles, metal nanoclusters, metal
oxide nanoparticles, metal and carbon quantum dots, graphene, carbon nanotubes
and nanocomposites. Sensors include electrochemical nanosensors, optical nano-
sensors, electronic nose and electronic tongue, nano-barcode technology and wire-
less nanosensors. The sensitivity of these sensors is due to unique electrochemical,
optical, Raman, catalytic and super-paramagnetic properties. They can detect food
contaminants such as preservatives, antibiotics, heavy metal ions, toxins, microbial
load and pathogens. They can also monitor temperature, traceability, humidity, gas
and aroma of food stuff.

Keywords  Nanosensors and nanobiosensors • Agriculture • Food quality • Precision

agriculture • Electrochemical nanobiosensors

A.K. Srivastava • A. Dev • S. Karmakar (*)

Institute of Nano Science and Technology, Habitat Centre,
Phase-10, Mohali 160062, Punjab, India
e-mail: surajit@inst.ac.in

© Springer International Publishing AG 2017 41

S. Ranjan et al. (eds.), Nanoscience in Food and Agriculture 5, Sustainable
Agriculture Reviews 26, DOI 10.1007/978-3-319-58496-6_3
42 A.K. Srivastava et al.

3.1  Introduction

Food and agriculture sector are two promising area decide the sustainable and eco-
nomic growth of a country. Modern food industry deal with food production and
management, innovation in the food formulation, processing, packaging, safety and
quality assessment, storage and efficient distribution (Roos et al. 2016). The food
engineering involves the use of pH, temperature, and solvent activity that advances
the choice of raw materials, formulations of food products, provide a thrust to man-
ufacturing and bioprocessing and enhances the self-life of the food (Heldman and
Lund 2011). The principle of sustainable agriculture to meet our present need with-
out compromising the resources for future generation depends on two prospects;
first is the agriculture practices should be self-sustained by conservation of protec-
tive resources, i.e., maintaining soil fertility, protecting ground water, developing
renewable energy and the alternative for tolerating the consequences of climate
change. Second; the considering sustainability by managing the nearby urban area
with proper recycling of sewage waste, developing rural employment and contribu-
tion to construct a rural landscape (E. Lichtfouse et al. 2009). The transition from
conventional agriculture farming to industrial farming dramatically enhances the
food production but not able to manage the limited use of pesticides and fertilizers.
The affirmative agriculture productivity compromised with the consequences of soil
erosion, ground water pollution, river eutrophication, development of weed and
resistant to the chemical control (Lichtfouse et al. 2005). The Food and Agricultural
output exert a significant and fascinating impact on the health and nutritional assur-
ance that heavily dependent on the consumer’s perception, opinion, and satisfaction
(Martins et al. 2016).The negative events related to the food and agriculture prac-
tices led to the most stringent regulation over the agronomy, production, quality
control, quality assessment, safety and distribution (Luvisi 2016). The implementa-
tion of the nanotechnology is promising and provided a new edge to the agro-­
technology, improved irrigation and fertilizer utilization, enhances the food
production and processing, packaging, and storage. The nanotechnology-based
sensing gain enormous momentum and provided broad spectrum application in
food and agriculture sector (Neethirajan and Jayas 2011).
The nanotechnology involves the study, manipulation, creation, and use of materi-
als, devices, and systems typically with dimensions smaller than 100  nm.
Nanotechnology put the impetus to revolutionize the area of diagnostics in health,
medicine, food, environment, and agriculture sector, transitioning theoretical aspects
into the practical output (Dasgupta et al. 2017; Shukla et al. 2017; Walia et al. 2017;
Balaji et al. 2017; Maddinedi et al. 2017; Sai et al. 2017; Ranjan and Chidambaram
2016; Janardan et al. 2016; Ranjan et al. 2016; Jain et al. 2016; Dasgupta et al. 2016).
In turn, it playing a crucial role in the development and innovation which enhance the
sensitivity and attributes the nanosensors and nanobiosensors based applications
(Momin et al. 2013). The generalized definition of a chemical sensor is a device that
transforms chemical information, ranging from the concentration of a particular sam-
ple component to total composition analysis, into an analytically useful signal.
However, Biosensors are defined as an analytical device for the quantitative detection
3  Nanosensors for Food and Agriculture 43

of an analyte with a biologically active element such as an antibody, enzyme, oligo-

nucleotide or receptor attach to the surface of a transducer. The biological recogni-
tion molecule interact with target compound and the physical transducer converts the
biological response to a detectable signal, quantitated as redox changes and detected
electrochemically, optically, acoustically, mechanically, calorimetrically, or electron-
ically, which can be correlated with the analyte concentration (Rogers and Sharma
1994). The characteristic of a biological entity to interact with a particular analyte or
substrate are employ in the designing of biosensors. Specifically, the nanobiosensors,
constitute transducer is based on nanomaterials, having physically nano-scale con-
finement or nanofabrication of nanoparticles or nanostructured surfaces. Biosensors
cover well-established bioanalytical techniques while nano-biosensors with integra-
tion of nanotechnology revolutionizing this field with potential alternatives by mini-
mizing the load of standard laboratory methods and protocols, along with the benefit
of quick response time, enhanced sensitivity, robustness and portability for a point on
use (Gomes et al. 2015).
The present review emphasizing various nanotechnological approaches in con-
struction and designing of new nanosensors and nanobiosensors. The nanoconfined
metallic nanoparticle like gold nanoparticle, silver nanoparticle; magnetic nanopar-
ticle, quantum dots, upconversion nanoparticle, graphene oxide, single and multi-
walled carbon nanotubes, nanostructure-based sensors in the e-nose and e-tongue,
and wireless nanosensors functionalization or fabrication have been used to achieve
the enhanced sensing. Based on transducer the nanosensors, bionanosensors, elec-
trochemical nanosensors, optical nanosensors, wireless nanosensors, nano-barcode
technology is discussed in detail. Nanosensors and nanobiosensors have potential
application in the food sector as in monitoring food processing, food quality assess-
ment, food packaging, food storage, monitoring of shelf life and viability, indicator
of food safety and microbial contamination, toxin and residual contamination in
food. The major implication in the area of agriculture are physical monitoring of
temperature, humidity, soil quality and fertility, sensing microbiological microenvi-
ronment of the soil, indicator for seed viability and shelf life, response sensors for
irrigation and safety in agronomy, precision agriculture, detection of residual pesti-
cides, fertilizers and toxins, and plant pathological monitoring (Fig. 3.1) (Rai et al.
2012). The innovation and designing of some nanosensors are correlated with the
particular application in the respective area of the food and agriculture sectors. The
commercializations of the presently designed nanosensors are crucial for the sus-
tainable use of the technology, possible after firm utilization of intellectual property
right and patent rights.

3.2  Nanosensors and Nanobiosensors

As aforementioned previously the biosensor operates on the basis of two principles;

first, is biological recognition of specific analyte and second, is sensing operate in a
connected manner. The prefix nano in the sensors and biosensors are integrated after
functionally transforming the sensing component with nanostructures for enhanced
44 A.K. Srivastava et al.

Fig. 3.1  Schematics depicting the major nanostructures used in the area of food and agriculture
sector. Nano barcode technology and electronic NOSE are the major nanotechnological integration
utilized in the development of the suitable nanosensors or nanobiosensors. At present, a major
application of nanosensor or nanobiosensor in the area of agriculture and food industries are
inscribed. MNP magnetic nanoparticles, AuNP gold nanoparticles, UCNP upconversion nanopar-
ticles, QD quantum dots, SWNT single-wall carbon nanotubes, MWNT multi-wall carbon
nanotubes

output. The crucial function of the recognition system is to provide specific receptor
for initial recognition and attachment. The selectivity for the particular analyte pro-
vides functional sensitivity to the sensor. The transducer serves as a sensor are fab-
ricated with the nanomaterial such as metallic gold and iron oxide nanoparticle,
quantum dots, graphene oxide and carbon nanotube. The nanoconfinement, flexible
morphology, enhanced optical, mechanical, electrical, thermal properties, and high
specific surface area of the nanomaterial enhance the transducing capability to a
certain degree. Nanosensors or nanobiosensors are categorized based on transduc-
tion mechanism for generation of output; as electrochemical nanosensors rely on
the nanomaterial or CNT-based electrode; optical nanosensors are attributes with
the enhanced optical property of the metallic nanoparticle, upconversion nanopar-
ticle, and quantum dots. The third category of mass Nanosensors with compara-
tively fewer implications in the area of food and agriculture sector relies on the
mechanical and piezoelectric properties of micro-cantilever and crystals respec-
tively, represented in the schematic (Fig. 3.2).

3.3  Electrochemical Nanosensors

Electrochemical sensors are most commonly used and widely accepted sensors
functions on the principle of electrochemistry. The electron consumed or generated
during bio interactions produces electrochemical signals, is measured by electro-
chemical methodologies. The electrochemical nanosensors rely on chemical
reactions between nano-fabricated chemical, biomolecule, and the biological
­
­element, target analyte to produce or consume ions or electrons, measured as
­voltage, current or impedance (Chaubey and Malhotra 2002). The high sensitivity
3  Nanosensors for Food and Agriculture 45

Fig. 3.2  A typical nanobiosensors comprises of essential components starting from sample ana-
lyte to bioreceptor, transducer with integrated nanostructures and finally detectors (Left to right);
Analytes are chemical or biological entity serve as a sample for quantitation or detection, which is
unique to the bioreceptor. Bioreceptor is the recognition molecule of biological origin that could
be the functional or structural protein, oligonucleotide including aptamers, complete microbes or
its component, cells, specific tissue and any subcellular organelle. The biological response is trans-
ferred to the detector via transducer integrated or functionalized with nanostructures, i.e., Metal
Nanoparticles, Magnetic Nanoparticles, Upconversion Nanoparticle, Quantum dots, Carbon based
material such as Graphene Oxide and Carbon nanotubes for enhanced detection via electrochemi-
cal, optical and mass detection methods. Here, NPs abbreviated for nanoparticles

of electrochemical transducers, their compatibility with modern miniaturization/

nano-fabrication technologies, minimal power requirements, robustness, economi-
cal cost, low maintenance, rapidity, low detection limits and simplicity make it
applicable for the sensing applications. The electrochemical signal generated quan-
titatively correlated with the amount of analyte present in a sample. Based on their
working principle electrochemical Nano-sensors device could be categorized in
amperometry, voltammetry and potentiometry.
The amperometric sensor is a variant of an electrochemical sensor that continu-
ously measures current generated due to the redox reaction of an electroactive spe-
cies. The potential is fixed at a constant value, and the Faradaic current measured to
determine the concentration of the electroactive species (Chaubey and Malhotra
2002). The Clark oxygen electrode having platinum as working electrode and Ag/
AgCl as reference were used to measure the oxygen concentration is an example of
Amperometric detection. The peak value of current observed over the linear voltage
range shows the proportionality with the electroactive analytes. The real application
of amperometric Nanosensors initiated in the area of health care and diagnostic with
the development of ATP sensor (Kueng et al. 2004), advance pregnancy test based
on beta HCG sensor (Santandreu et  al. 1999). The nanofabrication methodology
makes amperometric biosensors more reliable, cheaper and highly sensitive make it
expand the application from clinical to environmental, food and agriculture sector.
46 A.K. Srivastava et al.

Detection of Organophosphates (Yan et al. 2013), sulphonamides (Xu et al. 2013),

ractopamine and salbutamol (Lin et al. 2013a), fructose content (Antiochia et al.
2013), Hydrogen peroxide (Nasirizadeh et al. 2015) are the example of Amperometric
based nano-sensors and being discussed in the detail in application section.
Voltammetry is a subsequent measurement of current by varying a potential in a
controlled way. Cyclic voltammetry preferably used to get the redox potential and
electrochemical reaction rates of the electrochemical reaction with analyte. The
voltage parameter varies between the reference electrode and working electrode, by
measuring the current between the working electrode and the counter electrode. The
obtained data plotted as current vs. voltage known as a voltammogram. The cyclic
voltammetry having some application in agriculture and food sector like detection
of carbosulphan in rice (Nesakumar et  al. 2016), Salmonella typhi (Singh et  al.
2015), heavy metal contamination in food sample (Yavuz et al. 2016). Potentiometric
sensors measure potential at working electrode with respect to the reference elec-
trode. The output signal generated because of accumulation of ion at ion-selective
electrodes and ion-sensitive field effect transistors at equilibrium. ISE detect ions
such as Na+, K+, Ca2+, H+ or NH4+ in complex biological matrices by sensing changes
in electrode potential (Koncki et  al. 2000). The Implications of electrochemical
nanosensor in the detection of various analytes such as preservatives, antibiotics,
pesticide and heavy metal in various food and agriculture are discussed in the later
sections (Duran and Marcato 2013).

3.4  Optical Nanosensors

Optical detection biosensors rely on the detection of the change in the optical signal
that made it highly compatible with various kinds of spectroscopic measurements,
such as absorption, fluorescence, phosphorescence, Raman, Surface Enhanced
Raman Scattering, and refraction, etc. Also, these spectroscopic methods can all
measure different properties, such as energy, polarization, amplitude, decay time,
and phase. The component like fiber optics probes transmits signals detected as
changes in wavelength, phase, time, intensity and polarity of the light. In general, a
large variety of optical methods has been used in biosensors, based on fluorescence
spectroscopy, surface Plasmon resonance, interferometry, and spectroscopy
Luminescence is the emission of light from any substances and having two compo-
nent, i.e., fluorescence and phosphorescence. The electron in the ground state
excited by incident light leads to excited singlet electron in an excited state which
upon returning to the ground state emits photons. Fluorescence-based nanosensing
has emerged as powerful techniques owing to their high sensitivity, fast response,
and ability to afford high spatial resolution through imaging and spectroscopic
methodologies. The implications of metal nanoparticle such as gold nanoparticles,
silver nanoparticles, and quantum dots possess the inherent property of fluorescence
heavily depend on the size and morphology of the nanoparticle. Some instances
such as detection of nitrite (Chen et al. 2016), reactive oxygen species (Hu et al.
3  Nanosensors for Food and Agriculture 47

2014), pathogenic bacteria such as S. aureus, V. parahemolyticus, and S. typhimurium,

E.coli (Wu et al. 2014); detection of organophosphates have been done by fluores-
cence base nanosensors (Dasary et al. 2008).
Quantum Dots are the nanoclusters of few hundred to thousand atoms in the form
of a binary compound as CdSe, GaAs, InAs, SiC, CdTe and a ternary compound of
InGaN, InGaP, and InGaAs. The small size of the quantum dots ranges between 1
and 20 nanometer which changes its behavior with the light. The small spatial
dimension exhibit frequent quantized energy level state by the transition of a single
electron from valance band to conduction band after interaction of photons.
Quantum dots shows the inverse relation between size and band gap, as the size of
quantum dots increases, the band gap, and emission wavelength decreases.
In the nanoconfinement, quantum dots exhibits full wavelength multicolored
fluorescence with high quantum yield, longer fluorescence lifetime, enhanced pho-
tostability as well as a narrow emission spectrum. The size and band gap in the
quantum dots are determinant of the emission wavelength that gives a unique appli-
cability to be used as a suitable fluorescent donor in fluorescent resonance energy
transfer, FRET. The exceptional multiwavelength emission fluorescence, initiated
with its application as a fluorescent label in the bioimaging and biomolecular assay
with further progress with the application as quantum dots-FRET based examina-
tion of enzyme activity, tracking intracellular gene delivery, single molecule detec-
tion and biophysical studies, detection of specific cellular and subcellular targets,
multicolor barcodes, and imaging. Moreover, the innovation in the quantum dots
based sensing system progressed with selective functionalization of the quantum
dots open doors for the application of functionalized quantum dots agriculture and
food industry. Recently the CdSe and ZnS quantum dots are surfaces modified with
the silane group and conjugated with the methyl acrylate functionalized molecularly
imprinted polymer to develop a quantum dots based optosensor for detection of
dicyandiamide in the milk product. The concentration of the dicyandiamide could
be linearly correlated with the fluorescent quenching of the quantum dots (Liu et al.
2016). In another work highly sensitive and rapid response graphene quantum dots
was prepared and developed as a resistive micro sensor interdigitated electrode
which selectively measures the soil moisture content by reading gravimetric mois-
ture content in the form of ionic conductivity (Kalita et al. 2016).
Surface Plasmon Resonance (SPR) is another domain of optical sensing utilized
for highly sensitive and rapid detection. The collective coherent oscillations of free
electrons in the conduction band of metal is first excited by the interactive electro-
magnetic field at a metal/dielectric interface, and these created charge density oscil-
lations are called surface plasmon polaritons (SPPs). The SPPs leads to the
appearance of the electric field that exponentially decays and diminished after pen-
etrating few nanometer in surrounding matrix. Resulting, the evanescent field which
is highly sensitive towards the refractive-index change of the surrounding medium.
Even small fluctuations in the refractive index of the medium alter the characteris-
tics of the incident light beam such as wavelength, phase, and angle; and SPR exci-
tation will change accordingly. Nanomaterials including metallic nanoparticles,
magnetic nanoparticles, carbon-based nanostructures, latex nanoparticles and
48 A.K. Srivastava et al.

l­iposome nanoparticles are engineered to show enhanced SPR sensing system for
detecting concanavalin A, antibiotics, mycotoxins and pathogen like E.Coli
(Evtugyn et al. 2013; Huang et al. 2013; Zeng et al. 2014).
The amplification of the signals in Surface Enhanced Raman Scattering (SERS)
arises by electromagnetic interaction of light with the metallic nanoparticle, which
produces large amplifications of the laser field through excitations, known as plas-
mon resonances. Surface-enhanced Raman scattering is being a promising analyti-
cal technique that can be used to overcome problem-related with a sensitivity of
detection. When analyte molecules are deposited on the nanoparticle surface, their
SERS signals are greatly increased at SERS-active sites known as “hot spots”
because of electromagnetic, and chemical enhancement effects. The detection sen-
sitivity increased up to 1014 orders of magnitude used for detection of antibiotics,
pesticides such as malathion and sulphonamides (Dasary et al. 2008; Guillén et al.
2011).

3.5  Nano-Barcode Technology

Barcode technology follows the principle of symbology by interpreting the encoded

data or information in the form of a map. Formally “Bio-barcode” or “DNA bar-
code” technology is novel tool extensively utilized for the identification of single
species of animal, plant, microbes by taking a small stretch of a single gene (Ferri
et al. 2009). The methodology includes a collection of short DNA sequences from
different species and analysis of the data by constructing phylogenetic tree via
distance-­based neighbour-joining method. A 650 bp short sequence of mitochon-
drial cytochrome c oxidase subunit I gene abbreviated as COX-I or COI was exten-
sively used for taxonomical identification of American birds, Australian fishes
(Yancy et al. 2008), and tropical lepidopterans with the success rate of 98–100%.
The recombinant DNA technology opens the door for construction of universal
DNA-based barcode technology that enables the sample to analyzed with one poly-
merase chain reaction-based sequencing by utilizing universal primers. The non-­
coding nucleotide sequence inserted in between the construct with common begin
and end sequence in an orientation that recognized by universal primer in PCR to
amplify the whole construct. The above construct could be transformed in the tar-
geting organism to provide a tag for detection. The bio-barcode constructed almost
unaffected by frameshift mutation or any single point mutation in PCR amplifica-
tion (Gressel and Ehrlich 2002). Similar oligonucleotide index demonstrated as bio-
barcode with the PCR-based sequencing of 17 species of Scombridae family
members frequently present in the processed sea food (Botti and Giuffra 2010). In
last decade several biocide sensing application has been developed such as monitor-
ing physiological condition of Saccharomyces cerevisiae in the food processing and
fermentation technology (Delneri 2010), identification of fish species (Arami et al.
2011; Asis et al. 2016; Chang et al. 2016; Handy et al. 2011; Yang et al. 2012), dis-
crimination between mixed meat specimen (Colombo et  al. 2011), analysis of
3  Nanosensors for Food and Agriculture 49

Lathyrus clymenum adulterants (Ganopoulos et al. 2012), estimation of nematodes

in flowerbed and agriculture soil (Morise et al. 2012), identification of food associ-
ated insect pests (Cho et al. 2013), food and vegetable safety and quality control
observation (Jones et al. 2013; Maralit et al. 2013; Qiao et al. 2013).
Pragmatically, the DNA component system of bio-barcode technology priorly
characterizes it in the nanometer dimension. The recent development has been made
by utilizing the nanotechnology with the use of metallic and magnetic nanoparticles
in practice. The dual gold nanoparticle and iron oxide nanoparticle has been sepa-
rately conjugated with two different DNA barcode for rapid and robust detection of
Salmonella enteric serovar Enteritidis in the food sample (Zhang et al. 2009).

3.6  e-NOSE and e-TONGUE

The electronic nose and electronic tongue are functionally analogous to the human
sensory perception of odor and taste. The odor of volatile component and taste of
nonvolatile component keep crucial information about the quality and quantity of
the material in food, beverages, agriculture, pharmacology, personal care product
manufacturing and processing (Baldwin et al. 2011). The e-NOSE and e-TONGUE
are becoming the alternatives and substitute of the human sensory expert panel and
consumer panel established for the quality assessment and quality control during
the manufacturing processes to fulfill maximum consumers satisfaction. e-NOSE
comprises four components as Sampling headspace system, a sensor array, elec-
tronic data acquisition control system and a pattern recognition software. The sen-
sor array composite of the chemical sensors which upon contact with the volatile
analyte changes the conductance and gives a detection signal to the acquisition sys-
tem. Metal Oxide Sensors, Conductive Polymer Sensors, Quartz Crystal
Microbalance Sensors, Optical Sensors, Surface Acoustic Wave Sensors, gas sensi-
tive field effect transistors are the major kind of sensors used as a component of an
electronic nose (Martin et  al. 2001). The metal oxide sensor array prepared by
depositing the thin layer of doped metal oxide on the ceramic or the high-­temperature
resistant plate. The concentration of dopant material determines the sensitivity and
response time of the sensor to the analyte. Conductive polymer based Nanosensors
constructed by electrochemical deposition of conductive polymer precursor over
the silicon substrate. The metal oxide sensor and conductive polymer based sensors
are the most common type of the sensor array used for the detection. The Quartz
crystal balance is a coated resonator element gives the response by changing the
oscillation frequency after contact of the analyte (Di Natale et al. 1997). The data
from the sensor array is being analyzed and classified by the subsequent electronic
component by multivariate signal processing, which in turn processed by the pattern
recognition software based on parametric and non-parametric algorithm such as
principal component analysis (PCA), linear discriminate analysis (LDA), partial
least squares (PLS), functional discriminate analysis (FDA), cluster analysis (CA),
fuzzy logic or artificial neural network (ANN) and probabilistic neural network
50 A.K. Srivastava et al.

Fig. 3.3  The typical electronic nose with its component; Sample head space, Nanosensor array,
unit for algorithmic processing and classified data after the detection in form of a map. In the
functional aspects, volatile organic compound from the specific sample source of food, fruits and
vegetables, microbes, pesticides, plant components and waste reach to sensory array from sample
head space. After post sensory multivariate algorithmic processing, the signal is forwarded to pat-
tern recognition software for mapping and result output

(PNN) analysis (Scott et al. 2006). e-TONGUE is complementary in the principle of

detection and post analysis. The major two difference, first in the selectivity of the
liquid sample and second, it gives the result output in the form of saltiness, bitter-
ness, sweetness, sourness, and metallic taste (Fig.  3.3). The compound having
higher vapor pressure and low boiling points are small molecular weight (<350
Daltons) organic compounds with several polar and non-polar groups are highly
volatile called volatile organic compounds (VOCs). The VOCs like pyruvic acid,
glyphosate, acetic acid and citrinin are specifically present in the plant cell, pesti-
cides, microbes and food product respectively (Wilson and Baietto 2009). The
selectivity, sensitivity, redundancy, accuracy of the sensors, response time and reli-
ability of the e-NOSE and e-TONGUE make it most suitable device for the sensing
application in agriculture, forestry, and food industry. The VOCs release from the
food components are making the e-NOSE and e-TONGUE more applicable in area
of food technology from monitoring of raw and manufactured product, cooking and
fermentation process, product packaging, storage and quality assessment for long
term storage (Concina et al. 2012; Peris and Escuder-Gilabert 2013). Recently the
e-NOSE and e-TONGUE has been used for the evaluation of aroma transfer from
food plastics bags (Torri and Piochi 2016), quality assessment of beef fillets
(Mohareb et al. 2016), detection of Alicyclobacillus acidoterrestris spawned spoil-
age in apple juice (Huang et  al. 2015), detection of mixed edible oil (Men et  al.
2014) and identification of adulterated milk (Yu et al. 2007).
3  Nanosensors for Food and Agriculture 51

3.7  Wireless Nanosensors and Wireless Sensor Network

A wireless sensor network abbreviated as WSN is self-organizing with intelligent

decision-making capability; self-dynamic topological configuration, self-­diagnostics
with context awareness and fault tolerance, and self-healing autonomous operating
mode with information security system made up of several components of radio-­
frequency transceivers, sensors or nanosensors node, microcontrollers and power
sources. The micro-electro-mechanical and nano-electro-mechanical system based
sensors node minimized the cost, size, and power consumption and gave a reliable
measurement of small change in pressure, temperature, humidity along with the tem-
poral observation like proximity, position, speed, acceleration and vibration at the
place of observation. The limitless sensor flexibility and enhanced network robustness
give enormous applications in environment, defense, agriculture and food industries.
Precision agriculture term used for the agriculture practices with the integrated
information and wireless control technology in the farming or forestry. The agro-
nomical input such as fertilizers and irrigation are being applied very precisely con-
trolled by the crop growth response in a spatio-temporal manner. In practice the
wireless sensors network uniformly deployed in the soil, which collects and relays
the soil information to the control central via sensors nodes. The control server ana-
lyze and precisely decide the particular place where irrigation or fertilizer is required
(Sahota et al. 2011). The design and deployment of the wireless sensors network are
continuously expanding with multiple monitoring and control. A wireless sensor
network based irrigation management system WiPAM has been deployed, which
follow the workflow of taking soil moisture and temperature information at certain
time interval, relaying and saving data in coordinator node, forwarding the data to
remote monitoring system via a gateway node, and response value stored in coordi-
nator node directs the opening or closing of the irrigation valve. The whole work-
flow utilizes the several components such as wireless network, moisture and
temperature sensors, co-ordinator node, gateway node and automated irrigation
valve. ZigBee is an IEEE 802.15.4 is low cost and low power consuming personal
area networking protocol used for the wireless sensor networking. The sensors
deployed in the 40 cm in the deep soil around the root zone of the plant to sense the
water potential, soil moisture potential, and temperature. The irrigation system
comprises solenoid valves with optocouplers and switching transistors to control
the on/off of the valves. Self-sustained irrigation management system collects the
information at very 30 min, relayed and make the automated irrigation response
(Mafuta et al. 2013).In addition to irrigation management system, the wireless sen-
sors technology are being deployed for many application such as sensing leaf wet-
ness and leaf area index in the agriculture field (El Maazouzi et al. 2014; Shimojo
et al. 2013), precise green house management (ArunKumar and Alagumeenaakshi
2014), in mango and black pepper farming (Kodali et al. 2013; J. Li et al. 2013a).
Moreover the some instances of application of wireless sensing network in the food
industries are real-time traceability and food chain management system (Ko et al.
2014; Wang et al. 2015), under water wireless sensor network for marine fish farm-
ing and sustainability monitoring (Lloret et al. 2015).
52 A.K. Srivastava et al.

3.8  A
 pplication of Nanosensors and Nanobiosensors in Food
Sector

3.8.1  Detection of Preservative Food Contaminant

The distinct shape and size dependent properties of metallic nanoparticles offer
enormous potential applications in the area of food technology. The desirable opti-
cal, mechanical, chemical, antimicrobial and electronic properties of metallic
nanoparticle make it novel for conjugation with enzymes, antibodies, ligands, drugs,
colorimetric and fluorimetric agents and other biomolecules thus opening the way
for sensitive diagnostic assays, radiotherapy, thermal ablation, gene and drug deliv-
ery, optical imaging, labelling of biological systems, effective antimicrobial activi-
ties and detoxification of hazardous compounds (O’Neal et al. 2004). Additionally,
metallic NPs have a huge role in food production, packaging, consumption, ability
to quick response against pathogens, pesticides, and other toxic residues through
detection of microbial deterioration of food quality and contaminant. Among the
metallic nanoparticles, the colloidal gold nanoparticle has been mostly applied for
various applications because of the flexible size range of sub 10–250 nm and com-
plex shape dependent optical and mechanical properties (Castro et al. 1990).
In the context of optical property, the extinction spectra of gold nanoparticles are
dominated by localized surface Plasmon resonance, as coherent excitation of the
conduction band electrons by oscillating electromagnetic field induces coherent
oscillation on the positive metallic lattice. The incorporation and aggregation of
gold nanoparticle particles on nanosensor platform greatly enhance the sensitivity
of localized surface plasmon resonance by two to ten folds and Surface-enhanced
Raman scattering by 106–109 fold (Jain et al. 2007). The strong local surface plas-
mon resonance absorption with extremely high extinction coefficients in the visible
wavelength range is the characteristics of gold nanoparticle and gives a color transi-
tion from wine red being in dispersion state to blue after attaining aggregation state.
The estimation of the residual amount of antibiotics in milk, dairy product and meat,
is one of the demanding prospects in food technology. The gold nanoparticle syn-
thesized using pyrocatechol violet as a reducing agent in such a way that it gives
surface hydroxyl group functionality could be linked with hydroxyl and amide
group of the antibiotic via hydrogen bonding. The quantity of antibiotics like kana-
mycin, neomycin, streptomycin, and bleomycin could be detected by general color
change even with the less concentration of 1 × 10−9 M. Alternately, with advance-
ment in approach the sensitivity of detection enhanced by functionalizing gold
nanoparticles with thioaniline and mercaptophenyl boronic acid. Here thioaniline
serve as an electropolymerized agent, whereas mercaptophenyl boronic acid pro-
vide the pH dependent reversible binding capability, stabilize the complex and pre-
vent from precipitation. The thioaniline-cross-linked gold nanoparticles composites
create a molecularly imprinted matrix comprises high sensitivities toward the sens-
ing of the antibiotic analytes. The quantity of neomycin, kanamycin, and streptomy-
cin detected by analyzing the surface plasmon resonance curve before and after
3  Nanosensors for Food and Agriculture 53

imprinting with the sensitivity of 2.00 ± 0.21 pM, 1.00 ± 0.10 pM, and 200 ± 30 fM
respectively (Frasconi et al. 2010).
Nitrite is essential food preservative but highly carcinogenic pollutant. Silver
nanoparticle-based nanosensor developed for the detection of nitrile utilizing hyper-
branched polyethyleneimine as scaffolds which protected silver nanoparticles. The
mechanism completes in two steps: the reaction of nitrite with hydrogen peroxide,
generates peroxynitrous acid under acidic conditions, induces the aggregation of
silver nanoparticle and fluorescence quenching has been correlated with the concen-
tration of nitrite within the limit of detection of 100 nM (Chen et al. 2016).
Gold nanoparticles enhanced surface plasmon resonance sensing approach used
for detection of Ochratoxin A is a mycotoxin produced by Aspergillus and
Penicillium species often contaminates food and agricultural stuff and has strong
toxic effects on the visceral oragn of both human and animals. Thiolated aptamer
sequences specific to Ochratoxin A is covalently attached to gold nanoparticles via
Au-S bond for detection of Ochratoxin A toxin (Evtugyn et al. 2013). The highly
reactive oxygen species is known to quench the strong fluorescence of gold nanopar-
ticles. A straightforward and selective spectroscopic method for antioxidant sensing
and imaging successfully demonstrated. The sensing mechanism is based on the
ability of antioxidants to protect the fluorescence of gold nanoparticles. Fresh fruits
and vegetables are promising sources of antioxidants that protect the cells and
organs from oxidative stress. This fluorescence protection based method is used for
evaluating the antioxidant content in commercial fruit juices and proves to be supe-
rior to existing spectroscopic sensing methods regarding rapid response, ease of use,
and good biocompatibility (Hu et al. 2014).
The contamination of natural honey with residues of sulphonamides is a major
concern to food companies, these residues of antibacterial drugs in honey gives
toxicological risks and allergenic effects. In the approach, polyclonal antiserum
against sulphathiazole conjugated to colloidal gold nanoparticles serve as detection
reagent for Lateral Flow Immunochromatographic Assay (Fig. 3.4). This device for
the detection of sulphathiazole is a cost-efficient and portable single-antigen directed
immunoassay. The device constructed on a plastic support with over mounting of
nitrocellulose membrane of thickness 15 ± 1 μm. Protein hapten conjugate OVA-S2
attached at the “test line” wherase goat anti-rabbit antibody at “control line” posi-
tion. On despensing gold nanoparticles conjugated to purified sulphathiazole antise-
rum onto sample port “S” of the device, leads to rapidly wet through of the conjugate
pad, solubilizes the gold-conjugated antiserum. The gold nanoparticle-conjugate
from conjugation pad migrates down to the nitrocellulose membrane by capillary
action. Control experiments made with buffer or honey without sulphathiazole dis-
play two red lines as “C” line and the test area “T” line indicating a negative assay,
whereas honey samples containing sulphathiazole yield a bright red line at the con-
trol area “C” line without any change at the test line “T” line showing the positive
test. The intensity of the test line is inversely correlated to the concentration of sul-
phathiazole present in the sample. The developed assay is showing a fascinating
rapid detection nanobiosensor with a limit of detection of 10 ng and detection time
of 10 min (Guillén et al. 2011).
54 A.K. Srivastava et al.

Fig. 3.4  Lateral Flow Immunochromatographical Assay (LFIA) is used for the detection of sul-
phonamides as contaminant in the honey sample. The single antigen directed immunoassay based
device constructed on nitrocellulose membrane of 15 μm, the protein hapten conjugate OVA-S2
was printed at test line “T”, while goat anti-rabbit antibody at control line “C”; the gold nanopar-
ticle conjugated sulphathiazole antiserum is adsorbed on the conjugate pad. The sample containing
sulphathiazole after passing through sample pad binds with the conjugates in conjugate pad and
shows only red color on “C” line, whereas control without sample passes through conjugate pad
and develop red color at both the “C” and “T” line, respectively

The nanofunctionalization apprach gives the flexibility to coat the desirable ana-
lyte over the such as a glassy carbon electrode modified with gold nanoparticles and
used for the quantitation and sensig of butylated hydroxyanisole, butylated hydroxy-
toluene and butylated hydroquinone by linear sweep voltammetry with detection
limit of 0.039 gmL−1, 0.080 gmL−1 and 0.079 gmL−1 respectively (X.  Lin et  al.
2013b). Zearalenone, is an estrogenic mycotoxin produced by Fusarium species,
induce the accumulation of high levels of estrogen in animals and, thus give harmful
side effects associated with the reproductive system. To meet the early detection one
chemiluminescence immunoassay developed by replacing streptavidin−HRP with
streptavidin−HRP−gold nanoparticles (Wang et al. 2013).
Nanostructures with chemical entity used for linking the substrate with enzymes
and other biological elements. Here, the xanthine oxidase enzyme specific to sub-
strate xanthine was immobilized covalently onto chitosan bound gold-coated iron
nanoparticles, the whole component electrodeposited on the surface of pencil
3  Nanosensors for Food and Agriculture 55

graphite electrode to construct a working electrode. By considering Ag/AgCl as

reference and Pt as auxiliary electrode electrochemical detection of the xanthine has
been done with the limit of detection of 0.1 μM (Devi et al. 2013).
Aflatoxin M1, a hydroxylated metabolite of aflatoxin B1, is often found in milk
from animals fed with aflatoxin B1 contaminated feeds, several qualitative and quan-
titative methods have been developed to detect Aflatoxin M1 in milk and other dairy
product. Generally, Dynamic light scattering used to measure the hydrodynamic
diameter of micro and nanoparticles dispersed in the particular solvent. In the
approach, gold nanoparticles labeled with the conjugate of Aflatoxin M1 and bovine
serum albumin with surface lysine residues, and the anti-AFM antibody linked on the
surface of magnetic beads by the oriented coupling effect of recombinant protein
G. After incubation, the bulk solution was separated from the magnetic beads by a
magnet and directly transferred into a cuvette for Dynamic light scattering analysis.
The Dynamic light scattering intensity of nanoprobe in bulk solution is positively
proportional to the concentration of Aflatoxin M1 in a sample solution with the lower
possible measurement limit of 27.5 ngL−1 (Zhang et al. 2013b). A Sensitive and rapid
immuno-dipstick colloidal gold-antibody probe developed for the detection of vita-
min B12 in various food samples. The optimized concentration of BSA – vitamin
B12 was immobilized on the surface of nitrocellulose membrane was dipped in an
optimized concentration of vitamin B12 IgY antibodies labeled with gold nanopar-
ticles. The intensity of color development was inversely proportional to the vitamin
B12 concentration upto detection limit of 1 ng mL−1 (Selvakumar et al. 2013).
Carbon nanotubes exhibit the enormous hope for generating nanosensors and
nanobiosensors for uncountable applications and revolutionizes the area of nanobio-
sensor technology with properties such as tiny size, high strength, high electrical and
thermal conductivity, and high specific surface area (lijima 1991).
­Quinoxaline-­2-­carboxylic acid is the marker residues of Carbadox, which is constitu-
ent of food as additives in pork, chicken and fishes having strong mutagenic and car-
cinogenic effects (Vontorkov and Cihák 1983). Consequently approach to detect the
trace level of Quinoxaline-2-carboxylic acid, multi-walled carbon nanotubes func-
tionalized with chitosan fabricated on glassy carbon electrode. Chitosan is a cationic
biopolymer with efficient film-forming ability, high mechanical strength, adhesion,
and biocompatibility used for chemical modification of electrodes. Sol–gel molecu-
larly imprinted polymer film used to coat the surface possessing excellent permeabil-
ity and uniform porosity and serve as recognition element (Tkac et  al. 2007). The
constructed electrode demonstrated as reproducible and reliable electrochemical sen-
sor for accurate quantification of Quinoxaline-2-carboxylic acid at trace levels in meat
samples with a low detection limit of 4.4 × 10−7 molL−1(Y. K. Yang et al. 2013b).
In another approach single-walled carbon nanotube has been used for detection
of D-Fructose, which is an important sugar and low-cost sweetener in fruit juices,
honey, soft and energy drinks; require easy and rapid monitoring during the biopro-
cessing and quality control (Stredansky et  al. 1999). An immobilized Fructose
dehydrogenase enzyme based biosensor developed by using osmium redox polymer
as redox mediator, shuttle the electrons between the immobilized Fructose dehydro-
genase enzyme and the single-walled carbon nanotube pasted on the working
56 A.K. Srivastava et al.

e­ lectrode. The Enzyme entrapped into the paste by using poly (ethylene glycol)
glycidyl ether as a cross-linking agent. The optimized biosensor required only five
unit of enzyme and kept the 80% of its initial sensitivity after 4 months. The biosen-
sor having a detection limit for fructose to estimate 1 μM with a high sensitivity,
good reproducibility and a fast response time of 4 s (Antiochia et  al. 2013).
Additionally, Sudan I as the red-orange color dye used in chili powder as a coloring
agent is prohibited due to carcinogenic potential (Puoci et al. 2005). A sensitive and
convenient method for the determination of Sudan I developed by multi-wall carbon
nanotube thin film-modified electrode. Enhancement of electrochemical oxidation
on the electrode surface by Sudan I dye was determined by an electrochemical
method with the limit of detection 5.0 μgL−1 (Gan et al. 2008).

3.8.2  Detection of Foodborne Pathogens and Microbial Load

The presence of pathogenic microorganisms in the foodstuff is the serious concern

of food industry. The failure or minor delay in the detection of contaminating patho-
gen leads to spoiling of the food and fatal health issues. The real-time detection of
the pathogen is a prerequisite for food safety and quality management. The recent
advancement in the sensing technology provided a platform to detect some micro-
bial contamination, chemicals, and toxins in specific, sensitive and in less time. The
food borne pathogens species such as Campylobacter spp., Salmonella spp., Listeria
monocytogenes, and Escherichia coli O157:H7 have been found to be responsible
for the majority of food-borne outbreaks (Velusamy et al. 2010). Here in this sec-
tion, we are elaborating the nanosensors and nanobiosensors based approaches to
detect some pathogens in real food samples which are listed in the Table 3.1.
Brucellosis is a global zoonotic infectious disease caused by Brucella spp. in
cattle. The disease transmits to humans through consumption of unpasteurized dairy
products and direct contact with afflicted animals. Antigen tagged fluorescent silica
nano-probes utilized to detect Brucella IgG antibodies in milk samples from afflicted
animals. The sensing is accurate and repeatable, with high specificity and sensitiv-
ity; require a small amount of sample, i.e., 50 μL and need 10  min (Vyas et  al.
2015). In another approach, Liposome-amplified plasmonic immunoassay is over-
coming the requirement of sophisticated spectroscopic and imaging instrument and
protocol. This method is ELISA inspired detection approach even though the limit
of detection ranging from the femtomolar (10−15 M) to attomolar (10−18 M) is still
consistent. The dependency of the optical property of plasmonic nanostructures on
their size, shape, distribution and composition has been exploited here to demon-
strate an enzyme-less, naked-eye detection of a single-digit pathogen using plas-
monic colorimetry of gold nanoparticles combined with signal amplification via
cysteine loaded liposomes. The immunocomplex is directly labeled with cysteine-­
loaded nanoliposomes using a biotin − streptavidin linkage. Gold nanoparticle solu-
tion is then added to the assay, followed by the addition of a hydrolytic agent or a
buffered surfactant such as Tween 20 in phosphate buffer saline. In the presence of
a pathogen, the surfactant induces immediate hydrolysis of the liposomes, leading
Table 3.1  Summarizes the various pathogens and contaminant interferes with production, processing and storage and quality of the food products
Target element Nanomaterial Detection method Limit of detection References
Pathogens:
Listeria monocytogenes Thiol – gold NPs-PCR product Colorimetric 0.015 and 0.013 ng/mL Devi et al. (2013); Fu
and Salmonella enterica et al. (2013)
Brucella spp Fluorescent silica nanoparticle Fluorescence 50 μL Vyas et al. (2015)
E. coll, Salmonella spp, Cysteine-loaded nanoliposomes Liposome-amplified 6.7 attomolar Bui et al. (2015)
and Listeria and AuNPs Plasmonic immunoassay
(LAPIA)
S. aureus, V. Multicolor Luminescence bioassay 25 cfu mL−1 10 cfu mL−1 Wu et al. (2014)
parahemolyticus, UCNPs-MNPs-­aptamers 15 cfu mL−1
SAyphimurium
Escherichia coll 0157.H7 Fluorescent-silica nanoparticles Fluorescence 1000 times Zhao et al. (2004)
3  Nanosensors for Food and Agriculture

S. typhimurium AuNPs-GBP-ProA protein Surface Plasmon tenfold Ko et al. (2009)

Resonance (spr)
immunosensors
Escherichia coll Multi-walled carbon nanotubes Electrochemical 4.57 × 103 cfu/ml and Dou et al. (2013)
0157:H7and (MWCNTs)/sodium alginate immunosensor 3.27 × 103 cfu/ml
Enterobacter sakazakli (SA)/carboxymethyl chitosan
composite films
Salmonella Paratyphi A Single-walled carbon nanotubes Chemiluminescence 103 cfu/mL Yang et al. (2013a); Yang
(SWNTs) and DNAzyme- Apt22 et al. (2013b)
Food Contaminants
kanamycin mono sulfate, AuNPs Strong local surface 1 × 10−9M Zhang et al. (2013a);
neomycin sulfate, Plasmon resonance Zhang et al. (2013b)
streptomycin sulfate and
bleomycin sulfate
neomycin, kanamycin, b/saniline-cross-linked AuNP Surface Plasmon 2.00 ± 0.21 pM, 1.00 + Frasconi et al. (2010)
and streptomycin resonance 0.10 pM, and 200 ± 30
fM
57

(continued)
Table 3.1 (continued)
58

Target element Nanomaterial Detection method Limit of detection References

Nitrite Hyperbranched Fluorescence quenching 100 nM Chen et al. (2016)
polyethyleneimine
scaffolds-AgNPs
Ochratoxin A Au nanoparticles Enhanced SPR 60 pgmL1 Evtugyn et al. (2013)
Quinoxaline-2-­carboxylic MIP/sol-gel/MWNTs-CS/GCE Electrochemical 4.4 × 10−7 molL−1 Yang et al. (2013a); Yang
acid detection et al. (2013b)
D-Fructose FDH- single-walled carbon Electrochemical 1 μM Peris and Escuder-­Gilabert
nanotube paste electrode detection (2013)
Sudan I Multi-wall carbon nanotube thin Electrochemical 5.0 μgL−1 Gan et al. (2008)
film-modified electrode Detection
Butylated AuNPs/GCE Linear sweep 0.039, 0.080 and 0.079 Lin et al. (2013a);
hydroxyanisole, butylated voltammetry μg/mL Lin et al. (2013b)
hydrox ytoluene and
butylated hydroquinone
Sulfathiazole OVA-hapten conjugate and Lateral flow 15 ng/g Guillén et al. (2011)
AuNPs immunoassay
hROS AuNPs Fluorescence-logic gate 5 μM Hu et al. (2014)
integration
Xanthine XOD/CHIT/Fe-NPs@Au/PGE Electrochemical 0.1 μM Devi et al. (2013)
Detection
Aflatoxin M1 DLS-­superparamagnetic Dynamic Light 37.7 ng L−1 in buffer Zhang et al. (2013a);
beads-AuNPs Scattering solution and Zhang et al. (2013b)
Vitamin B12 AuNPs immunodipstick 1 ng/mL Selvakumar et al. (2013)
The table represents the detection application, nanomaterial used for the construction of nanosensor, mode of detection, the limit of detection and the references
(left to right). The abbreviation used in the table AuNPs (gold nanoparticle), DLS (Dynamic light scattering), GCE (glassy carbon electrode) and UCNPs
(upconversion nanoparticles)
A.K. Srivastava et al.
3  Nanosensors for Food and Agriculture 59

to the release of encapsulated cysteine molecules. Due to their high affinity to the
gold surface, the thiol groups of cysteine will bind to the nanoparticles while the
free amine and carboxyl groups bind to other cysteine molecules via intermolecular
hydrogen bonding, thus By playing the role of a cross-linker, cysteine induces rapid
aggregation of a gold nanoparticle. Since assembled nanoparticles exhibit light
absorbance at higher wavelengths, the aggregation is reflected by a rapid and highly
distinctive color shift of the solution from red (650 nm) to dark-blue (520 nm),
which allows naked-eye assessment. This assay has been done to confirm the pres-
ence of E. coli, Salmonella, and Listeria in milk, ground beef, and apple juice with
the limit of detection of 6.7 attomolar (Bui et al. 2015).
Alternatively, Luminescence bioassay was demonstrated for simultaneous detec-
tion of three foodborne pathogenic bacteria utilizing three types of PAA-modified
NaYF4: Yb,Tm multicolor upconversion nanoparticles served as signal probes, with
independent fluorescence emission peaks. These multicolor upconversion nanopar-
ticles conjugated with the amino-modified aptamers specific to S. aureus, V. parahe-
molyticus, and S.typhimurium by a condensation reaction. Moreover, Magnetic
nanoparticles were conjugated with cDNA complementary to individual aptamers.
Aptamer and cDNA hybridization leads to the formation of a complex of upconver-
sion nanoparticles and magnetic nanoparticles, as signal probe showing maximum
luminescence at 477 nm as a negative control in the absence of bacteria. The subse-
quent reduction in the fluorescence on the addition of bacteria correlated with the
bacterial load. This biosensing strategy is utilizing multicolor upconversion
nanoparticles in conjunction with magnetic nanoparticle and aptamers as analytical
methods for detection of pathogenic bacteria S. aureus, V. parahemolyticus, and S.
typhimurium in the minimum count of 25, 10, and 15 CFU mL−1 (Wu et al. 2014).
Efficient immobilization of antibodies on a sensing platform and sensitivity
enhancement are crucial in designing surface plasmon resonance based immune
sensors. Colloidal gold nanoparticles directly assembled onto a surface of the gold
chip with 2-aminoethanethiol which enhances the sensitivity and gives a label-free
detection system. A novel fusion protein was constructed by genetically fusing gold
binding polypeptides to protein A as a crosslinker for efficient immobilization of
antibodies. The GBP-ProA protein directly immobilized onto both bare and gold
nanoparticle assembled on surface plasmon resonance sensor chip surfaces via the
GBP portion, followed by the oriented binding of the antibody. This signal enhance-
ment in the gold nanoparticle assembled chip causes a ten-fold in detection of S.
typhimurium compared to the bare one (Ko et al. 2009). Escherichia coli O157: H7
is one of the important agents of food-borne diseases, Therefore, a simple, quick,
and precise detection of E. coli O157: H7 is crucial for minimizing or eliminating
potential infections. In this particular sensing technique, fluorescent Tris(2,2-­
bipyridyl) dichlororuthenium(II) hexahydrate dye-doped silica nanoparticles used
for detection of E.coli and showing 1000 times enhanced fluorescence signal in
comparison of pure dye. This approach connected with the fact that each mesopo-
rous silica nanovesicles can encapsulate thousands of organic dye molecules and
capable of tagging the bacterium (Zhao et al. 2004).
60 A.K. Srivastava et al.

Gold nanoparticles used for sensitive colorimetric detection of two foods borne
pathogenic bacteria Listeria monocytogenes and Salmonella enteric using poly-
merase chain reaction based amplification of bacterial genes to directly distin-
guished by naked eyes. The thiol labeled PCR primer gives PCR products with
thiol-label, which upon mixing with unmodified gold nanoparticles solution results
in the formation of gold nanoparticle – PCR products, show that the target patho-
genic bacteria sample could be specifically recognized and detected (Fu et al. 2013).
Alternatively, in another approach, a polyclonal antibody coated colloidal gold par-
ticles used to develop a rapid and sensitive sandwich immunochromatographic
assay based device can detect staphylococcal enterotoxin B contamination in food
sample with the limit of detection of 1 ng/mL within duration of 5 min. In sampling
process in LFA-device, the toxin initially reacted with polyclonal antibody coated
colloidal gold particles and then reacted with the fixed Pab on the membrane gives
a red line at the detection zone that correlated with the amount of Staphylococcal
enterotoxin B (Rong-Hwa et al. 2010).
Salmonellosis with the symptom of paratyphoid a fever is one most frequently
reported bacterial foodborne illnesses (Maskey et al. 2006). The rapid and reliable
method to overcome the laboratory based culture detection method imposed by non-­
covalent self-assembly of single-walled carbon nanotubes and DNAzyme-labeled
aptamer as detection probes. Aptamer Apt22 with the lowest Kd value of 47 ± 3 nM
developed by an iterative approach called Systematic Evolution of Ligands by
Exponential Enrichment (SELEX). Carbon nanotubes possess the ability to protect
ssDNA by π-stacking interactions between the nucleotide bases (Tuerk and Gold
1990). Binding of P0 to SWNT gives a stable P0/SWNTs complex, interfere with
the formation of free hemin-containing active DNAzyme and the system do not
generate any detection signals. Addition of the target bacteria and hemin, will spe-
cifically bind to the probe and compete with the individual SWNTs, tends P0 to be
away from SWNTs and leads to formation of hemin/G-quadruplex horseradish
peroxidase-mimicking DNAzyme which in turn act as a catalyst for the generation
of chemiluminescence (λ = 420 nm) through the oxidation of luminol by H2O2 with
detection limit of 103 CFU/mL (M. Yang et al. 2013a).
An electrochemical immunosensor was constructed to detect the two pathogenic
bacteria Escherichia coli O157: H7 and Enterobacter sakazakii. The fabrication of
the sensor was done by screen-printed carbon arrays constitute four carbon working
electrode, an integrated carbon counter electrodes, and an integrated Ag/AgCl refer-
ence electrode. Multi-walled carbon nanotubes/sodium alginate/carboxymethyl chi-
tosan composite films were coated on all the working electrodes to enhance the
sensitization of the electrode. Horseradish peroxidases labeled antibodies of two
bacteria were immobilize on the different working electrode. The results demon-
strate the LOD of 4.57 × 103 CFU/mL and 3.27 × 103 CFU/mL for E.coli O157: H7
and E. sakazakii respectively (Dou et al. 2013).
3  Nanosensors for Food and Agriculture 61

3.9  A
 pplication of Nanosensors and Nanobiosensors
in Agriculture

The longstanding application of nanosensors and nanobiosensors is to estimate the

presence and concentration of toxic chemicals in soil and wastewater. The net land
contaminant such as pesticides, herbicides, heavy metals and residues of fertilizers
are accumulating and causing a decline in the resources and agricultural productivity.
As discussed in the previous sections that nanomaterials are being used in the area of
nanosensing and new strategies are revolutionizing the agriculture and food sector.
The nanosensors are being used for quantitative and qualitative suitability of the
farming soil in the context of soil fertility and microorganism present. Among the
plethora of Nanosensors and nanobiosensors in agriculture (Table 3.2), few are being
elaborated in the framework of the utilized nanostructure such as gold nanoparticle,
the magnetic nanoparticle, quantum dots and carbon nanomaterial. The metallic
nanoparticle pursues enhanced optical property at nanosize confinement and heavily
dependent on the size and morphology. Here, the colloidal gold nanoparticles of
40 nm size are conjugated with the micron-sized polymer by modifying the surface
with 2-aminoethanthiol. This modification allows the controlled deposition of gold
nanoparticle on functionalized polymer. The micron-size polymer has been used
synthesized by precipitation polymerization reaction using methacrylic acid and eth-
ylene glycol dimethacrylate as the co-monomer precursor in acetonitrile. The
aptamer specific to Malathion was thiolated at the terminal and attached to the gold
nanoparticle surface by thiol-gold chemistry. The micron-sized aptamer containing
gold nanoparticle serves as an apta-sensing microsphere, specifically, interact and
bind with the malathion and being detected by surface enhanced Raman spectros-
copy with the sensitivity of detection of 3.3 μg/mL. Malathion is organophosphate
insecticide frequently used in the agriculture and to improve crop production. The
surface enhanced Raman spectroscopy based nanobiosensor developed could be pre-
ferred over classical technique such as mass spectrometry and HPLC because of
quick and sensitive measurement (Barahona et al. 2013).
In another work, the hollow, 50 nm gold nanoparticles are being synthesized and
the surface functionalized with L-cysteine. The cysteine assembles the chitosan
electrostatically on the surface of hollow gold nanoparticle through Au-S chemistry.
Moreover, the whole conjugated are deposited on a glassy carbon electrode. The
assembly of enzyme Acetylcholinesterase over the hollow gold nanoparticle is the
crucial step in the process; which is covalently attach to the hollow gold nanoparti-
cle surface via – COOH group incorporated by L-cysteine. The nanobiosensor con-
structed by the subsequent assembly on working electrode and the immobilized
enzyme AChE interact with the substrate acetylthiocholine chloride to produce the
electroactive compound thiocholine, the inhibition of the enzyme was measured by
the oxidation current of thiocholine in the presence of chlorpyrifos and carbofuran.
Linear relationships between inhibition percentage and the concentration of chlor-
pyrifos and carbofuran were used for quantitation with the detection limits of 0.06
μg/dm3 for chlorpyrifos and 0.08 μg/dm3 for carbofuran. The chlorpyrifos and
 62

Table 3.2  Summarizes the various contaminants such as residual pesticides and a heavy metal ion interferes with soil fertility, crop production and harvesting,
processing, storage and quality of the agriculture products
Limit of
Target element Nanomaterial Detection method detection References
Malathion Aptamer-polymeric SERS 3.3 μg/mL Barahona et al. (2013)
microsphere-AuNPs
Chlorpyrifos and carbofuran AChE/L-cys/HGNs/Chits/GCE Electrochemical 0.06 μg/dm3 and Sun et al. (2013)
0.08 μg/dm3
Carbofuran and triazophos Lateral-flow Immunochromatographic Optical 32 μg/L and 4 Guo et al. (2009)
μg/L
Pinacolyl methylphosphonate, Eu(lll)-AuNPs Surface enhanced fluorescence 1 μmol/dm3 Dasary et al. (2008)
methylphosphonic acid,
glyphosate
N-Methyl carbamate AChE-AuNPs SPR 7 pM and 12 pM Huang et al. (2009)
Parathion ZrO2/Au nano-composite Square wave voltammetry 3 ng/mL Wang and Li (2008)
Methyl parathion AChE/F-ZnSe/GR-Chi/GCE Chronoamperometry 0.2 nM Dong et al. (2013)
Methyl parathion BSA-CdTe bioconjugate Fluoroimmunoassay 0.1 ng mL−1 Chouhan et al. (2010)
Deltamethrin CdTe-SiO2-MIPs Fluorescence quenching 0.16 μgmL−1 Ge et al. (2011)
Paraxon AChE/CNT-NH2/GC electrode Electrochemical 0.08 nM Yu et al. (2015)
Mg2+ Ca2+,Sr2+ Ba2+ bis-aniline-bridged AuNPs composites SPR Femto molar Ben-Amram et al.
(2012)
A.K. Srivastava et al.
Concanavalin A GO/DexP-AuNPs SPR 0.39 μgmL−1 Huang et al. (2013)
Dichlorvos MWCNTs/ALB)n/GCE Electrochemical 0.68 ± 0.076 Yan et al. (2013)
μg/L
Acetamiprid Aptamer-AuNPs Optical 0.1 ppm Weerathunge et al.
(2014)
Acetamiprid AuNPs-multiwall carbon nanotube-­ Impedimetric 1.7 × 10−14 mol/ Jampilek and Kral’ova
reduced graphene oxide nanoribbon dm3 (2015)
composites
Malathion, Chlorpyrifos, AChE/Chit-PB-MWNTs-HGNs/Au Electrochemical Nano molar Zhai et al. (2013)
Monocrotophos and Carbofuran range
Br− MWNTs-chitosan-GCE Electrochemical 9.6 × 10−8 Zeng et al. (2005)
μgmL−1
Carbofuran Multiwall carbon nanotubes-graphene Electrochemical immunoassay 0.03 ng/mL Zhu et al. (2013)
3  Nanosensors for Food and Agriculture

sheets-ethyleneimine polymer-Au
nanocomposites
The table represents the detection application, nanomaterial used for the construction of nanosensor, mode of detection, the limit of detection and the references
(left to right). The abbreviation used in the table AuNPs (gold nanoparticle), GCE (glassy carbon electrode), AchE (acetylcholinesterase), SPR (surface plasmon
resonance), MWNT (multi walled carbon nanotubes) and GO (graphene oxides)
63
64 A.K. Srivastava et al.

c­ arbofuran are organophosphate and carbamate insecticide used in the agriculture

field, the monitoring of trace amount of above pesticide is crucial for public health
and security (Sun et al. 2013). The strategy represents the morphological change in
the gold nanoparticle to hollow gold nanoparticle could significantly improve elec-
tron transfer and decrease the over-potential of substrate oxidation better than other
biosensors.
The gold nanoparticles labeled antibody-based lateral-flow immunochromato-
graphic was constructed for simultaneous detection of pesticides as carbofuran and
triazophos. Bispecific monoclonal antibody specific to both the pesticides imprinted
on one nitrocellulose strip, parallel to this gold-labeled monospecific monoclonal
antibody specific to carbofuran and triazophos separately immobilized on conjugate
pads of the another strip. The presence of carbofuran and triazophos can be visual-
ized even in less concentration of 32 and 4 μg/L respectively, representing the
method for rapid identification and quantification of pesticide as a contaminant
(Guo et al. 2009).
The surface enhanced fluorescence is highly depending on the local electromag-
netic environment of the fluorophore. Surface enhanced fluorescence obtained near
the nanostructured metal is concentrating effect of the incident light into local elec-
tromagnetic ‘hot spots,’ on the surface of fluorophores; alternatively, metal nano-
structures could alter radiative and non-radiative decay rates ultimately changing
both fluorescence lifetime and quantum yield. The correlation observed in the strat-
egy where gold nanoparticle-based surface-enhanced fluorescence spectroscopy for
quick screening of organophosphorus agents such as pinacolyl methylphosphonate,
methylphosphonic acid, glyphosate with high sensitivity of 1 μmol/dm3. The Eu(III)
ions within the proximity of gold nanoparticle experience strong electromagnetic
field and produce large fluorescence enhancement natively, but organophosphates
preferably bind with Eu(III) ions induce dissociation from gold nanoparticle surface
altered the fluorescence intensity which is correlated with the quantity of organo-
phosphates (Dasary et al. 2008).
While increasing sensitivity and accessibility of the metallic nanoparticle, here
single detection platform has been used for detection of more than one substitute of
the single pesticide. The N-Methyl Carbamate as insecticides targets AChE, even
though it is widely used agriculture. Here Two carbamate inhibitors with different
ether linkages and the terminal lipoate were synthesized and labelled with gold
nanoparticles, specific interactions between the gold nanoparticle labelled carba-
mate inhibitors such as ALC1 and ALC2 were immobilized AChE on sensor chip
surface by surface Plasmon resonance with the possible limit of detection of 7 pM
and 12 pM (Huang et al. 2009). Apart from gold nanoparticles, other metal nanopar-
ticles are also known for the construction of Nanosensors and nanobiosensors. Here,
Zirconium oxide nanoparticle having a high affinity toward the phosphate group on
organophosphate provides a basis for construction of ZrO2/Au nanocomposite film
electrode. Which can measure the presence of parathion with a limit of detection of
3 ng/mL by square wave voltammetry (M. Wang and Li 2008).
Quantum dots are nanocrystals with the unique property of high photo-stability,
full wavelength absorbance, fluorescence spectra and controlled fluorescence
­emission. These properties of QDs are making it useful for the sensing and imaging
3  Nanosensors for Food and Agriculture 65

applications. These quantum dots are surface functionalized with the capping agent
like mercaptoacetic acid or mercaptopropionic acid to provide the carboxylic func-
tional group for the conjugation and make it water soluble for the further applica-
tions (Ruedas-Rama et al. 2011). The Acetylcholine esterase with Mercaptophenyl
boronic acid functionalized ZnSe quantum dots electrostatically adhered on gra-
phene–chitosan nanocomposites cast on a glassy carbon electrode was used for the
quantitative electrochemical detection of methyl parathion with the limit of detec-
tion of 0.2 nM. Here, mercaptophenyl boronic acid derivatives have been used for
its inherent capability to recognize cis-diol configuration in saccharides and to form
a covalent bond via the formation of cyclic esters and used here for the fabrication
purpose. The AChE/F–ZnSe/GR–Chi/GCE was constructed and used to detect
methyl parathion by chronoamperometric measurement in the presence of ATCl
substrate before after inhibition with methyl parathion of different concentrations.
The observed oxidation current variation could easily correlate with the concentra-
tion of methyl parathion. This method introduced improved electron transfer rate on
the electrode interface with enhanced immobilization of enzyme for methyl para-
thion detection (Dong et al. 2013).
Moreover, intrinsic fluorescence property of quantum dots was utilized for sensi-
tive detection of methyl parathion at picogramme level by using the strategy of
competitive binding between free methyl parathion and CdTe quantum dots biocon-
jugate methyl parathion immobilized anti-MP IgY antibodies and was observed in
a flow-injection system. Here, the binding of methyl parathion-Bovine Serum
Albumin–cadmium tellurium quantum dots bioconjugate depends on the antibody
remaining after the binding of free methyl parathion in the immune-reactor column.
The higher the parathion methyl concentration, lower will be the binding of methyl
parathion-Bovine Serum Albumin–cadmium tellurium quantum dots bioconjugate
and elute out of the column will have the maximum fluorescence signal. Thus, the
fluorescence intensity of methyl parathion-Bovine Serum Albumin–cadmium tel-
lurium quantum dots bioconjugate eluted from the column be directly proportional
to the free methyl parathion concentration. This fluoroimmunoassay technique
gives a sensitivity of 0.1 ng mL−1 concentration within the time range of 10–15 min
(Chouhan et al. 2010). In agricultural practices, deltamethrin (DM) is used for the
control of a wide range of pest but have consequences such as high toxicity, long
persistence, hard to degrade and severe health issues. Thus, the tool for rapid and
sensitive detection of deltamethrin food and vegetable samples was developed by
utilizing highly fluorescent silica nanospheres embedded cadmium tellurium quan-
tum dots with a limit of detection of 0.16 μgmL−1. In this particular approach, the
intensity of fluorescence quenching of CdTe–SiO2-MIPs was correlated with the
DM concentration (Ge et al. 2011).
In addition to several applications of metal nanoparticle based Nanosensors and
nanobiosensors, the Graphene oxide and functionalized carbon nanotubes control
the efficient immobilization of entities on the surface which opens the door for con-
struction of enzyme-based biosensors. With the advantage of guiding the protein
orientation by reducing randomly bounded proteins to improve the sensitivity; the
close confinement leads to efficient electron transfer between enzyme and electrode
66 A.K. Srivastava et al.

and simplifying the immobilization steps, thus improve the reproducibility and
operability. Amino-functionalized carbon nanotubes control the effective immobili-
zation of AChE onto the surface of the glassy carbon electrode and use for develop-
ment of a very delicate organophosphorus pesticide biosensor electrode. These
electrodes have been successfully employed for detecting paraoxon and other pesti-
cides from vegetable samples with a limit of detection of 0.08 nM (Yu et al. 2015).
The compatibility of carbon nanotubes and gold nanoparticles provide a refer-
ence for the simultaneous use of both the nanostructure in the construction of
Nanosensors and nanobiosensors. In the method, the gold nanoparticles functional-
ized with electro polymerizable thioaniline were electropolymerized on glass sur-
faces along with the alkaline-earth metal ions Mg2+, Ca2+, Sr2+ or Ba2+, to yield the
respective ion-imprinted bis-aniline-bridged gold nanoparticle composites. After
removal of the ion from the composite, specific imprinted ion recognition sites were
generated. Selective binding of the individual ions to the imprinted sites leads to the
development of highly sensitive sensing method that can detect the ions even in
femtomolar concentration (Ben-Amram et al. 2012).
Concanavalin A is a plant derived lectin, specifically bind with the plasma mem-
brane receptors containing mannose and glucose residues, and affect the signaling
to promote proliferation of the cells. The method to detect Concanavalin A, gra-
phene oxide deposited on the gold sensor film followed by assembly of phenoxy-­
derivatized dextran over the graphene oxide-modified gold sensor chip surface
through π–π interaction. The prepared graphene oxide/ phenoxy derivatized dextran
sense interface and specifically captured Concanavalin A which could further react
with phenoxy-derivatized dextran-gold nanoparticle through the specific interaction
between Concanavalin A and phenoxy-derivatized dextran, forming a sandwich
configuration and detected by surface plasmon resonance signal with the lesser con-
centration of 0.39 μgmL−1. This method provides a designed surface plasmon sen-
sor having high sensitivity, good selectivity and reproducibility for Concanavalin A
detection (C. F. Huang et al. 2013).
With the progress in construction of carbon nanotube based nanosensors, here
self-assembled monolayers of single-walled carbon nanotubes fabricated by thiol
labeled oligonucleotide on gold nanoparticle was utilized to prepare nanometer size
polyaniline matrix for acetylcholinesterase enzyme immobilization. The electro-
chemical biosensor constructed detect pesticides methyl parathion and chlorpyrifos
up to limit of detection 1 × 10−12 M (Viswanathan et al. 2009). In another strategy
multiwall carbon nanotubes, chitosan, and AChE liposomes bioreactor layers were
combined to construct a multilayer films on glass electrode and used to detect
organophosphate such as dichlorvos up to detection limit of 0.68 ± 0.076 μg/L by
electrochemical measurement (Yan et al. 2013).
Acetamiprid is neonicotinoid-based pesticide acts as a neurotoxin by causing
agonistic effects against nicotinic acetylcholine receptors (Shi et al. 2013). Aptamer-­
controlled reversible inhibition of Gold nanozyme (nanoparticles enzyme mimick-
ing) activity for acetamiprid sensing has been utilized for the sensing. The
peroxidase-like activity of bare gold nanoparticle to oxidize colorless TMB into a
purplish-blue product and specificity of the acetamiprid-specific S-18 aptamer to
3  Nanosensors for Food and Agriculture 67

detect neurotoxic pesticide in a highly rapid, accurate and sensitive manner, allowed
the detection of 0.1 ppm acetamiprid within the assay time of 10 min (Weerathunge
et al. 2014). Moreover, in alternative strategy gold nanoparticles decorated multi-
wall carbon nanotube-reduced graphene oxide nanoribbon composites used as the
support for aptamer immobilization that enables to develop an ultrasensitive label-­
free electrochemical impedimetric aptasensor for acetamiprid detection. The varia-
tion of electron transfer resistance represents the acetamiprid-aptamer complex at
the modified electrode surface in the linear pattern could be correlated with the
acetamiprid concentration even with an extremely low detection limit of 1.7^10−14
mol/dm3 (Jampilek and Kral’ova 2015).
Chitosan–Prussian Blue–multiwall carbon nanotubes-hollow gold nanospheres
film was deposited on the gold electrode surface utilizing electrodeposition method.
The acetylcholinesterase and Nafion were modified on the film to prepare an AChE
biosensor. Prussian blue oxidize thiocholine, which is the product of the hydrolysis
of acetylthiocholine catalyzed by AChE (Sun and Wang 2010). Integration of mul-
tiwall carbon nanotubes and hollow gold nanospheres into Chitosan Prussian blue
hybrid film evoke electron transfer reaction, raised the electrochemical signal and
improved the microarchitecture of the surface gives electrode as a biosensor to
sense pesticides such as malathion, chlorpyrifos, monocrotophos and carbofuran
(Zhai et al. 2013).
Industrial wastes are the credible source of Bromine ion which contaminates the
environmental water and at elevated concentration pose the adverse side-effect. In
turn, a multiwall carbon nanotube – chitosan modified glassy carbon electrode was
utilized for sensitive cathodic stripping voltammetric measurements of bromide
(Br−) with the limit of detection of 9.6 × 10−8 μgmL−1 (Zeng et al. 2005).
Carbofuran (2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate) a
broad-spectrum Insecticide widely used in agriculture was quantitated by an ampero-
metric immunosensor. The monoclonal antibody specific to carbofuran was cova-
lently immobilized on the gold nanoparticles using glutathione. Multiwall carbon
nanotubes and graphene sheet-polyethyleneimine polymer-gold nanocomposites
modified onto the surface of a glass carbon electrode via self-assembly. The modified
graphene sheet-polyethyleneimine polymer-gold electrode coated with gold nanopar-
ticles-antibody conjugate which has been detected by the simultaneous Amperometric-
immunosensing method with the limit of detection of 0.03 ng/mL. The correlated
electrochemical and immunological strategy gives a high specificity, good reproduc-
ibility, acceptable stability and regeneration capability (Zhu et al. 2013).

3.10  Nanosensors for Intelligent Food Packaging

The utilization of nanotechnology in food packaging is one of the promising appli-

cations, where nanoparticle and polymeric nanomaterial is being used to prevent the
spoilage by ceasing the gas and moisture loss and prolonged the self-life of the food
product. Apart from the objective of efficient packaging, the application of the
68 A.K. Srivastava et al.

nanotechnology extended by being integrated with the food during production, pro-
cessing, shipment of food products and storage. Much innovation has been made to
incorporate the Nanosensors and nanobiosensors at the time of packaging that per-
sists with the food stuff and detect the food condition, freshness, and aroma. The
Nanosensors is being integrated into the packaging’s to sense the storage condition
by estimating the physical parameter such as temperature, humidity, pH, oxygen
content, pathogens, toxins and freshness by estimating the fermented byproduct in
the preserved food.
OxyDot® is the commercialized nanosensor is being used to quantitate the dis-
solved oxygen into the packaged food and sealed drink product. The principle
behind oxygen measurement technique is fluorescence intensity and life time
quenching of the metallic-organic fluorescent dye immobilized on the gas perme-
able hydrophobic polymer dot. The whole construct is small diameter dot that just
stacked over the surface of sealed drink bottle or on the wrapper of packaged food
stuff. The excitation wavelength of the dye falls into blue light reason and emit in
the red spectrum. The presence of oxygen in the proximity and high collision
dynamics it withdraws the excited electron of the dye molecule and in turn quenches
the fluorescence and fluorescence lifetime of the dye. The OxyDot proves to be a
reliable, sensitive up to 5% of reading, non-destructive and rapid (less than 0.1 s)
oxygen sensing technique that can measure the oxygen concentration in real time.
The Insignia CO2Detection Pallet Intelligent Labels and SMART DOTS are
designed utilizing a cost effective pigment system that exhibits a quick response to
the CO2 concentration and temperature change. Thus the patented system provides
a smart food labeling technology and ultimately improves the safety and food qual-
ity. Similarly, one another patented product named RipeSense® labels is intelligent
ripeness indicator developed to detect the volatile compound released by the rip-
ened food. The detection output is simply based on the color change of the label
from red to orange and finally into the yellow. The RipeSense labels are used in the
horticulture to detect the aroma and foul smell and provide the information about
the ripening of the fruits.
The time-temperature indication is needed in processing and storage of the tem-
perature sensitivity food stuff or material. The Timestrip Plus®, Timestrip Complete
and 3M MonitorMark are the patented time temperature indicator. The construction
of the indicator strip is done that it consists a combination of sensor and response
element. The sensor system senses the temperature breach and pigment system give
a differential color generation that strongly depends on the change of the tempera-
ture in reference to calibrated temperature point. The Timestrip Plus are manufac-
tured specific to different temperature range start from −20 °C to 86 °F from the
time breach range of 12–48 h. Whereas the Timerstrip Complete equipped with the
intelligent recognition and generated response as white to red on deciding 2 °C
breach otherwise white to blue on ascending 8 °C breach. The 3M MonitorMark
give the similar response in the temperature range of 15–31 °C.
Fresh-Check is another time temperature indicator manufactured by
TEMPTIMES, generally, be used for the health and food stuff to be stored for a long
time. This label based sensor has the potential to withstand long with long shelf life
3  Nanosensors for Food and Agriculture 69

product and gives a visual response after exposure to heat or high temperature. The
smart time Temperature Indicator developed by Vitsab International, coolVu Food
and Innolabel functions on a similar principle and used as an indicator in the refrig-
erated fruits, vegetables and food product.
Recently the Thermochromic inks based colored thermometer labels, and strips
have been developed by Chromatic Technologies, Inc and Matsui International, the
USA for its diverse application in retail food safety and storage.
ToxinGuard is an antibody-based biosensing approach developed by Toxin Alert,
Canada for detection of pathogenic bacteria such as Salmonella sp., Campylobacter
sp., E. coli and Listeria sp. The strategy utilized is the use for pathogen-specific
antibodies in the plastic wrap used for the food packaging, and the accumulation of
the labeled detector antibodies after interaction with the contaminant in the particu-
lar area gives a visible colored indication of the presence of toxin and pathogens.

3.11  Intellectual Property Rights and Recent Patents

Intellectual property rights are the legal rights obtained on creativity or inventions,
which allow the holder to prevent unauthorized open use of their inventions.
Generally, IPRs is broadly demarcated in to two sections; first comprises the prop-
erty, patents, trademarks and industrial design; whereas second domain deal with
the copyright of artistic creatures, literary works, performances and broadcasts
(Bastani and Fernandez 2002). The patent system gives an exclusive flexibility to
defense when any challenge of the ownership has been raised with clear documen-
tary evidences of terms of boundary and area of protection (Hwang et al. 2016). It
also gives the flexibility to make the partners, establishing collaborations and shar-
ing. Trade Related Aspects of Intellectual Property Rights Agreement abbreviated
as TRIPs with in the World Trade Organization having certain framework criteria
and eligibility of issuing the patent rights mentioned in the Article 27 of “Patentable
Subjects Matter”(Kochhar 2008). In more generalized way the criteria’s for patent-
ability are:
1 . Invention must be patentable subject matter
2. It should be Novel
3. Inventive steps; it would be nonobvious
4. Usefulness as for industrial application
The territorial constrain of patents rights make it effective in one country, as the
patent rights issued in Europe would be limited in European countries and not valid
in US. Alternatively, World Intellectual Property Organization manages the interna-
tional patent protection under the Patent Cooperation Treaty system and allows the
protection of intellectual property right in 148 countries around the world (Havas
2014). The United State Patent and Trademark Office (USPTO), European Patent
Office (EPO) and Japan Patent Office (JPO) are the three major organizations pro-
vide the patent right in area of nanotechnology. Taking concern from continuous
70 A.K. Srivastava et al.

inventions and increasing patent in the area of nanotechnology, the world Intellectual
Property Organization specified the class B82, which further divided in to two sub
classes, First; B82B include the nanostructures formed by manipulation of indi-
vidual atoms, molecules, or limited collections of atom or molecules as discrete
units; and second, specific uses or applications of nano structures; measurements or
analysis of nano structures, manufacture or treatment of nano-structures (Keserű
2013). Similarly, The EPO made the classification of the nanotechnological inven-
tions under Y01N, which is further sub categorized in several classes such as Y01N2,
nanobiotechnology or nanomedicine; Y01N4, nanotechnology for information pro-
cessing, storage and transmission; Y01N8, Nanotechnology for material and surface
science; Y01N10, nanotechnology for optics; and Y01N12, nanomagnetics (Ranjan
et al. 2016). The innovation in the area of food and agriculture sector should suffi-
ciently enough for the commercialization of product output. Recently several pat-
ents right has been issue in area of nanosensors have direct applicability in the
detection. The strip based nanosensors has been developed by utilizing the nano-
platform assembly of two different colorimetric nanoparticle linked with the prote-
ase consensus sequence or ester linkage. The protease enzyme present in the milk
product cleaves the amino acid sequence of consensus and because of the enzymatic
activity and plurality of the nanoparticles a visual colour change is generated. The
patented nanosensors approaches have implications in the detection of enzymatic
activity in dairy product for further safety (Troyer et  al. 2016, WO2016018798
(A1)). The another approach the Molecular imprinted conductive polymer and gold
nanoparticle nano-junction has been used for the construction of molecular
imprinted nanosensor device and could be used for the detection of desirable ana-
lytes (Li et al. 2013, US2013092547 (A1)). Many more instances of the recent pat-
ents rights are being mentioned in the Table  3.3; with the respective analyte,
nanostructure has been utilized and the mode of detection. The innovation in the
area of sensors and its commercialization still needed thrust that could be possible
with the flexibility in the academia-industrial participation, amendments in the rule
patents right and ultimately making the smooth patent application process.

3.12  Conclusion

Research activity and innovation in the areas of nanosensors and nanobiosensors

has extraordinary growth in the last one decade. This chapter made an effort to pro-
vide the current trend and innovation in nanosensors and nanobiosensors construc-
tion or designing along with their potential applications in the area of food and
agriculture sector. The kind of nanomaterials such as Gold nanoparticle, Silver
nanoparticle, magnetic iron oxide nanoparticle, quantum dots, Graphene oxide,
Single-walled and multi-walled carbon nanotubes has been used preferably because
of unique chemical, optical, thermal and mechanical properties. Incorporation of
these nanoparticles via covalent/ non-covalent linkage and fabrication in the sensing
component has enhanced the sensitivity and specificity of the sensors. The
3  Nanosensors for Food and Agriculture 71

Table 3.3  Recent patents globally accepted on nanosensors and nanobiosensors.

Detection Nanostructure used Mode of detection Patent ID/ Year
Chemical analyte Graphene functionalized Electrochemical WO2016112079 (A1)/
with aptamer (2016)
Chemical or Silver and gold Surface plasmon US2016161407 (A1)/
biological agent nanoparticles resonance (2016)
Water quality Single walled carbon Microfluidics US2016129455 (A1)/
nanotubes (2016)
Ammonia Semiconductor Electrical US2016123947 (A1)/
nanoelectronics (2016)
Enzyme activity Nanoparticle assembly Colorimetric WO2016018798 (A1)/
in dairy product (2016)
Nucleic acid Nanowires Electrical US2016033498 (A1)/
(2016)
Pathogenic Hybridizing magnetic Electrical US2014220565 (A1)/
bacteria relaxation nanosensors (2016)
Chemical analyte Photoluminiscent carbon Optical US2014080122 (A1)/
nanotubes (2014)
Chemical analyte Molecular imprinted Electrochemical US2013092547 (A1)/
conducting polymer (2013)
nanojunctions
Pathogens Quantum dots Optical US2011177585 (A1)/
(2011)
pH in food Functionalized Electrochemical US2010330686 (A1)/
sample nanoparticles (2010)
Toxins and Luminescent protein– Optical WO2006083269 (A2)/
contaminants quantum dots (2006)
The table represents the detection application, nanostructure used in the construction of nanosen-
sor, mode of detection and the patent detail with the year of approval (left to right)

construction and working principle of recent nanosensors such as nanobarcode

technology, electronic nose and electronic tongue, wireless nanosensors, rapid
detection technology, optical nanosensors has been extensively discussed. The
application of the nanosensors and nanobiosensors in the area of food technology
from detection of food preservative contaminants and food-borne microbial load to
agriculture sector for the presence of the pesticides, herbicides, heavy metal ions
and fertilizer residues have been extensively reviewed. In reference to increasing
applications of the nanomaterial-based sensor in the area of agriculture and food
sector; many more advancement is anticipated.

Acknowledgment  The author gratefully acknowledges the financial support from Council of
Scientific and Industrial Research (CSIR), and Science & Engineering Research Board (SERB)
New Delhi, India.
72 A.K. Srivastava et al.

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Chapter 4
Nanoemulsions for Nutrient Delivery in Food

DH Lohith Kumar and Preetam Sarkar

Abstract  Nanoemulsion-based encapsulation is an effective method to improve

the solubility of hydrophobic bioactive compounds in food matrices. There is indeed
increasing interest for food-grade nanoemulsions as delivery vehicles for the encap-
sulation of essential oils, phytochemicals, polyunsaturated acid, carotenoids, vita-
min, minerals, plant extracts and polyphenols. There is little knowledge on the
incorporation of nanoemulsions in real food matrices, on their toxicity and fate in
human gut. This chapter reviews nanoemulsion-based encapsulation strategies cur-
rently available to food scientists and technologists.

Keywords  Encapsulation • Bioactive compounds • Structured nanoemulsions •

Nanoemulsion clusters • Emulsomes

4.1  Introduction

Food matrix is a combination of natural sources of nanostructures, where it can be

designed and manipulated to improve the functionality of bioactive compounds by
altering its structure. Combination of bioactive molecules such as vitamin, peptides,
probiotics, antioxidants, and antimicrobials into food matrices leads to the develop-
ment of novel nutraceutical foods and targets to reduce the risk of specific physio-
logical disorders. At the nanoscale, the properties of a substance are entirely
different when it is compared to its macroscale. Even during food fortification, the
major problem associated with conventional delivery systems is nutrient solubility.
However, at the nanoscale, the solubility of a nutrient can be improved and hence it
is believed that nutrient delivery at the nanoscale is a viable technique (Rohner et al.
2007; Kaya-Celiker and Mallikarjunan 2012). The perception of nanoscale nutrient
delivery appears to have started from research on targeted drug and therapeutics
delivery. For instance, certain hydrophilic functional molecules can be delivered to
fat rich food using nano-carriers. On the other hand, lipophilic molecules can also
be delivered and protected in water rich foods. It is expected that these nano-­delivery

DH. Lohith Kumar • P. Sarkar (*)

Department of Food Process Engineering, National Institute of Technology Rourkela,
Rourkela 769008, Odisha, India
e-mail: sarkarpreetam@nitrkl.ac

© Springer International Publishing AG 2017 81

S. Ranjan et al. (eds.), Nanoscience in Food and Agriculture 5, Sustainable
Agriculture Reviews 26, DOI 10.1007/978-3-319-58496-6_4
82 DH. Lohith Kumar and P. Sarkar

Emulsions Characteristics

Conventional Emulsion
• They are colloidal solutions
Oil • Droplet size > 10μm
Droplet • Required emulsifier concentration is high
• They are optically turbid
Water Phase • They are thermodynamically unstable

• They are colloidal dispersions

Micro-Emulsion
• 10μm< Droplet size >200nm
• Required emulsifier concentration is moderate
• They are optically turbid / opaque
• They are thermodynamically stable
• They are colloidal dispersions
Nano-Emulsion
• 200nm< Droplet size >20nm
• Required emulsifier concentration is moderate
• They are optically transparent
• They are stable to gravitational separation

• Continuous Phase: Water

Oil-in-Water Emulsion

• Dispersed Phase: Oil

• Example: Milk
• Application: Used in encapsulation of hydrophobic
bioactive compounds

• Continuous Phase: Oil

Water-in-Oil Emulsion

• Dispersed Phase: Water

Water
Droplet • Example: Butter
• Application: Used in encapsulation of hydrophilic
Oil Phase bioactive compounds

Fig. 4.1  Characteristics of different emulsions. Oil-in-water or water-in-oil emulsions are types of
conventional emulsions. Micro/nano emulsions are classified based on droplet size of conventional
emulsion

systems will completely fragment and the encapsulated bioactive material will be
released in the digestion tract (Jain et al. 2016; Dasgupta et al. 2016; Nandita et al.
2016; Ranjan et  al. 2014; D ​ asgupta et  al. 2017; Shukla et  al. 2017; Walia et  al.
2017). Earlier, different nanomaterials (except nanoemulsions) have been investi-
gated for their antioxidant, antimicrobial, anticancerous, as well as their interactions
with different biomaterials (Tammina et  al. 2017; Sannapaneni et  al. 2016;
Maddinedi et al. 2017; Balaji et al. 2017; Ranjan and Ramalingam 2016)
Emulsions are one of the matrices and could potentially be used as delivery vehi-
cles in food. Emulsions are classified based on size and dispersed phase properties.
Based on droplet size of an emulsion it can be classified as conventional emulsion,
microemulsion, and nanoemulsion. Based on dispersion phase properties, emul-
sions can be classified as oil-in-water emulsion and water-in-oil emulsions (Fig. 4.1).
Nanoemulsion based approach has various benefits over conventional emulsion sys-
tem such as stability against gravitational separation and droplet aggregation. As a
result nanoemulsions are used to prolong the keeping quality of food products
(Otoni et al. 2014; Jo et al. 2015; Ranjan et al. 2012). Attention to the improvement
of food grade nanoemulsion as delivery vehicles for the encapsulation of bioactives
(essential oils, phytochemicals), functional food ingredients (polyunsaturated acid,
carotenoids) and nutraceuticals (vitamin, minerals, plant extracts, polyphenols) has
increased in the last decade (Ghosh et  al. 2013; McClements and Rao 2011)
(Table. 4.1). The characteristic droplet size of nanoemulsions helps in improving
Table 4.1  Examples of bioactive compounds and advantage of encapsulation system
Bioactive compounds Factors affecting Advantage of
group Example Functional properties functionality encapsulation system References
Bioactive Lipids Short chain fatty acids Polyunsaturated fatty Oxidation reduces the Permits to incorporate Klinkesorn and Julian
(butyric acid), medium acids have cholesterol functionality of in water rich functional McClements (2010),
chain fatty acids (caproic reducing effect. bioactive lipids along foods. Mao and Julian
acid, caprylic acid), long with reduced shelf life McClements (2012),
chain fatty acids (oleic of functional food. Donsì et al. (2011),
acid, linoleic acid, Oleic acid has a Solubility of bioactive Hinders chemical Djordjevic et al.
4  Nanoemulsions for Nutrient Delivery in Food

linolenic acid, potential role in lipids limits their deprivation of lipids. (2008), Gulotta et al.
eicosapentanoic acid, reducing Alzheimer’s incorporation into water (2014), Kobayashi
docosahexaenoic acid) disease and inhibits the rich or functional et al. (2005) and
endopeptidase enzyme beverage foods. Otoni et al. (2014)
(causes formation of
amyloid in brain).
Medium chain Enhances the
triglycerides induce systematic
thermogenesis and helps bioavailability through
in reducing body mass sustained release.
index.
Butyrate is used as
substrate in the
regeneration and growth
of large intestine cells.
83

(continued)
 84

Table 4.1 (continued)
Bioactive compounds Factors affecting Advantage of
group Example Functional properties functionality encapsulation system References
Antimicrobials Essential oils (eugenol, Improves the stability of Volatility nature of Improves the Mohanty et al. 2016;
carvacrol), bioactive food products against essential oil. compatibility of active Davidov-Pardo and
peptides (nisin, microbial compounds in food McClements (2015),
casecidins, contamination. matrix and reduce Donsì et al. (2011),
lactoferricin-f) interaction with other Dorman and Deans
food components (2000), Gallucci et al.
Essential oils induce Hydrophobicity of Essential oils (2009) and Jo et al.
aroma to food products. essential oils. encapsulation mask (2015)
undesirable off flavor
pH and temperature Protects from
dependence of environmental stress
antimicrobial activity. and overcome volatility
problems of essential
oils
Sensory effects Increase effectiveness.
Antioxidants Phenolic compounds, Evade undesirable Polyphenols undergo Retard bio-chemical Lu et al. (2016),
ascorbic acid, tocopherol, oxidative reactions. rapid oxidation. degradation. Scalbert and
carotenes. Carotenes add color to Carotenes color Increase effectiveness. Williamson (2000),
food. degradation. Helgason et al.
(2009), Qian et al.
(2012b) and Soong
and Barlow (2004)
DH. Lohith Kumar and P. Sarkar
Bioactive compounds Factors affecting Advantage of
group Example Functional properties functionality encapsulation system References
Vitamins Fat soluble vitamins (A, Essential for growth and Solubility. Improve stability Dasgupta et al.
D, E, and K), water development of body. (physical and (2016), Ozturk et al.
soluble vitamins (B and chemical). (2015), Saberi et al.
C) They are hormones, Oxidative stability Solubility issues can be (2015) and Loveday
antioxidants, cofactors, during UV treatment, solved. and Singh (2008)
and coenzymes. thermal processing.
Low stability in Improved adsorption in
gastrointestinal tract. gastrointestinal tract.
Reduced bioavailability
during thermal
processing such as
pasteurization, baking.
Others Probiotics (lactic acid Enhances gut Food matrix Protection against Hou et al. (2003),
bacteria, Bifidobacterium micro-flora. compatibility. processing stress Krasaekoopt et al.
spp.). factors. (2003), Iyer and
Kailasapathy (2005)
4  Nanoemulsions for Nutrient Delivery in Food

Prebiotics (inulin, Lowers cholesterol by Survival of Targeted delivery of

fructo-oligosaccharides, converting them into microorganisms during encapsulated and Chávarri et al.
fructan, galacto-­ coprostanol and processing. compounds. (2010)
oligosaccharides, produces short chain
lactulose) fatty acids in presence
of prebiotics.
Improve colon health Improved survival of
microorganism in
gastrointestinal tract.
85
86 DH. Lohith Kumar and P. Sarkar

Water Phase

δ (Steric Thickness)

Emulsifier
Oil Phase
Bioactive Compound
r

Fig. 4.2  Schematic representation of an oil droplet dispersed in water which is stabilized by an
amphiphilic emulsifier. The bioactive compound entrapped inside the oil droplet is a lipophilic
molecule which possesses health benefits and disease prevention properties

the bioavailability of encapsulated functional ingredients through the high surface

area to volume ratio. Nanoemulsions are widely used as therapeutic compound car-
riers to targeted functional food matrix whose characteristic droplet size is less than
100 nm. The word ‘nanoemulsion’ was first designated by Nakajima, and it also
referred to as ultrafine emulsions (Solans and Solé 2012; Yang et al. 2012; Nakajima
et al. 1993). Intense attention is being given on nanoemulsions for their application
in food and beverage industries (Qian and McClements 2011). Nanoemulsions are
translucent or transparent systems comprising of two immiscible liquids preferably
water and oil, where dispersed phase liquid is held within a continuous phase with
an amphiphilic interfacial material which inhibits the recombining of droplets by
electrostatic interfacial stabilization.
Nanoemulsions are increasingly being used for encapsulation of lipophilic com-
pounds to enhance their bioavailability in food. Nanoemulsions can be utilized in
concentrated, diluted, gel-like or highly viscous forms depending on the food matrix
structure (McClements 2011; Garti and Leser 2001). However, nanodroplets of the
emulsion are stable against gravitational separation, flocculation, coalescence, and
creaming which is attributed to high Brownian motion and steric stabilization at the
interface of liquid. The efficiency of steric stabilization can be enhanced by increas-
ing the ratio of steric layer thickens (δ) to droplet radius (r) (Fig. 4.2) (Wooster and
Augustin 2006; Wooster et al. 2008).
4  Nanoemulsions for Nutrient Delivery in Food 87

4.2  Components of Nanoemulsions

The major components of a nanoemulsion are oil phase, aqueous phase and inter-
face. Based on end-use of formulation, composition varies accordingly. For instance,
food-grade interfacial stabilizing molecules are used in fortification of functional
beverages, whereas pharmaceutical grade surfactants are used for emulsion-based
drug formulations in pharmaceuticals.

4.2.1  Oil Phase

Oils of food-grade materials such as corn, linseed, coconut, olive, sesame, and sun-
flower are important sources of lipids. In special cases such as formulation of anti-
microbial or flavor nanoemulsions, a blend of nonpolar oils (essential oil or flavor
oil) with any other normal oils are used as the oil phase (McClements 2015a, b). The
important properties of the oil phase such as water-solubility, density, interfacial
tension, chemical stability, viscosity, chemical stability and phase behavior influ-
ence the nanoemulsion formulation, bioavailability of nutrients and encapsulation
efficiency.

4.2.2  Aqueous Phase

Aqueous phase principally defines the organoleptic properties of food nanoemul-

sions. Minerals, salts, sugars and biopolymers can be used to alter the bulk proper-
ties of aqueous phase in emulsion. Stability against creaming in nanoemulsion is
dependent on the viscosity and density of aqueous phase (McClements 2015a). In
addition, colligative properties of solutes in the aqueous phase affect the long term
stability and texture of nanoemulsions. For instance, crystallization in emulsion-­
based ice creams defines the mouth-feel and texture which is perceived as sandy or
grainy (Kumar et al. 2016; McClements 2015a).

4.2.3  Interface

Interface comprises of a thin membrane made of surface-active emulsifiers at the

interface of oil and water. Interfacial properties such as interfacial tension, rheology,
charge, contact angle and composition influence emulsion stability and functional-
ity. In food grade nanoemulsion formulations, proteins, polysaccharides and
protein-­polysaccharide conjugates are preferred over synthetic surfactants due to
88 DH. Lohith Kumar and P. Sarkar

their non-toxicity and nutritional benefits. Some of these materials are briefly dis-
cussed here.

4.2.3.1  Protein

Proteins have both lipophilic and hydrophilic groups which help in stabilizing the
emulsions. Low molecular weight proteins are preferred in forming emulsion due to
rapid diffusion to the interface (McClements and Li 2010). Once after adsorption at
the interface, proteins undergo partial denaturation which is induced by external
energy. Partial denaturation creates structural changes in proteins and makes them
more reactive species (McClements and Rao 2011). Emulsion stability is also influ-
enced by the physico-chemical characteristics of proteins. For example, their sur-
face hydrophilic or hydrophobic nature interferes in adsorption, where better
integration leads to more emulsion stability. In contrast, the solubility of the protein
in an aqueous phase is driven by surface charge, where higher adsorption rate can
be expected at high solubility. However, the viscoelastic interfacial layer formed
around the droplet resist environmental stresses and delivers steric and electrostatic
stabilization. The charge around the droplet after protein diffusion to the interface is
dependent on the pH (Karaca et al. 2011). However near isoelectric point, aggrega-
tion or flocculation of emulsion droplet dominates which leads to instability.
Proteins have ionisable groups that alter the charge of oil droplet in acidic or basic
condition. In acidic condition, COOH, H+, or COO– ions and NH3+ or NH2 at basic
conditions are responsible for the change in charge of oil droplets (Damodaran et al.
2007). However, steric stabilization property of proteins against droplet coalescence
is influenced by its structure and size. Nevertheless, extended tails of hydrophilic
amino acids controls steric stabilization at the interface (Jafari et al. 2008).
Partial hydrolysis of protein molecules with the assistance of enzymes showed
enhanced emulsifying properties. Protein hydrolysis changes the structure, increases
solubility, surface hydrophobicity, exposes the hidden amino acids and reduces the
molecular weight which permits faster diffusion to the oil-water interface (Lamsal
et al. 2007). However, improvement in functionality of protein through hydrolysis
is dependent on aspects such as temperature, time, and enzyme (Tsumura 2009).
Low degree of protein hydrolysis is desired in emulsion formation. At higher degree
of hydrolysis, increasing protein concentration in continuous phase leads to phase
saturation rather than adsorption at interface (Conde and Patino 2007). The compo-
sition of the continuous phase also affects the interfacial adsorption of proteins.
When high molecular weight proteins adsorb at the interface, they undergo confor-
mational changes to reduce the interfacial tension between oil and aqueous phases.
However, when low molecular weight proteins adsorb, they undergo little or no
conformational changes before saturation of the interface to produce thicker inter-
facial layers at high concentration (Bouyer et al. 2012). Hence, an understanding of
4  Nanoemulsions for Nutrient Delivery in Food 89

the structural mechanisms of protein stabilization is essential to improve their func-

tionality. By controlling processing conditions and biopolymers properties, the
interfacial characteristics could be controlled. This is essential for creation of tai-
lored delivery vehicles used for nutrients encapsulation.

4.2.3.2  Polysaccharides

Investigation of encapsulation application of polysaccharides especially in bioactive

delivery systems continues to be an important area of food research. Natural and
modified polysaccharides are promising interfacial stabilizing molecules in nano-
emulsion formation. Cellulose, chitosan, pectin, starch, guar gum, alginate, cyclo-
dextrin, and new or modified native gums are used for the stabilization of emulsion
systems. Polysaccharides are preferred in the food industry for their multifaceted
structures and functions. Stabilization of emulsions using polysaccharides is due to
the increased viscosity of continuous phase and generation of gelled droplet net-
works (McClements and Rao 2011).
Polysaccharides are biocompatible, biodegradable and can be structurally modi-
fied to improve essential properties. In contrary to other interface stabilizing materi-
als, polysaccharides can interact with a wide range of bioactive molecules through
their functional groups, which makes them unique and flexible nutrient carriers to
bind and entrap lipophilic and hydrophilic compounds. Polysaccharides are pre-
ferred over proteins as shell materials in encapsulation processes due to their high
thermal stability. The stabilizing mechanism (steric stabilization) of polysaccha-
rides differ from proteins and they tend to deliver relatively better stability to stress
factors such as salt, pH, freezing, and heat (Charoen et al. 2011; Ozturk et al. 2015).

4.2.3.3  Protein-Polysaccharide Complex

Protein and polysaccharides can be combined to create conjugates. Addition of

polysaccharides can improve the colloidal stability of primary viscoelastic interfa-
cial layer formed by proteins. The secondary layer formed by polysaccharide
enhances stability through gelation and thickening behavior in the water phase.
Protein-polysaccharide complexes at the interface of the liquid phase in emulsions
can be obtained by two unique mechanisms (Fig. 4.3). When polysaccharides are
added in bulk to interact with proteins before adsorption at the interface is known as
mixed emulsion and if polysaccharides are added after protein adsorption at the
interface is called bilayer emulsion (Fig. 4.3).
Complexation of protein and polysaccharides through thermal treatment and pH
adjustment can be used for the preparation of mixed emulsions. Electrolyte charge
properties of protein and polysaccharides are used to diffuse to the interface using
the layer-by-layer technique to form bilayer emulsions. The electrostatic force is the
90 DH. Lohith Kumar and P. Sarkar

Protein
Polysaccharide
a) Polysaccharides b)

Protein

Polysaccharide-Polysaccharide Polysaccharide-Protein particle Polysaccharide-Protein particle

Heteroaggregation Heteroaggregation Layer by Layer

Fig. 4.3  Schematic representation of (a) Mixed emulsion and (b) Bi-layer emulsion. In polysac-
charide-polysaccharide systems, hetero-aggregation complexation is possible by steric stabiliza-
tion. Polysaccharide-protein complex formation is governed by electrostatic and polysaccharide
steric forces

primary driving mechanism in complexation at the interface. Hydrophobic interac-

tion in emulsion along with the degree of hydrogen bonding helps in stabilizing the
protein-polysaccharide aggregates (McClements 2006). However, emulsion stabil-
ity is dependent on temperature, for instance emulsions stabilized by pea protein
and acacia gum aggregates are more stable at low temperatures. At higher tempera-
tures, they destabilize due to decreased hydrophobic interactions (Liu et al. 2009).
This thermodynamic compatibility also depends on electrical charge of the biopoly-
mers which is affected by ionic strength and pH.
Adsorption of polysaccharides at the interface of protein stabilized layer increases
the viscosity of continuous phase and slows down creaming rate. Associative phase
separation is of major interest in food science. Depending on factors such as molec-
ular charge density, binding affinity, and molecular conformation, different kinds of
structures are often formed between proteins and polysaccharides.
Emulsion stabilizing property of the protein-polysaccharide conjugates can be
improved by using high molecular weight polysaccharides during complexation (Kato
2002; Samant et al. 1993). Further, improvement in functional properties of conju-
gates through Maillard reaction are reported, few are listed in Table 4.2. The conjuga-
4  Nanoemulsions for Nutrient Delivery in Food 91

Table 4.2  Examples of improved functional properties of protein through Millard reaction
Protein-­ Improved functional
Polysaccharide property Reaction condition References
Peanut protein Improved thermal 1:1 weight ratio of Liu et al. (2012)
isolate with stability, solubility at peanut protein isolate
dextran pH 4.5 to 6.0, foaming and dextran were dry
and emulsifying heated at 60 °C and
property. 79% relative humidity
for 7 days.
Milk proteins Increased antioxidant 1:2 weight ratio of Hiller and Lorenzen
with lactose, capacity for milk whey protein isolate (2010)
pectin and dextran protein-glucose, higher and glucose, pectin,
surface hydrophobicity lactose or dextran were
for milk protein-lactose, heated at 70 °C and
enhanced heat stability 65% relative humidity.
in milk protein-dextran,
increased overrun for
milk protein-pectin.
Rice protein Maillard reaction 1:1 weight ratio of rice Li et al. (2013)
hydrolysates with enhanced the solubility, protein hydrolysates
glucose, emulsification activity and other
maltodextrin and emulsification polysaccharides are
DE20, lactose, stability by a factor of dispersed in water and
and dextran T20 3.5, 5 and 7.3 times, adjusting pH to 11.0
respectively. followed by heating at
100 °C.
Egg white protein Increased emulsion 1:1 weight ratio of Nagodawithana and
with pectin viscosity and stability. protein-polysaccharides Reed (1993)
were mixed in solution
and followed by freeze
drying. Incubation of
dry materials at 60 °C
and 79% relative
humidity for 6 - 48
hours.
Soy protein Improved solubility at 1:1 weight ratios of Xue et al. (2013)
isolate with isoelectric point and protein-polysaccharides
maltodextrin and emulsifying properties. were dry heated at 60
gum acacia °C and 79% relative
humidity.
Wheat germ Improved solubility and 1:1 weight ratio of Niu et al. (2011)
protein with emulsifying properties. wheat germ protein and
glucose, xylose, saccharides were
dextran, dispersed in water at pH
maltodextrin and 11.0 and heated at 90
lactose °C.
(continued)
92 DH. Lohith Kumar and P. Sarkar

Table 4.2 (continued)
Protein-­ Improved functional
Polysaccharide property Reaction condition References
Soy whey protein Improved emulsion 1:3 wright ratios of Kasran et al. (2013)
isolate with stability property at protein and
fenugreek gum protein-polysaccharide polysaccharides were
ratio of 1:3 and 1:5. mixed in distilled water,
followed by freeze
drying. Incubation of
dry powder for 3 days
at 60 °C.
β-lactoglobulin Reduced antigenicity of Protein-polysaccharide Bu et al. (2010)
with glucose protein. powder at a weight ratio
ranging from 0.17 to
7.83 was incubated at
different temperature
(40-60 °C) at 79%
relative humidity.
Milk protein with Improved emulsion 1:3 weight ratios of Yadav et al. (2010)
corn fiber gum stability under high protein and
acidic condition and salt polysaccharide were
concentration. incubated for 7 days at
75 °C and 79% relative
humidity.

Flocculation Steric Stabilization Emulsion Destabilization

Polysaccharide Concentration

Fig. 4.4  Illustration of protein-polysaccharide stabilization as a function of polysaccharide con-

centration. Flocculation begins at low polysaccharide concentration through droplet bridging. At
optimum polysaccharide concentration, steric stabilization hinders the droplet instability. At con-
centrations beyond the critical polysaccharide concentration, depletion flocculation takes place
4  Nanoemulsions for Nutrient Delivery in Food 93

tion between protein and polysaccharides through Maillard reaction in a dry state is
very effective in enhancing the emulsifying property and thermal stability of proteins.
For example, conjugation of galactomannans with lysozyme improved the emulsify-
ing property of the conjugate. In general, heating of lysozyme in aqueous solution
results in unfolding of proteins which forms insoluble lysozyme aggregates and leads
to loss in activity. This aggregation can be inhibited through polysaccharide attach-
ment and formation of conjugates. It is favorable in the encapsulation of heat stable
functional compounds in food (Shu et al. 1996). Besides, the antimicrobial property of
lysozyme against Gram-negative bacteria can be improved by conjugating with galac-
tomannan as well as with dextran (Nakamura et al. 1991; Nakamura et al. 1992a).
Gluten can be made more soluble by complexing with dextran and antioxidant prop-
erty of ovalbumin can be enhanced through covalent bonding with galactomannan or
dextran (Nakamura et al. 1992b; Kato et al. 1991).
Several factors influence utilization of protein-polysaccharide interaction for
emulsification. When an electrically charged polysaccharide is adsorbed on protein
layer at the interface, different structural changes are likely to influence depending
on its concentration (Fig. 4.4). At low concentration of polysaccharide, flocculation
occurs, at intermediate concentration steric stabilization is possible. However, when
concentration increases above critical concentration required for steric stabilization,
emulsion destabilization occurs due to depletion flocculation. Charged polyelectro-
lytes favor emulsion stability by creating repulsive conditions which hinder the
destabilization mechanism. Such behavior was observed in whey protein isolate and
chitosan or pectin combination (Laplante et al. 2005; Neirynck et al. 2007). Gelatin
and acacia gum are the most studied combination which is used for encapsulation of
flavors and nutrients in foods (Junyaprasert et al. 2001). Gelatin and guar gum com-
plexes are used for encapsulation of flavor in baked foods (Yeo et al. 2005). Bilayer
emulsion technique can be efficiently used to protect the bioactive compounds
against oxidation, temperature and other depletion factors (Benjamin et al. 2012).

4.3  E
 ncapsulation of Different Bioactive Molecules Using
Nanoemulsion

Utilization of bioactive molecules in the formulation of functional foods is gaining

attention in food research area. Due to developments in biochemistry and molecular
biology, unknown phytochemicals and nutrients that are present in traditional foods
are being identified as health promoting bioactive molecules (Sarkar et al. 2015).
Encapsulation can be used to protect the bioactivity of these molecules. One such
encapsulation system is nanoemulsions which is one of the most popular nutrient
carrier systems in food. Nanoemulsions are lipid based encapsulation systems; they
94 DH. Lohith Kumar and P. Sarkar

can enhance the bioavailability and solubility of hydrophobic compounds. There are
few factors that support this functionality enhancement. Firstly, bioactive com-
pounds release rapidly in nanoemulsions due to large surface area, which helps in
quick digestion and absorption of active ingredients (McClements and Rao 2011).
Secondly, in the small intestine, nanoemulsions are easily adsorbed into lymphatic
vessels through mucous layer, which helps in easier absorption and distribution of
bioactive molecules (Jenkins et al. 1994). Thirdly, depending on surface charge, size
and hydrophobicity level, the released amount from emulsion matrix are transported
through epithelial mucus and adsorbed via mucosa-associated lymphoid tissues (Lu
et al. 2012). Few bioactive compounds which have been encapsulated using nano-
emulsions are discussed below.

4.3.1  Polyphenol

Polyphenols are aromatic molecules with phenol structural units. These are classi-
fied under secondary metabolic compounds generated through the polyacetate path-
way and shikimate pathway. Polyphenols are regarded as micronutrients which are
abundant in diet and important for their role in the prevention of degenerative dis-
eases such as cardiovascular and cancer diseases. These phytochemicals signifi-
cantly impact organoleptic and color characteristics of foods. Polyphenols also
exhibit antioxidant properties during protein-polyphenol conjugation (Liu et  al.
2016).
Oil-in-water emulsions show enormous potential for encapsulation of polyphe-
nols. However, there are disadvantages that exist in emulsion-based encapsulation
systems. Oil-in-water emulsion is usually sensitive to environmental stresses such
as coalescence, Ostwald ripening, flocculation, creaming, and oxidative stress fac-
tors. All these instability factors can cause imbalance in emulsion stability leading
to decreased bioavailability of encapsulated polyphenols. However, nanoemulsions
can override these instability problems. On the other hand, it is challenging for pre-
cise control of the release of polyphenols from oil-in-water emulsions because a
simple interfacial structure rapidly diffuses the polyphenols from inside to outside
of the oil droplets. The major categories of dietary polyphenols are coumarin, tan-
nin, stilbenes and flavonoids (Scalbert and Williamson 2000). Curcumin is a lipo-
philic polyphenol. Due to its poor solubility (at pH 5.0 maximum solubility is 11 ng/
mL) and reduced stability in the gastrointestinal tract, curcumin is poorly absorbed
in the body (Tønnesen 2002). However, conjugation of curcumin nanoemulsions
with peptides enhanced bioavailability compared to its free components through
rapid and more efficient cellular uptake (Simion et al. 2016).
Epigallo-catechin-gallate (EGCG) is a hydrophilic flavanol present in green tea
leaves (Camellia sinensis). This flavanol is susceptible to oxidation in the intestine.
4  Nanoemulsions for Nutrient Delivery in Food 95

To increase the bioavailability and stability, emulsion systems can be used. Besides,
improving the systemic bioavailability of EGCG through encapsulation, it also
enhances bioactivity in emulsion matrix (Ru et al. 2010). In another study, encapsu-
lation of green tea extract in water-in-peanut oil emulsion system showed the high-
est oxidative stability (Lante and Friso 2013). Chaiittianan et.al, extracted
polyphenols from Phyllanthus emblica and encapsulated in nanoemulsions. They
have observed that loading ratio of phenolic compounds were in the descending
order of epigallocatechin, epigallocatechin gallate, vanillinic acid, gallic acid and
ellagic acid (Chaiittianan and Sripanidkulchai 2014). However, several factors limit
the use of polyphenols in food matrices. The major limiting factor is stability of
natural polyphenols in different food matrices. Polyphenols oxidize very rapidly,
resulting in decreased functionality. Also, many polyphenolic molecules possess
limited solubility in water. This limited solubility is often connected with lower
instability in gastrointestinal tract and low intestinal permeability which results in
reduced bioavailability. Finally, the bitter and astringent taste of many polyphenolic
compounds should be masked before use in food formulations (Lu et al. 2016).

4.3.2  Bioactive Lipids

Lipids are one of the food constituents that possesses diverse structures. Butyric
acid, long chain fatty acids (polyunsaturated, mono unsaturated fatty acids, conju-
gated linoleic acids, and eicosapentaenoic acids) and medium chain fatty acids are
considered as bioactive lipids. The functional properties of several lipids directed
researchers to encapsulate and protect their functionality. Poly-unsaturated fatty
acids such as arachidonic, linolenic, and linoleic acids are considered as essential
nutrients for humans (Augustin and Hemar 2009). Physiological properties of lipids
have been recognized which provides multiple health benefits. For instance, eicosa-
pentaenoic acid demonstrates hypotriglyceridemic and antiatherosclerotic effects.
Arachidonic, linolenic and linoleic acids are considered to reduce hypercholesterol-
emia. Lipophilic vitamins (A, D, E, and K) and aromatic compounds are often solu-
bilized in medium chain triglycerides and used as oil phase in emulsion-based
delivery systems. Triglycerides of long chain are preferred over medium chain due
to high stability against oxidation, higher rate of metabolism and adsorption
(McClements et al. 2007).
The encapsulation of volatile aromatic molecules such as essential oil and flavors
dissolved in medium chain fatty acids favors the controlled release of volatile mol-
ecules into food matrices. The controlled release of volatiles from the emulsions is
attributed to reduced vapor pressure and diffusion coefficient due to interfacial film
formation. The benefits of using nanoemulsion based encapsulation systems for
bioactive lipids are reduction of autoxidation, compatibility with wide range of food
96 DH. Lohith Kumar and P. Sarkar

products, improved stability in food matrices, enhanced functional properties, solu-

bilization of flavor or volatile compounds in lipids, masking of bitter or astringent
tastes and protection of bioactive molecules in the gastrointestinal tract until reach-
ing the targeted location.

4.3.3  Carotenoids

Carotenoids are natural lipophilic pigments demonstrating health benefits in reduc-

ing certain cancers and eye protection (Johnson 2002). Chemically, carotenoids are
formed from 40 carbon atoms connected by eight isoprene units. They are catego-
rized into hydrocarbon and oxygen carotenoids. Hydrocarbon carotenoids refer to
carotenes includes lycopene, α-carotene, β-carotene and phytoene. Oxygen carot-
enoids are xanthophylls which include cryptoxanthin, lutein and astaxanthin
(Bagchi et al. 2010). Carotenoids are used in food industry for recovering the color
loss associated with processing or to impart color to food products. On the other
hand, carotenoids exert antioxidant properties and helps in inhibiting oxidation in
oil-in-water and water-in-oil emulsions such as in mayonnaise, salad dressings, fat
and dairy spreads (Santos and Meireles 2010). However, the bioavailability of carot-
enoids is often reduced due to poor solubility, degradation during assimilation and
release patterns from the food matrix. Moreover, oxidative degradation of carot-
enoids reduces the nutritional value of food along with the development of off-­
flavor, discoloration and lipid pro-oxidants. Therefore, conveying carotenoids to the
human body via encapsulation can enhance the bioavailability and release kinetics
in food matrices.
Encapsulation of carotenoids in nanoemulsions proves to be an efficient delivery
system. Though microemulsions are also considered for encapsulation, nanoemul-
sions are preferred due to increased physical stability, high optical transparency,
processability and greater bioavailability. The biochemical stability of carotenoids
during storage and emulsification depends on droplet properties (zeta-potential,
interfacial composition, droplet size), emulsion composition (type of carotenoid,
concentration of oil, surfactant properties, and presence of free radicals or oxygen
scavengers), extrinsic conditions (oxygen, light, temperature) and intrinsic condi-
tion (ionic strength, pH, droplet surface charge) (Qian et  al. 2012b; Qian et  al.
2012a).
Interfacial engineering of oil-in-water emulsions such as modifying the emulsion
phase (oil phase, water phase, and interfacial layer) enhances the biochemical sta-
bility of the carotenoids. It was affirmed that the oxidation pattern of carotenoids
present in emulsion matrix and bulk phase matrix are significantly different. In the
bulk phase, oxidation of carotenoids is initiated by oxygen transport at the oil-air
interface, whereas, in emulsions carotenoids are less prone to oxidation due to oxy-
gen dissolution in continuous water phase, and barrier properties of interfacial layer
4  Nanoemulsions for Nutrient Delivery in Food 97

(Qian et  al. 2012a). The composition of the interface and interface stabilizing
material affects the retention of carotenoids in the oil phase. For example,
­
β-lactoglobulin interface stabilized emulsions showed better retention of β-carotene
compared to Tween 20. β-lactoglobulin demonstrated free radical scavenging ability
via thiol groups, disulfide bonds and cysteine residues through complexation, which
improved the barrier properties at the interface and enhanced the retention of caro-
tene in oil phase (Qian et al. 2012b). Formulation of carotenoid nanoemulsion at pH
range of 3.0–7.0 increased the degradation kinetics due to formation of carotenoid
carbocation via cis-trans isomerization (Qian et al. 2012b; Boon et al. 2009).

4.3.4  Essential Oils

Essential oils have received particular attention in food preservation and safety
because they are natural antimicrobials with strong bioactivity and potential health
benefits. The antimicrobial effects of different essential oils and their constituents
have been studied against a broad range of microorganisms. Hydrophobic, volatile
and reactive nature of essential oil components limits their incorporation into foods
directly (B Sowbhagya 2015). Aldehydes, terpenes and phenols are the major frac-
tions of essential oils. Several research reports suggest that antimicrobial activity of
essential oil is primarily the result of reduction in percent unsaturated fatty acid on
cytoplasmic membrane due to hydrophobic nature (Knobloch et al. 1989).
The mode of action of phenols, terpenes and aldehydes are similar. Carvacrol, a
phenolic molecule, acts as a carrier of protons through the lipid bilayers. It causes
dissipation of protons and impairment in cellular metabolism. Limonene is an
example of terpenes which acts on cytoplasmic membranes. This reduces mem-
brane integrity and inhibits the respiratory enzymes. The antimicrobial activity of
cinnamaldehyde is due to disintegration of the electron transport chain in cells (Gill
and Holley 2004; Gallucci et al. 2009). The antimicrobial activity of phenolic com-
pounds is associated with partial disruption of membrane integrity causing an out-
flow of small ions instead of large molecules. But aldehydes such as cinnamaldehyde
can disintegrate the membrane and access the periplasm and deeper parts of the
cells causing cell death (Dorman and Deans 2000). On the other hand, antimicrobial
effect of essential oils are more on Gram-positive species than Gram-negative
microorganisms owing to differences in cell wall structures (Knobloch et al. 1989).
Essential oils are chemically active species like other bioactive molecules. This
nature of essential oils may cause significant undesirable effects within the food
matrix. They may also interact with food components due to hydrophobic interac-
tions resulting in reduction of active concentration. Hence, nano-encapsulation of
essential oil is a feasible and efficient approach to protect these bioactive substances.
However, in the case of other antimicrobial compounds, encapsulation possibly
98 DH. Lohith Kumar and P. Sarkar

increases the absorption of antimicrobials where microorganisms are ideally

located, for example liquid-solid interfaces or water-rich phases (Donsì et al. 2011).
In deliberation of the hypothetical mechanism of the antimicrobial activity of
essential oils, the design of nanoemulsion-based encapsulation structures follows
two diverse principles. In the first principle, the encapsulation structure is capable
of carrying the antimicrobial molecule through the cellular membrane and will
release around the membrane following the disintegration of cytoplasmic mem-
brane. In the second principle, the encapsulation structure is considered to act as a
reservoir of antimicrobials molecules, and ensures a sustained release into the bulk
phase. This approach is particularly vital in the encapsulation of limited soluble
antimicrobial molecules. However, encapsulation of the antimicrobial compounds
in oil-in-water emulsions at concentration greater than their water soluble concen-
tration helps in sustained release of the antimicrobial to the continuous phase (Donsì
et al. 2011).

4.3.5  Flavor

Flavor is a perception brought by non-volatile and volatile chemical complexes at

dynamic equilibrium. Flavor and fragrance are two different kinds of concepts
where flavor affects the sense of taste while fragrance affects the sense of smell.
Generally flavor molecules are volatile in nature; encapsulation helps in protection
against degradation (enzymatic, chemical, and mechanical), stabilizes them for
extended period of time and enables sustained release during ingestion (Yeo et al.
2005). Encapsulated aroma or flavors compounds are extensively used for bakery
products, confectioneries, particulate food products, and beverages. The essential
features of a colloidal (emulsion) based encapsulation system depends on food
matrix properties. For example, specific stress induced release of flavor molecules
is necessary for powdered foods, while sustained release is required in chewing
gum. Moreover, flavor must be reserved throughout the storage time (Madene et al.
2006).
In general flavor compounds are in liquid phase at ambient temperature and most
of them are hydrophobic in nature. Flavor compounds generally have molecular
weights in the range of 100–250 Da and consist of various types of chemical struc-
tures including alcohols, aldehydes, hydrocarbons, ketones, acids, esters (Madene
et  al. 2006). Flavor retention in the food matrix is affected by the association
between flavor compounds and food components. The interaction between food
components and flavor molecules is often associated with intermolecular interac-
tions such as covalent bond interactions, hydrogen bond interactions, ionic bond
interactions, hydrophobic interactions and van der Waals forces (Zuidam and
Heinrich 2010).
Interaction of flavor compounds with proteins, polysaccharides and lipids varies
and depends on the presence of reactive species in their structure. Proteins are
4  Nanoemulsions for Nutrient Delivery in Food 99

amphiphilic in nature; they interact with flavor compounds through their lipophilic
groups via hydrophobic interactions, ionic interactions and hydrogen bonds. As fla-
vor compounds are hydrophobic in nature they are partitioned into the lipid phase in
food, and can be dissolved through lipophilic interactions via van der Waals forces.
Polysaccharides, starches and sugars are also essential food structures, they bind
through hydroxyl group via hydrogen bonding. For example, cyclodextrin is a cyclic
oligosaccharide which shows hydrophobic inner cavity and the periphery is rela-
tively hydrophilic (Given 2009). When a flavor compound is entrapped within
cyclodextrin, it forms an inclusion complex. Complexation is beneficial for the
encapsulation of flavor compounds having defined geometries since they can fit in
the narrow space (Astray et al. 2010). However, amylose is used for stabilization of
flavor compounds since it forms inclusion complexes via hydrophobic interactions
(Heinemann et al. 2005).
Many research studies suggested that emulsion based encapsulation system is
effective in protecting flavors against degradation and enhances their bioavailability
in the gastrointestinal tract (Mirhosseini et al. 2008; Given 2009). The release of
flavor compounds from emulsions within the food matrix is affected by mass trans-
fer and partitioning in the dispersed phase, continuous phase and headspace.
However, efficient emulsion encapsulation system design relies on droplet size, vis-
cosity, distribution of flavor in the matrix, environmental factors and interaction
between other food components (Djordjevic et al. 2008).
Utilization of higher interfacial area between oil and water phases often increases
the flavor release rate in the food matrix. Research have shown that reducing the size
of oil droplets in emulsion enhances the sustained release properties of lipophilic
flavor compounds. But conversely, reducing the oil droplets in emulsions also
increases the viscosity, which may limit the flavor release to a certain extent.
However, the composition and properties of interfacial film formed between oil
phase and water phase decides the flavor release properties into the continuous
phase. Increased adsorption of emulsifiers restricts the mass transfer of flavor mol-
ecules at the oil-water interface. However, when proteins are at the interface, the
nature and polarity of proteins also interfere in the release of flavor from oil droplets
to water phase. For example, when mustard oil droplets was stabilized with β and
α-lactoglobulin, the release of isothiocyanate (pungent flavor) and ethyl hexanoate
(fruity flavor) was low in the presence of β-lactoglobulin at the interface compared
to the presence of α-lactoglobulin at interface (Guichard and Langourieux 2000). In
the case of hydrophilic flavor compounds such as butanol and diacetyl, the nature of
protein has no effect on the release of flavor. In the presence of polysaccharides at
the interface of emulsion droplets, the release rate is influenced by droplet size. An
increased flavor release referred as salting out effect can be observed at higher drop-
let size and enhanced flavor retention can be witnessed with small oil droplets
(Guichard 2002).
100 DH. Lohith Kumar and P. Sarkar

4.3.6  Probiotics

Probiotics are microorganisms which improves intestinal health and are considered
as pharmacological products. However, due to increasing trend towards functional
foods, probiotics are currently being used in the formulation of health promoting
foods. Normally fermented dairy foods such as yogurt, curd and other milk products
are considered as probiotic functional foods which are available in refrigerated con-
ditions in markets. However, processing conditions of dairy products influence the
survival rate of probiotic microorganisms in fermented dairy foods. Although the
viable number of microorganisms in foods varies from strain to strain, the signifi-
cant number (106–108 CFU/g) should be present in the final functional food (Martín
et al. 2015; Huq et al. 2013). The growth of microbes in food matrix is governed by
the environmental conditions (relative humidity, temperature) along with intrinsic
factors such as water activity, pH, nutrient availability and buffering capacity.
Hence, selection of suitable food matrix is a vital factor in the formulation of probi-
otic functional foods as it might support microbial colonization and survival in the
gastrointestinal tract. Emulsion-based encapsulation systems have been effectively
applied for the protection of lactic acid bacteria. Encapsulation of probiotic micro-
organisms in emulsion droplet matrix has proven to enhance the survival of micro-
organisms in different simulated intestinal and stomach conditions. For example,
encapsulation of lactic acid bacteria in the droplets of sesame oil emulsions
improved cell viability rate approximately 104 times compared to un-encapsulated
cells under simulated gastrointestinal tract conditions (Hou et al. 2003).

4.4  Advanced Nanoemulsions

4.4.1  Structured or Designer Emulsions

In structured emulsions, the interface between oil and water phase is tailored to
meet the special requirement for the encapsulation of bioactive compounds.
Formulations of structured emulsions are often considered under microstructural
engineering. The oil droplets of nanoemulsions can be used as templates to formu-
late the complex structure that can be utilized as nano-delivery system. These struc-
tured emulsions will provide enhanced chemical and physical stability of the
encapsulated bioactive compound within the food matrix as well as gastrointestinal
tract (McClements 2015a). Different structured emulsions are depicted in Fig. 4.5.
 4  Nanoemulsions for Nutrient Delivery in Food

Structuring of an Emulsion Droplet

Fig. 4.5  Illustration of nanoemulsion structuring. Hydrogels are semi-solid nanoemulsions. In clustered emulsions, two different oil species are adsorbed on
each other based on charge and relative droplet size. Multiple emulsions consists of three phases (inner oil phase-middle water phase-outer oil phase or inner
water phase-middle oil phase-outer water phase). Solid lipid nanoparticles are formed by controlled crystallization of nanoemulsions. Multilayer emulsions are
formed by layer-by-layer nanolamination of primary nanoemulsion interface with polyelectrolytes
101
102 DH. Lohith Kumar and P. Sarkar

4.4.1.1  Multilayer Emulsions

The functionality of nanoemulsions can be tailored and improved by adsorbing

electrically charged surface-active biopolymers onto oil droplets to form nanometer-­
ranged interfaces. This type of structuring can be accomplished by electrostatic
deposition using layer-by-layer approach. Nanoemulsions are initially formed by
coating the oil droplet using charged biopolymers (positive or negative) followed by
dilution of the primary nanoemulsion with oppositely charged biopolymers (nega-
tive or positive) (Güzey and McClements 2006a). Multilayer nanoemulsion
improves the stability of emulsion droplets and bioactive components in food matri-
ces. Different charge, rheology and thickness can be obtained by diluting the pri-
mary layer at various dilution factors. The primary interfacial layer around the oil
droplets helps in protecting the sensitive bioactive compounds, whereas secondary
or tertiary layer helps in improving the stability and performance of bioactive com-
pounds. For example, when different levels of lipid digestion in the gastrointestinal
tract are needed, lipid digestion can be retarded as well as extended by selecting
indigestible biopolymers (Güzey and McClements 2006b). Examples for encapsu-
lation of bioactive compounds in structured multilayered emulsions are given in
Table 4.3.

4.4.1.2  Multiple Emulsions

Multiple emulsions are used in the formulation of low-calorie food products, to

mask the undesirable odor or taste. They are efficient in controlling lipid oxidation
and sustained release of flavors in water rich matrices. In the case of double emul-
sions (for example, water-in-oil-in-water) whole emulsion system consists of two
interfacial layers i.e. primary interface between internal water and oil phase, sec-
ondary interface between oil and outer water phase. However, there are difficulties
encountered during preparation of multiple emulsions such as stability due to diffu-
sion of internal aqueous phase into bulk phase and coalescence (in the case of water-­
in-­
oil-in-water emulsion). Though multiple emulsions are extensively used in
pharmaceutical industry, food products need food grade interface stabilizers with
low molecular weight (Muschiolik 2007). Food grade biopolymers such as protein
and polysaccharides are amphiphilic molecules. They enhance the interfacial cover-
age which results in better stability against creaming and improved release of bioac-
tive components in the internal phase of double emulsions (Muschiolik 2007;
McClements 2015a). Few examples of multiple emulsion based encapsulation are
shown in Table 4.4.

4.4.1.3  Hydrogels

Hydrogels are semi-emulsions formed through phase separation process. Hydrogels

are often considered as multiple emulsions because the bioactive compound solubi-
lized in oil droplets are trapped inside a hydrogel particle which is dispersed inside
Table 4.3  Composition of structured multilayered emulsion based encapsulation of bioactive compounds
Encapsulated
Primary layer Secondary layer Tertiary layer Bioactive compound References
Interface Stabilizing Material Tween Adsorbed Material Chitosan Adsorbed Material chitosan- Capsaicin Choi et al.
80 Alginate complex (2011)
Zeta potential, (mV) –14.2 ± Droplet Size, (nm) 10.07 ± 0.34 Droplet Size, (nm) 12.21 ± 0.76 to
1.96mV 15.67 ± 0.82
Emulsion composition 1:3 ratio of Zeta potential, (mV) –26.3 ± 2.7 Zeta potential, (mV) –8.97 ± 0.43
oleoresin capsicum and tween 80
4  Nanoemulsions for Nutrient Delivery in Food

Continuous Phase volume- 0.5% Continuous Phase volume 0.05% of

w/v of chitosan chitosan and 0.05% of alginate
Interface stabilizing material Adsorbing material OSA- starch Adsorbing material Chitosan Vanillin Noshad et al.
Soybean protein isolate (2015)
Emulsion composition 1% w/v Continuous phase volume 0.8 % Continuous phase volume 0.5 % w/v
soybean protein isolate aqueous w/v in sodium acetate buffer at pH in in sodium acetate buffer a pH 3.5
solution and 5wt% sunflower oil in 3.5
sodium acetate buffer pH 3.5
Interface stabilizing material Sodium Adsorbing material ɛ-polylysine Adsorbing material Dextran sulfate Retinol Pan and Nitin
dodecyl sulfate (2015)
Droplet size, (nm) 133±30 Droplet size, (nm) 194 ± 10 Droplet size, (nm) 111 ± 40
Zeta potential, (mV) –67.3 ± 0.1 Zeta potential, (mV) +11.7 ± 0.7 Zeta potential, (mV) –46.3 ± 0.4
Emulsion composition 2 w/v% of Continuous phase volume 4 w/v % Continuous phase volume 4 w/v % of
emulsifier and 4 w/v% of oil at pH 6.5 of ɛ- poly lysine dextran sulfate
103

(continued)
 104

Table 4.3 (continued)
Encapsulated
Primary layer Secondary layer Tertiary layer Bioactive compound References
Interface Stabilizing Material Soy Adsorbed Material High methoxyl – Polyunsaturated fatty Xiang et al.
β-conglycinin pectin acid (flaxseed oil) (2016)
Droplet size, (nm) 5.35 ± 0.13 Droplet Size, (nm) 7.48 ± 0.04
Zeta potential, (mV) –26.7 ± 1.3 mV Zeta potential, (mV) –15 ± 1.0
Emulsion composition 0.5 % v/v soy Continuous Phase volume 0.05%
β-conglycinin and 2% fish oil in w/v of high methoxyl pectin in
citric acid buffer pH-3.0 citric acid buffer pH 3.0
Interface Stabilizing Material Milk Adsorbed Material Beet pectin – Citral flavor Xiang et al.
Proteins (BP) (2015)
Droplet size (nm) Lactoferrin (184.2 Droplet Size(nm)- Lactoferrin BP
± 3.11), α-Lactalbumin (198.8 ± (226.3 ± 3.54), α-Lactalbumin-BP
3.89), β-Lactoglobulin (226.3 ± 3.54) (319.0 ± 3.67), β-Lactoglobulin
(340.9 ± 6.51)
Zeta potential (mV) Lactoferrin Zeta potential(mV)- Lactoferrin
(38.6 ± 0.89), α-Lactalbumin (36.6 ± BP (–13.9 ± 0.46),
0.50), β-Lactoglobulin (36.7 ± 0.57) α-Lactalbumin-BP (–14.7 ± 0.74),
β-Lactoglobulin (–14.9 ± 0.81)
Emulsion composition 0.7 wt % Continuous Phase volume 0.7
protein solution and 10 wt% oil wt% of pectin solution
phase
DH. Lohith Kumar and P. Sarkar
 Encapsulated
Primary layer Secondary layer Tertiary layer Bioactive compound References
Interface Stabilizing Material Whey Adsorbed material Pectin – Probiotic Zhang et al.
protein isolate or sodium caseinate Lactobacillus (2015)
Probiotic concentration 6 %w/v Continuous phase volume 1% w/v salivarius
pectin at pH 3.0
Emulsion composition 1% w/v whey Encapsulation efficiency (%)
protein isolate or sodium caseinate at Whey protein-pectin (91.51 ±
pH 7 4.32), sodium caseinate-pectin
(87.61 ± 1.56)
Encapsulation efficiency (%) Viability of cells log (CFU/mL)
Whey protein-pectin (5.62 ± 0.02),
sodium caseinate-pectin (5.52 ±
0.06)
Whey protein emulsion (78.53 ±
2.40), sodium caseinate emulsion
(77.78 ± 5364)
4  Nanoemulsions for Nutrient Delivery in Food

Viability of cells log (CFU/mL)

Whey protein isolate emulsion
(4.91±0.06), sodium caseinate
emulsion (4.76±0.07)
Interface stabilizing material Adsorbing material Chitosan and – β-carotene Wei and Gao
α-Lactalbumin (LA) or sodium (-) eoigallocatechin-3-­gallate (2016)
caseinate (SC) conjugate (CEC)
Droplet size, (nm) LA (223.7 ± 3.6), Droplet size, (nm) LA-CEC (236.3
SC (257.4 ± 2.1) ± 0.8), SC-CEC (284.0 ± 0.7)
Zeta potential, (mV) LA (–21.0 ± Zeta potential, (mV)
0.9), SC (–19.8 ± 1.1) LA-CEC(+20.3 ± 0.6), SC-CEC
(26.8 ± 0.3)
Emulsion composition 0.8 wt% of Continuous phase volume 1.4 wt
emulsifier and 10wt% of medium % of CEC at pH 7.0
chain triglycerides oil at pH 7.0
105

(continued)
106 DH. Lohith Kumar and P. Sarkar

Table 4.4  Examples of multiple emulsion based encapsulation of bioactive compounds

Encapsulated
Encapsulation Droplet Size bioactive
Phase Emulsifier (Diameter) compound References
Inner aqueous Primary interfacial layer Primary emulsion Rutin Akhtar et al.
phase Polyglyceryl-3 128 nm (quecertin-3-­ (2014)
polyricinoleate Secondary Multiple emulsion rutinoside)
interfacial layer Brij-78 21–26 μm
Inner aqueous Primary interfacial layer Primary emulsion Saffron Esfanjani
phase Whey protein concentrate 436 ± 0.25 nm compounds et al. (2015)
Secondary interfacial Multiple (saffranal,
layer Whey protein- pectin emulsion 536.3 ± picrocrocin
layer 0.18 and crocin)
Inner aqueous Primary interfacial layer Primary emulsion Caffeine Hernández-­
phase Polyglycerol and 0.27 ± 0.01 μm Marín et al.
polyriciniolate fatty acids (2016)
or soy lecithin
Secondary interfacial Multiple
layer Whey protein emulsion 3.18 ±
concentrate-­ 0.1 μm
carboxymethylcellulose-­
whey peptide soluble
complex
Inner aqueous Primary interfacial layer Primary emulsion Magnesium Bonnet et al.
phase Polyglycerol and 1.1 ± 0.3 μm (mineral) (2009)
polyriciniolate fatty acids
Secondary interfacial Multiple
layer Sodium caseinate emulsion 9.2 ±
2.3 μm
Inner aqueous Primary interfacial layer Primary emulsion Lipophilic Li et al.
phase and Oil Polyglycerol and 4.0 μm Vitamin E, (2012)
phase polyriciniolate fatty acids and
Secondary interfacial Multiple hydrophilic
layer Whey protein emulsion Vitamin-B2
isolate (WPI)-low WPI-LMP (83.4
methoxyl pectin complex ± 7.6μm),
(LMP) or whey protein WPI-CGC (69.8 ±
isolate- κ-carrageenan 1.1μm)
complex(CGC)
Inner aqueous Primary interfacial layer Multiple Probiotic Shima et al.
phase (MRS Hexaglyceryl condensed emulsion bacteria (2006)
broth) ricinoleate 11.0 – 27.1 μm (Lactobacillus
Secondary interfacial layer (depending on acidophilus)
Decaglycerol monolaurate process
parameters)
(continued)
4  Nanoemulsions for Nutrient Delivery in Food 107

Table 4.4 (continued)
Encapsulated
Encapsulation Droplet Size bioactive
Phase Emulsifier (Diameter) compound References
Inner oil Primary interfacial layer Primary emulsion Resveratrol Hemar et al.
phase Whey protein isolate, or 1.0–1.4 μm (2010)
gelatin
Secondary interfacial Multiple
layer Sodium caseinate emulsion They
showed bimodal
distribution
(small droplets,
0.1– μm; larger
droplets, 1–100
μm)

a water matrix. Entrapped oil droplets increase the effective volume fraction that
leads to enhancement in viscosity of dispersed phase. There are multiple problems
associated with hydrogel-based encapsulation systems such as flocculation, gravita-
tional separation and coalescence. The oil droplets trapped inside the gel matrix are
susceptible to Ostwald ripening, coalescence and flocculation (McClements and Li
2010). There is considerable scope for hydrogel-based encapsulation in the food
industry especially for high volume entrapment of lipophilic bioactive compounds
in aqueous matrices. The release kinetics of bioactive compounds from the hydro-
gels can be controlled by manipulating the dimensions of the gel matrix. For exam-
ple, release of flavor from the gel matrix is delayed with increased dimension of
hydrogel due to increased path length denied by diffusion to aqueous phase
(McClements et al. 2007).

4.4.1.4  Clustered Emulsions

Clustered emulsions are formulated by controlled flocculation or aggregation of

lipid droplets. Flocculation can be hetero-flocculation (unlike fat droplets) or homo-­
flocculation (similar fat droplets). Flocculation is caused by the repulsion and
attraction between the lipid droplets in an emulsion matrix. A nanoemulsion con-
taining flocculated droplets has different physicochemical properties such as optical
density, stability, appearance, rheology and adsorption in the gastrointestinal tract.
During formulation of functional foods, the final texture decides the possible bioac-
tive compounds that can be incorporated into the matrix. In this way, viscosity and
ingredient composition in the functional food matrix influences the structural design
principles. For example, flocculated nanoemulsion possesses high viscosity com-
pared to non-flocculated nanoemulsions at the same oil droplet concentration due to
large effective volume fraction. Depending on the oil droplet concentration, floc-
culation leads to formation of paste-like or gel-like structures (Aboalnaja et  al.
2016). However, few studies revealed that digestion in small intestine is hindered
108 DH. Lohith Kumar and P. Sarkar

for highly flocculated nanoemulsion compared to non-flocculated nanoemulsion.

This affirms that controlled release and digestion may be possible with clustered
emulsion formulations. Properties of emulsion clusters can be controlled by droplet
size, interfacial properties, number of flocculation, ionic strength, pH, mixing con-
ditions, and emulsion concentrations (Mao and Julian McClements 2012). As dis-
cussed earlier, the principle behind formation of flocculation between similar and
dissimilar lipid droplets are different. By manipulating the steric repulsion balance,
reducing the repulsive force and increasing short range attractive force between the
lipid droplets, it is possible to formulate clustered nanoemulsions. In case of similar
lipid droplets, variation in pH can induce the formation of emulsion droplet clusters,
whereas charged biopolymer coated droplets attract each other and forms clustered
emulsion droplets. If the concentration of one type of droplet increases, then it will
be surrounded by the oppositely charged lipid droplet. Clustered emulsions can be
used to deliver two bioactive compounds at once. However, properties of clustered
emulsions can be useful in masking undesirable flavor or feature of other bioactive
compounds.

4.4.1.5  Solid Lipid Nanoparticles

This type of structuring of nanoemulsions involves the crystallization of oil phase to

improve the functional properties. Tailoring of oil phase through crystallization at
storage temperature enhances the physical stability even at low surfactant concen-
trations (Helgason et al. 2009). Release properties of active compounds differ based
on its location. For example, if the active compound is present in shell portion of the
solid lipid nanoparticles, then it follows burst release initially, followed by rapid
release. Whereas if active compound is present in core, then Fick’s law of diffusion
governs the release kinetics. After formation of nanoemulsions it is allowed for
controlled crystallization of oil droplets. This is an essential step and care should be
taken to avoid the expulsion of bioactive compounds and particle aggregation. Since
the solid lipid particles are aggregated, it promotes the digestion and high adsorp-
tion of bioactive compound in the body (Üner and Yener 2007).

4.4.2  Excipient Emulsions

Excipient emulsions are bio-inactive matrices which entrap bioactive components

but matrices never show bioactivity. However, when excipients reach the gastroin-
testinal tract it helps in adsorption and improves bioaccessibility of the active com-
pound. There are several factors that influence the ability of excipient nanoemulsions
to enhance the bioaccessibility of active compounds such as composition, size and
lipid amount. The concept of excipient emulsions is new in food research, but it
showed potential to be used as a delivery system. In a recent study it was shown that
the bioavailability of curcumin encapsulated in excipient emulsions depended on
4  Nanoemulsions for Nutrient Delivery in Food 109

Lipid bilayer
Hydrophilic inner core

Liposome Nanoemulsion Emulsome

Fig. 4.6  Schematic representation of an emulsome. Emulsions are incorporated into liposome
inner core to achieve functional emulsome

concentration, droplet size, interfacial properties, location of curcumin and struc-

ture (Zou et al. 2016; Aboalnaja et al. 2016).

4.4.3  Emulsomes

Emulsomes are lipoidal bioactive compound carriers and demonstrates both the
properties of emulsion and liposomes. The internal core of the emulsomes is made
up of triglycerides and fats which are stabilized in the form of oil-in-water emulsion
(Fig. 4.6). Due to high internal oil core, emulsomes provide better opportunity to
encapsulate lipophilic bioactive compounds in high concentrations. In a recent
study, curcumin was encapsulated in emulsomes which resulted in stable and water
soluble nanoformulated curcuemulsome. It also significantly extended the bioactiv-
ity and facilitated the effective concentration into targeted cells (Ucisik et al. 2013).

4.5  Synergy of Nanoemulsions and Food Matrices

The essential characteristics of nanoemulsions for using them in food matrices are
their optical clarity and stability. In a general way, food matrices can be categorized
into liquid matrix, solid matrix and semi-solid matrix. Brief description of applica-
tion of nanoemulsions in different food matrices are discussed below.
110 DH. Lohith Kumar and P. Sarkar

4.5.1  Liquid Matrix

In beverage industries, major application of nanoemulsions are as clouding agents

and can be used as delivery systems for flavor, color and other lipophilic nutrients.
Utilization of high level of surfactants, co-surfactants and co-solvents compared to
the oil level for nanoemulsion formulation is suitable for soft drinks and juices
where oil concentration is low. For sausages, desserts and dressing with high oil
concentration, nanoemulsion produced with low concentration of surfactants were
suitable to reach the optimum texture (Rao and McClements 2013). However in
beverage emulsions, “ringing” is the major problem observed due to droplet cream-
ing. The change in droplet size during storage caused by Ostwald ripening is respon-
sible for ringing effect in beverage emulsions. For encapsulation of flavor oil such
as citral in beverages, the droplet concentration should be higher and citral should
be primarily located in the oil phase rather than in aqueous phase (Piorkowski and
McClements 2014). In a recent study, curcumin nanoemulsion fortified milk was
formulated. The group concluded that lipid oxidation can be reduced in milk using
curcumin nanoemulsions (Joung et al. 2016). In another study, lycopene nanoemul-
sions were studied for beverage application and results showed that degradation of
lycopene in the beverage emulsion were stable at both 4 and 20 °C (Kim et  al.
2014). These studies clearly indicated that nanoemulsions could be studied in model
food matrices.

4.5.2  Solid Matrix

Food surfaces can be considered as solid matrices, where antimicrobials, antioxi-

dants and other functional molecules entrapped nanoemulsions can be used to
impact shelf life. In a special case, nanoemulsions were used to formulate edible
coatings for fresh cut surfaces (Zambrano-Zaragoza et al. 2014a). In a recent study,
the use of α-tocopherol nanoemulsion based edible coatings for fresh cut apple pres-
ervation was investigated. They inferred that particle size in the film forming disper-
sion have important implications on the product quality (Zambrano-Zaragoza et al.
2014b). However, more studies are required to evaluate the consumer acceptability
of these products.

4.5.3  Semi-solid Matrix

Cheese, ice cream and yogurt are considered as semi-solid matrices and they have
been used as models to study the efficacy of nanoemulsions. In a study, fish oil
emulsion was used as the fortification agent in processed cheese. They found that
lipid oxidation in cheese samples fortified with emulsions was lower compared with
4  Nanoemulsions for Nutrient Delivery in Food 111

non-encapsulated fish oil. In addition they concluded that use of milk proteins as
emulsifiers are better in elevating “fishy flavor” in processed cheeses (Ye et  al.
2009). Alfaro et  al. (2015) studied fortification of frozen yogurt with purple rice
bran oil nanoemulsion. They found that addition of nanoemulsions increased the
melting resistance of frozen yogurt and survival of lactic acid bacteria was unaltered
compared with unfortified frozen yoghurt. In another study, yogurt was fortified
with ω-3 rich algal oil nanoemulsion and they concluded that fortification of cheese
increased the bioavailability of ω-3 fatty acids compared with bulk oil (Lane et al.
2014).

4.6  Risk Assessments and Toxicology of Nanoemulsions

Emulsifier, droplet size, charge, interfacial composition and concentration of bioac-

tive compounds can be considered as the major factors in risk assessment of nano-
emulsions. Most food grade emulsifiers are anionic in nature, while lauricarginate
and chitosan are cationic emulsifiers. Non-ionic and zwitterionic emulsifiers have
also been used to prepare nanoemulsions due to their low toxicity (McClements and
Rao 2011). In a recent study on toxicological concern of food proteins (whey pro-
tein isolate, soybean protein isolate and β-lactoglobulin), nanoemulsion were pre-
pared and tested in Caco-2 cells. The overall results of toxicity studies were
encouraging as the food proteins stabilized nanoemulsions exhibited low toxicity
than traditional surfactants, suggesting a potential therapeutic application (He et al.
2011).
Droplet size of an emulsion was considered important to evaluate bioaccessibil-
ity of encapsulated compounds in food matrices. It is known that with decrease in
droplet size, bioavailability of functional compounds increases. In addition, nano-
emulsions undergo faster digestion compared to microemulsion, suggesting reduced
toxicity effect on cells (Li and McClements 2010; Yu et and Huang 2012). In a study
conducted by (Yu and Huang 2013), it was evident that compared with microemul-
sion with the same composition, nanoemulsion did not reveal significant toxicity on
Caco-2 cells. However, they observed higher nanoemulsion toxicity on HepG2 cells
compared to microemulsions. In these studies, modified starch and whey protein
isolate were used in nanoemulsion formulation.
Charge is important for immune cell stimulation, entry into cells and toxicity
(Naahidi et al. 2013). Positive charges are more susceptible to stimulate an immune
reaction than neutral and negative charges (Naahidi et al. 2013; Bertrand and Leroux
2012). However, toxicity is directly linked to the concentration of functional mole-
cules for absorption in digestive tract. In a research work carried out by Pinheiro
et  al. (2013) impact of nanoemulsion surface charge on curcumin bioavailability
was evaluated during digestion. They found that positive charge facilitates the
adsorption of anionic lipase and bile salts to the oil-water interface leading to phase
separation. In addition, digestive enzymes will not act effectively on lipid phase
resulting in low curcumin bioavailability. Similarly, interfacial composition also has
112 DH. Lohith Kumar and P. Sarkar

control on bioavailability of curcumin. Supporting to this, a study was conducted on

curcumin bioavailability in multilayer (lactoferrin-alginate) and primary (lactofer-
rin) nanoemulsion matrices. It was concluded that alginate coating modulates the
bioavailability of curcumin through lipid digestion (Pinheiro et al. 2016).
Li et al. (2015) have studied curcumin delivery using nanoemulsion which was
stabilized by β-lactoglobulin. Results showed that nanoemulsion could be used as
targeted delivery systems and demonstrated that curcumin concentrations up to 100
μg/mL were non-toxic to cells. Few special formulations like “NanoSolve” (combi-
nation of CoQ10 and vitamin E in nanoemulsions stabilized by a lecithin or carbohy-
drate matrix) were tried on human volunteers to check their bioavailability. Upon
administration of “NanoSolve” formulation, the bioavailability of CoQ10 was found
to increase fivefold and that of vitamin E was enhanced tenfold when compared
with the pure substances (Wajda et al. 2007). However, the current lack of appropri-
ate tools and knowledge gaps in regard to the potential effects of nanoemulsions
pose a number of limitations to risk assessment.

4.7  Regulations

Regulations for utilization of nanoemulsions in functional food formulations are

dependent on its components such as emulsifier, oil phase and water phase. The
concentration of emulsifier and the other two phases defines the toxicity of the for-
mulation. The critical concentration at which each of the components will be used
in the nanoemulsion formulation must also meet safety regulations (Duvall 2012).
According to Food and Drug Administration (FDA) guideline, individual character-
istics of nanoemulsions such as droplet size, charge, chemical composition and con-
centration will be considered to assess the safety of the nano formulation.
Nevertheless, as per FDA, at present there are no testing requirements (USFDA
2014a, b).
According to an amendment to regulation EU 1169/2011, there is a need to dis-
tinguish between manufactured and naturally occurring nanoparticles used in food
matrices (European Parliament 2011; Stamm et al. 2012). Currently, for the integra-
tion of nanomaterials into food matrices, there is a need to fulfill the food additive
regulation (EU 1333/2008). Specifically, European Food Safety Authority (EFSA)
released a guideline for the risk assessment of nanomaterials in foods as well as
consumer exposure considering their potential toxicity, characterization and bio-
logical fate (Stamm et al. 2012). According to the guidelines if complete digestion
of a nanoparticle in the gastrointestinal tract can be proven so that there is no risk of
potentially absorbed species and bioaccumulation in the human gut, the toxicologi-
cal evidence and regulation of the non-nano form can be used for commercial pur-
poses. This statement is specifically relevant in the case of nanoemulsions, which
are typically formulated with digestible oils and therefore would be exempt from
special toxicological regulations to be placed in the food market.
4  Nanoemulsions for Nutrient Delivery in Food 113

4.8  Challenges and Roadmapping the Future

There are a number of challenges that need to be overcome before nanoemulsions

are more widely used. Identification of suitable food-grade ingredients for formulat-
ing nanoemulsions is the primary concern. Although, nanoemulsions are useful in
functional food formulations, many of the processing methods are either impracti-
cal or expensive to implement on a commercial scale. Few commercially available
food grade nanoemulsion formulations are tabulated in Table 4.5. In addition, there
is a lack of proper regulations and toxicity studies on nanoemulsion based encapsu-
lation systems. Hence, there is a potential concern on the use of nanoemulsions in
food matrices for enhanced bioavailability of phytochemicals due to their
bioaccumulation.
Different food products have been formulated using nanoemulsions technology.
Recently, Central Food Technological Research Institute, Mysuru, India launched
vitamin-E and ω-3 fatty acid enriched ice cream (labelled as NutriIce-creams).
Therefore studies focusing on their biological fate, potential exposure pathways and
bioaccumulation are required. In addition, commercialization of any nanoemulsion
based foods and regulatory hurdles faced by food processors must be addressed if
nanotechnology has to play their part in a competitive economy.

Table 4.5  Commercially available nanoemulsion based formulations

Product Name Company Name Description
Color Emulsions WILD Flavors and Used to encapsulate annatto color, β-carotene,
Specialty apo-8-carotenal, paprika, turmeric
Ingredients, USA (Wildflavors[Internet]).
Aquanova Novasol Aquanova, Encapsulate CoQ10, vitamin A, D, D3, E and K,
Germany ω-3 fatty acids, β-carotene (Silva et al. 2012;
Nanoproject[Internet])
Fabuless DSM Nutritional A nanoemulsion that delays digestion until lower
Products, regions of the small intestine stimulating satiety
Netherlands and reduce food intake (McClements 2015b).
Canola Active Oil Shemen Industries, This technology is called NSSL (Nano-sized
Israel self-assembled structured liquids), which is a
development of minute compressed micelles,
which are called nanodrops. It is fortified with
phytosterols to reduce cholesterol level(Nanoproj
ect[Internet]).
Nano-Sized Self-­ NutraLease Ltd, These are related to the nano-sized vehicles that
assembled Liquid Israel are used as vehicles to targeted compounds such
Structures (NSSL) as nutraceuticals (Nanoproject[Internet]).
Supplements
114 DH. Lohith Kumar and P. Sarkar

4.9  Conclusion

Nanoemulsion based encapsulation systems are finding increasing utilization in

protection of hydrophobic functional molecules in food products. They have been
proven to be suitable matrices for encapsulating and transporting bioactive com-
pounds. High kinetic stability and small droplet size with narrow distribution helps
to improve the bioavailability of encapsulated functional molecules. However, for-
mation of nanoemulsion is dependent on the sensitivity of a functional molecule to
different stress factors such as heat, freezing, and pH.  Different bioactive com-
pounds require unique nanoemulsion design to enhance and protect their functional-
ity. There exists a lacuna in scientific evidence about their biological fate in human
guts and their toxicological safety. In spite of their recognized functionalities,
knowledge gap exists to incorporate them in real food matrices. Hence, there is a
genuine need for in-depth research on the application of nanoemulsions in real food
matrices.

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Chapter 5
Nanocarriers for Resveratrol Delivery

Divya Arora and Sundeep Jaglan

Abstract  There is a current interest in phytoalexin resveratrol due to its vast thera-
peutic effects such as anti-cancer, anti-viral, anti-amyloid antioxidant, anti-aging,
anti-inflammatory, cardio and neuroprotection. Resveratrol, of chemical name
3,5,4-trihydroxy-trans-stilbene, is a naturally occurring polyphenol, which is present
in several dietary sources such as grapes, soybeans, berries, pomegranate and pea-
nuts. However, resveratrol clinical efficacy is limited due to its poor systemic bio-
availability, of less than 1%, which is due to its low aqueous solubility, extensive first
pass metabolism and existence of enterohepatic recirculation. To overcome these
limitations various nanocarriers including polymeric nanoparticles, solid lipid
nanoparticles, liposomes, micelles, and conjugates have been developed. These
nanocarriers enhance the bioavailability of resveratrol due to their ability to modulate
the P-glycoprotein (P-gp), cytochrome P-450 enzymes, and bypassing the hepatic
first-pass effect. This chapter presents recent advances in application of nanocarriers
to deliver resveratrol for modulating its pharmacokinetics and clinical efficacy.

Keywords  Resveratrol • Bioavailability • Nanoformulation • Targeting • Anticancer

5.1  Introduction

Resveratrol (3,5,4′- trihydroxy-trans-stilbene; C14H12O3; Mw 228.25 Da) is a lipo-

philic (log Po/w 3.1) polyphenol present in various plants and plant products, such as
grapes, wine, berries, soybeans, pistachio, and peanuts (Neves et al. 2012; Singh and
Pai 2014c; Summerlin et al. 2015; Varoni et al. 2016). It was first isolated from the
roots of white hellebore (Veratrum grandiflorum O. Loes) in 1940’s (Takaoka 1940),
and later, in 1963, from the roots of Japanese plant Polygonum cuspidatum, where it

D. Arora • S. Jaglan (*)

Quality Control, Quality Assurance & CMC Division, CSIR-Indian Institute of Integrative
Medicine, Canal Road, Jammu 180001, India
Academy of Scientific and Innovative Research (AcSIR),
Jammu Campus, Jammu 180001, India
e-mail: sundeepjaglan@iiim.ac.in

© Springer International Publishing AG 2017 123

S. Ranjan et al. (eds.), Nanoscience in Food and Agriculture 5, Sustainable
Agriculture Reviews 26, DOI 10.1007/978-3-319-58496-6_5
124 D. Arora and S. Jaglan

is produced in response to environmental stress factors such as injury, fungal infec-

tions, ozone exposure and UV irradiation (Langcake and Pryce 1976; Nonomura
et al. 1963). It exists in nature as both cis and trans isomers, although trans form is
pharmacologically active and most abundant in nature. However, due to its photosen-
sitive nature, nearly 80–90% of the trans form undergoes isomerization to cis form
when exposed to sunlight or high intensity white light or ultraviolet (UV) light at 360
and 254 nm (Montsko et al. 2008; Trela and Waterhouse 1996; Vian et al. 2005).
The interest of scientific community in last few years has increased considerably
towards this molecule due to its pleiotropic effects i.e. they have the ability to down-
regulate multiple signaling pathways. It has demonstrated several pharmacological
activities such as anti-cancer (Rai et al. 2016;Yang et al. 2015), antioxidant (Albuquerque
et al. 2015), anti-inflammatory (Liu et al. 2015), neuroprotective (Rege et al. 2014),
cardioprotective (Cheserek et al. 2016), anti-diabetic (Yazgan et al. 2015) (Fig. 5.1) etc.
Infact, it has been found to be responsible for “French Paradox”, which demonstrates
the consumption of red wine decreases the incidence of cardiovascular diseases despite
intake of a high fat diet (Criqui and Ringel 1994; Renaud and de Lorgeril 1992). The
anti-cancer effects of resveratrol may be due to free radicals scavenging, suppression of
cyclooxygenase activity, inhibition of enzymes such as ribonucleotide reductase, DNA
polymerases and protein kinase C (Sirerol et al. 2015; Varoni et al. 2016). It has also
been demonstrated to increase the activity of SIRT 1 (a member of the sirtuin family of

Fig. 5.1  Therapeutic applications of resveratrol for treatment for various diseases (Modified from
Lavu et al. 2008. Drawing was performed using website http://www.servier.com)
5  Nanocarriers for Resveratrol Delivery 125

nicotinamide adenine dinucleotide-­dependent deacetylases) which ultimately results in

improved cellular stress resistance and longevity (Buhrmann et al. 2016; Lavu et al.
2008). The therapeutic use of resveratrol has been described in several reviews and
therefore a detailed discussion is beyond the scope of the chapter.

5.2  Nanocarriers for the Delivery of Resveratrol

Despite, a lot of therapeutic activities of resveratrol it has been associated with poor
bioavailability (less than 1%) due to its poor aqueous solubility (0.03 g/L) and its
extensive metabolism in the intestine and liver called enterohepatic recirculation
(Mattarei et al. 2013; Summerlin et al. 2015; Walle et al. 2004). Due to this entero-
hepatic recirculation, after its oral administration, a peak plasma concentration is
observed after 1 h and a second peak is seen after 6 h (Almeida et al. 2009; Summerlin
et al. 2015). It also undergoes extensive phase I (oxidation, reduction and hydrolysis)
and phase II (glucuronic acid and sulfate conjugation) metabolism to generate the
key metabolites; trans-resveratrol-3-O-glucuronide and trans-­resveratrol-­3-sulfate,
respectively (Gescher and Steward 2003; Kaldas et  al. 2003; Marier et  al. 2002;
Neves et al. 2012). These modifications decrease the cell permeability and resulting
into excretion of resveratrol. To tackle these challenges, various nanocarriers of res-
veratrol such as nanoparticles, liposomes, micelles, conjugates, hydrogels etc. has
been developed and evaluated in pre-clinical and clinical trials (Fig. 5.2, Table 5.1).

Fig. 5.2  Various kinds of nanocarriers used for resveratrol delivery along with their advantages.
The main advantages of developed nanocarriers of resveratrol are biodegradable, biocompatible
and ability for targeting towards specific sites. Moreover, these nanocarriers exhibit enhanced per-
meability and retention (EPR) effect
 126

Table 5.1  Various Nanocarriers developed for resveratrol delivery along with their major outcomes. The developed nanocarriers have been demonstrated to
have better efficacy than the native resveratrol. Moreover, the most of the excipients involved in development of these nanocarriers have been generally
recognized as safe (GRAS) status by FDA
Nanocarrier Main excipients Size (nm) Outcome References
Nanoparticles PS 80, PLA 200 RVT loaded nanoparticles displayed significant da Rocha Lindner et al.
neuroprotection against MPTP-induced behavioral and (2015)
neurochemical changes in C57BL/6 mice.
Liposomes PL 90G, Phospholipid 120 The co-encapsulation of RVT and 5-fluorouracil in Cosco et al. (2015)
Gmbh, Chol liposomes improved their anticancer activity on skin
cancer cells as compared to both the native drugs and the
single entrapped agents.
Nanoparticles Gelatin, glutaraldehyde 294 RVT-GNPs demonstrated enhanced anticancer activity in Karthikeyan et al.
NCI-H460 cells than native RVT by decreasing (2015)
antioxidant status and increased nuclear fragmentation
levels. Morover, RVT-GNPs demonstrated enhanced
apoptosis than native RVT with the decreased Bcl-2,
NF-kB expression and increased lipid peroxidation, Bax,
p53, p21 and caspase-3 protein levels.
Nanoemulsion Vitamin E, sefsol, tween 102 RVT nanoemulsion formulation demonstrated high Pangeni et al. (2014)
80, transcutol P scavenging efficiency using DPPH assay than ascorbic
acid and RVT solution. Further, in vivo pharmacokinetics
studies also demonstrated presence of a greater amount
of RVT in the brain as compared to the RVT solution
(i.n.) and RVT suspension (i.v.).
Liposomes Chol, DPPC 131 Enhanced in vitro cytotoxicity of RVT encapsulated Soo et al. (2016)
liposomes in HT-29 colon cancer cells as compare to
RVT solution.
Nanoparticles Au, Ag 8–21 RVT-AuNPs and AgNPs demonstrated higher Park et al. (2016)
antibacterial activity as compare to native RVT in both
gram positive and gram negative bacteria.
D. Arora and S. Jaglan
Nanocapsules PCL, SMS, PS80 196 The co-encapsulation of RVT and CUR into lipid Coradini et al. (2015)
nanocapsules demonstrated pronounced effects with an
inhibition of 37–55% between day 16 and 22 after
arthritis induction.
SNEDDS Lauroglycol FCC, 56 In vivo pharmacokinetics in Wistar rats studies Singh and Pai (2015b)
Labrasol, Transcutol P demonstrated enhanced AUC about 4.31 fold as
compared to the RVT solution.
Nanoparticles Zein, lysine, sodium 307 In vivo pharmacokinetics study demonstrated in wistar Penalva et al. (2015)
ascorbate rats demonstrated enhanced oral bioavailability of RVT
NPs up to 19.2-fold higher than for the RVT solution.
Further, administration of RVT NPs diminished
endotoxic symptoms, such as hypothermia or
piloerection, and increased the movement of LPS treated
5  Nanocarriers for Resveratrol Delivery

mice as compare with RVT solution.

SMEDDS Ethyl oleate, Tween-80, 50 SMEDDS formulation demonstrated higher antioxidant Chen et al. (2015)
and PEG-400 capacity with less toxicity than native RVT.
Nanoparticles CMCS, Tween-80 155 RVT-CMCSNPs demonstrated enhanced in vivo Zu et al. (2014)
absorption, prolonged duration of action and relative
bioavailability by 3.5 times in rats than that of native
RVT.
S-SNEDDS HPMC, Lauroglycol 212 In vivo pharmacokinetic studies in rats demonstrated Singh and Pai (2015a)
FCC, Transcutol P S-SNEDDS formulation ehnaced AUC0–8 by nearly
1.33-fold as compare to liquid SNEDDS, at a drug dose
of 20 mg/kg.
(continued)
127
 128

Table 5.1 (continued)
Nanocarrier Main excipients Size (nm) Outcome References
Nanoparticles Compritol 888 ATO, 191 In-vivo pharmacokinetic studies in rats demonstrated Singh et al. (2016)
Gelucire approximately 5-fold increase in the bioavailability of
RVT SLN (AUC0→∞ = 3411 ± 170.34 μg/mL/h) as
compared to RVT suspension
(AUC0→∞ = 653.5 ± 30.10 μg/mL/h). Moroover, decrease
in the serum biomarker enzymes (SGOT, SGPT and
ALP) after oral administration of RVN-SLNs was
observed as compared to control and marketed
(SILYBON®) formulations against paracetamol induced
liver cirrhosis.
Nanoparticles TPGS, tristearin, S-100 203 RVT-TPGS-SLN demonstrated higher in vitro Vijayakumar et al.
cytotoxicity and cellular internalization against C6 (2016)
glioma cell lines. In vivo pharmacokinetics in healthy
charles foster rats demonstrated higher AUC (11.12 fold)
and plasma half life (9.37 fold) of RVT-TPGS-SLN as
compare to RSV solution, respectively.
Nanocapsules PCL, Span 60, 150 RVT-nanocapsules reduced cell viability of B16F10 Carletto et al. (2016)
polysorbate 80 melanoma cells, decreased tumor volume, increased
necrotic area and inflammatory infiltrate of melanoma
tumor in mice.
Nanoparticles MCM-48 283 MCM-48-RVT NPs demonstrated enhanced in vitro Summerlin et al. (2016)
cytotoxicity in HT-29 and LS147T colon cancer cell
lines as compare to native RVT.
D. Arora and S. Jaglan
Nanoparticles PEG–PLA 233 RVT-NPs demonstrated comparable or enhanced Jung et al. (2015)
cytotoxicity, apoptotic cell death, 18F FDG uptake and
reactive oxygen species with respect to native RVT.
Nanoparticles Eudragit RL 100 180 In vivo pharmacokinetic studies in rats demonstrated Singh and Pai (2014a)
enhanced AUC0–24 (7.25-fold) of RVT-NPs as compare to
native RVT.
Nanoparticles PLGA 170 In vivo pharmacokinetic studies in rats demonstrated Singh and Pai (2014b)
enhanced AUC0-∞ (10.6-fold) of RVT-NPs as compare to
native RVT.
Nanoparticles CS, avidin, biotin 257–319 In vivo pharmacokinetic studies in kunming mice Bu et al. (2013)
demonstrated improved the drug bioavailability and liver
targeting index RVT NPs as compare to native RVT.
Table Abbreviations: MPTP 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine, RVT resveratrol, PS80 Polysorbate 80, PLA poly(lactide), Chol Cholesterol, PL
5  Nanocarriers for Resveratrol Delivery

90G Phospholipon 90G, i.n. intranasally, i.v. intravenously, DPPC 1,2-dipalmitoyl-snglycero-3-phosphocholine, CUR – Curcumin, PCL poly(Ɛ-caprolactone),
GSO grape seed oil, SMS sorbitan monostearate, SNEDDS self nanoemulsifying drug delivery systems LPS lipopolysaccharide from Salmonella enterica
serovar, SMEDDS self-micro-emulsified drug delivery systems, CMCS carboxymethyl chitosan, S-SNEDDS supersaturable self-nanoemulsifying drug delivery
system, HPMC hydroxypropyl methylcellulose, SLN solid lipid nanoparticles, TPGS D-α-tocopheryl polyethylene glycol 1000 succinate, AUC area under the
curve, S-100 soyaphosphotidyl choline, MCM-48 colloidal mesoporous silica, PEG-PLA polyethylene glycol polylactic acid, FDG fluorodexoyglucose, PLGA
poly (DL-lactide-co-glycolide), CS Chitosan
129
130 D. Arora and S. Jaglan

5.2.1  Nanoparticles

These are the small colloidal particles (preferably less than 200 nm) developed from
biodegradable polymers, lipids or inorganic materials. Various biodegradable poly-
mers have been used in order to deliver resveratrol such as poly(D,Llactic-co-­glycolic
acid) (PLGA), polye-caprolactone (PCL), albumin, gelatin, chitosan etc. These
nanoparticles have several key advantages such as improving the bioavailability by
increasing aqueous solubility, increasing resistance time in the body and ease of
surface modification due to the presence of functional groups for targeted drug deliv-
ery systems (Arora and Jaglan 2016; Mudshinge et al. 2011). Recently, polysorbate
80 (PS80)-coated poly(lactide) nanoparticles of resveratrol were developed in order
to improve the potential neuroprotective effect (da Rocha Lindner et al. 2015). PS80
is a hydrophilic surfactant and has ability to transpose the blood–brain barrier due to
its enhanced absorption via apolipoproteins, apolipoproteins mainly APO E (Kreuter
et al. 2002). The study demonstrated resveratrol -loaded PLA-PS80 nanoparticles
protected against 1-methyl-4-phenyl-1,2,3,6-­ tetrahydropyridine-­induced olfactory
discrimination deficits in mice and prevented the deficit in social recognition ability
induced by intranasal 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine. Further, the
nanoparticle formulation of resveratrol attenuates 1-methyl-4-phenyl-1,2,3,6-tetra-
hydropyridine induced lipid peroxidation.
Karthikeyan et al. developed resveratrol loaded gelatin nanoparticles and demon-
strated enhanced anticancer efficacy than free resveratrol in NCI-H460 cells
(Karthikeyan et al. 2013). Further, resveratrol-gelatin nanoparticles demonstrated
enhanced ROS generation, DNA damage and apoptotic incidence as compare to
native resveratrol. The mechanistic studies demonstrated enhanced apoptosis
induced by resveratrol gelatin nanoparticles was associated with the increased Bax,
p53, p21, caspase-3 protein levels, and decreased Bcl-2 and NF-kB proteins expres-
sion (Karthikeyan et al. 2015). In another study, resveratrol-loaded zein nanoparti-
cles were developed and demonstrated enhanced oral bioavailability of
resveratrol-NPs by 50% as compare to native resveratrol (Penalva et  al. 2015).
Further, administration of resveratrol-NPs daily for 7 days at 15 mg/kg diminished
the endotoxic symptoms induced in mice by the i.p. administration of LPS (lipo-
polysaccharide from Salmonella enterica serovar).
Solid lipid nanoparticles are made of natural, semi-synthetic or synthetic lipids
e.g., highly purified triglycerides, complex glyceride mixtures or waxes dispersed in
water or in an aqueous surfactant solution (Arora and Jaglan 2016; Niu et al. 2016).
These lipids remain in solid state at room and body temperature but degrade in the
intestinal fluid due to the presence of pancreatic lipase (Saneja et al. 2014a). Besides
this, solid lipid nanoparticles additionally incorporate an emulsifier and co-­
emulsifiers like lecithin, pluronics etc., which provides them with the adequate sta-
bility upon dispersion in water (MuÈller et  al. 2000). Recently, solid lipid based
nanoparticulate system of resveratrol were developed in order for the effective treat-
ment of liver cirrhosis (Singh et al. 2016). The study demonstrated oral administra-
tion of resveratrol  - solid lipid nanoparticles decreased the serum biomarker
5  Nanocarriers for Resveratrol Delivery 131

enzymes (serum glutamic oxaloacetic transaminase, serum glutamic pyruvic trans-

aminase and alkaline phosphatase) as compared to control and marketed
(SILYBON®) formulations against paracetamol-induced liver cirrhosis. Moreover,
pharmacokinetic studies demonstrated enhanced bioavailability
(AUC0→∞  =  3411  ±  170.34  μg/mL/h) as compared to resveratrol suspension
(AUC0→∞ = 653.5 ± 30.10 μg/mL/h). In an another study D-α-tocopheryl polyethyl-
ene glycol 1000 succinate coated solid lipid nanoparticles were developed in order
to enhance the circulation time, biological half life and passive brain targeting. In
vitro cytotoxicity against C6 glioma cells demonstrated higher cytotoxicity of
resveratrol-D-α-tocopheryl polyethylene glycol 1000 succinate-solid lipid nanopar-
ticles as compare to native resveratrol. Pharmacokinetic studies after i.v. administra-
tion of resveratrol- D-α-tocopheryl polyethylene glycol 1000 succinate-solid lipid
nanoparticles demonstrated higher area under the curve (~11.12 times) and plasma
half life (~9.37 times) as compare to resveratrol. Further, brain distribution of res-
veratrol- D-α-tocopheryl polyethylene glycol 1000 succinate-solid lipid nanoparti-
cles was found to be 9.23 times higher than that of resveratrol solution which
demonstrated the passive brain targeting potential of solid lipid nanoparticles.
Inorganic nanocarriers such as silica materials and metallic nanoparticles have
also been exploited for resveratrol delivery. Summerlin et al. developed resveratrol
loaded colloidal mesoporous silica nanoparticles and demonstrated enhanced satu-
rated solubility of resveratrol by ~95% (Summerlin et al. 2016). Further, in vitro
cytotoxicity in HT-29 and LS147T colon cancer cell lines demonstrated augmented
cytotoxicity that native resveratrol. In another study, gold and silver nanoparticles of
resveratrol and observed enhanced antibacterial activity against both Gram-positive
and Gram-negative bacteria as compare to native resveratrol (Park et  al. 2016).
Resveratrol  - gold NPs demonstrated effective antibacterial activity against
Streptococcus pneumoniae.

5.2.2  Liposomes

Liposomes are the spherical vesicles composed of cholesterol and natural non-toxic
phospholipids (Allen 1997). They consist of bilayer membrane structure having
central aqueous phase in which therapeutic molecules can be encapsulated. They
have also gained enormous attention for resveratrol delivery due to their biocompat-
ibility, biodegradability and ease of surface modification with targeting ligands
(Akbarzadeh et  al. 2013; Arora and Jaglan 2016). Recently, combinatorial lipo-
somes of resveratrol and paclitaxel have been developed in order to tackle multi-­
drug resistance of paclitaxel (PTX) (Meng et  al. 2016). In vitro cytotoxicity
demonstrated composite liposome could exhibit potent cytotoxicity against the
drug-resistant MCF-7/Adr cancer cells. Further, in vivo studies demonstrated com-
binatorial liposome improved the bioavailability of both resveratrol as well as pacli-
taxel and enhanced drug retention towards tumor. In another study, resveratrol and
5-fluorouracil co-encapsulated liposomes were developed for the potential
132 D. Arora and S. Jaglan

treatment of non-melanoma skin cancer (Cosco et  al. 2015). The study demon-
strated encapsulation of resveratrol and 5-fluorouracil in ultradeformable liposomes
enhanced the cytotoxicity as compare to free drugs and exhibited synergistic anti-
cancer activity on SK-MEL-28 and Colo-38 cells.

5.2.3  Micelles

Polymeric micelles are formed by the self-aggregation of amphipathic monomers,

each containing a hydrophilic and hydrophobic domain (Al-Achi and Lawrence
2013). These amphipathic monomers aggregate at a concentration known as critical
micelle concentration (CMC). The hydrophobic domains comprise the micelle
“core” while the external medium hydrophilic domains form the micellar corona
(Arora and Jaglan 2016). These micelles have ability to avoid opsonization by the
reticuloendothelial system (RES) and thus prolong the circulation times of thera-
peutic agents (Maeda et al. 2000). In a recent study, resveratrol micelles were devel-
oped using methoxy poly (ethylene glycol)-b-polycaprolactone (mPEG-PCL) and
d-α-tocopherol polyethylene glycol succinate (Wang et al. 2015). In vitro cytotoxic-
ity and cellular uptake demonstrated enhanced uptake efficiency of resveratrol by
doxorubicin (DOX) – resistant breast cancer MCF-7/ADR cells, and demonstrated
higher rates of apoptotic cell death. Further, the developed micelles enhanced the
cellular accumulation of doxorubicin downregulating the expression of
P-glycoprotein (P-gp). In another study, combinatorial Pluronic® micelles of resve-
ratrol and curcumin were developed in order to prevent doxorubicin induced cardio-
toxicity (Carlson et al. 2014). In vitro cytotoxicity in ovarian cancer (SKOV-3) and
cardiomyocytes (H9C2) cells demonstrated synergestic effects in SKOV-3 cells
while antagonistic in H9C2 cells. Further, the administration of co-encapsulated
micelles demonstrated alleviation of doxorubicin induced cardiotoxicity through
reduction in apoptosis and reactive oxygen species.

5.2.4  Nanoemulsions

Nanoemulsion is an emulsion system having the nanoscale droplets size (0.1–

500 nm) in which oil or water droplets are finely dispersed in the opposite phase
using a suitable surfactant in order to stabilize the system (Mason et al. 2006; Solans
et al. 2005). These are prepared with the help of oils, surfactants and co-surfactants
and aqueous phase. Various types of oils have been exploited for development of
nanoemulsions such as castor oil, olive oil, Captex 355, Captex 8000, Witepsol,
Myritol 318, Isopropyl myristate, Capryol 90, etc.(Arora and Jaglan 2016; Saneja
et  al. 2014b). Pangeni et  al. developed resveratrol nanoemulsion using vitamin
E:sefsol (1:1) as the oil phase, Tween 80 as the surfactant and Transcutol P as the
co-surfactant in order to improve its efficacy (Pangeni et  al. 2014). Their study
5  Nanocarriers for Resveratrol Delivery 133

demonstrated higher scavenging efficiency using DPPH assay and higher concen-
tration of the drug in the brain after intranasal administration of nanoemulsion. An
another type of nanoemulsion is self emulsifying formulations which emulsify in
gastro intestinal tract (GIT). Lu et al. developed resveratrol self-nanoemulsifying
drug delivery system (SNEDDS) using pomegranate seed oil (PSO) as an oil phase
in order to exert synergistic effects with resveratrol with it (Lu et al. 2015). In vitro
anticancer study against MCF-7 cell line demonstrated enhanced inhibitory rate of
resveratrol SNEDDS about 2.03- and 1.24-fold than that of SNEDDS prepared
using isopropyl palmitate at a concentration of 12.5 and 25 μg/mL, respectively. In
an another study, self-nanoemulsifying drug delivery systems were developed using
Lauroglycol FCC as lipid, and of Labrasol and Transcutol P as surfactants (Singh
and Pai 2015b). The pharmacokinetics studies demonstrated self-nanoemulsifying
drug delivery systems formulation enhanced area under curve about 4.3 fold as
compared to native resveratrol.

5.2.5  Conjugates

Polymer drug conjugates are a new form of nanomedicines in which drugs are cova-
lently attached through the polymer via cleavable bonds that cleaves at specific tumor
specific sites but stable in systemic circulation (Arora and Jaglan 2016; Pang et al.
2014). In a recent study, resveratrol-mPEG and mPEG-poly lactic acid conjugates
were developed in order to overcome its short half life (Siddalingappa et al. 2015).
Pharmacokinetics studies of the conjugate demonstrated improved pharmacokinetic
profiles with significantly higher plasma area under curve, slower clearance and
smaller volume of distribution as compare to native resveratrol. In an another study,
polymeric methoxy-poly(ethylene glycol)-block-poly(ϵ-­caprolactone) resveratrol
conjugates were developed and demonstrate the conjugate improved solubility and
stability of resveratrol as compared to resveratrol alone (Ng et al. 2015).

5.2.6  Hydrogels

Hydrogels (also called an aquagel) are three-dimensional (3-D), polymeric net-

works consisting of crosslinked hydrophilic components and have the ability to pro-
vide local, sustained delivery of resveratrol. Recently, hyaluronic acid-resveratrol
hydrogel conjugates were prepared using chemical crosslinking of oxidized (Oxi)-
hyaluronic acid with resveratrol solution (Sheu et  al. 2013). In vitro cytotoxicity
studies demonstrated the hydrogels were biocompatible and upregulated expression
of type II collagen, aggrecan, and Sox-9 genes; while down-regulating IL-1β,
MMP-1, MMP-3, MMP13 gene expression. Further, these hydrogels has ability to
reduce LPS-induced inflammation and chondrocyte damage.
134 D. Arora and S. Jaglan

5.3  Patents on Resveratrol Drug Delivery Systems

A number of patents have been filed and granted, indicating the potential of resve-
ratrol loaded nanocarriers for improving the efficacy of resveratrol (Table 5.2).

5.4  Conclusion

Resveratrol has emerged as one of the promising nutraceutical with a wide array of
pharmacological activities such as cancer preventive, cardioprotective, antioxidant
anti-inflammatory and neuroprotective. However, its clinical efficacy is hindered
due to its poor systemic bioavailability. As reviewed in the chapter, a number of
nanocarriers have been developed in order to overcome its pharmacokinetic limita-
tions and demonstrated superior outcomes. Further, the success of these nanocarri-
ers can be witnessed by approval of certain products which are in the market such

Table 5.2  Patents filed for the potential of resveratrol loaded nanocarriers for enhancing its
efficacy. The developed nanocarriers have proved to demonstrate the enhanced pharmacological
activity and lesser adverse effects
Patent Reference
Number Main excipients Outcome
CN 105055375A PLGA, PEG, CHOL Co-delivery of doxorubicin and resveratrol
using nanoparticles improves anti-tumor activity
and reverses the drug resistance.
CN 104688715A GMS, sodium The developed SLN of resveratrol has a small
cholate particle size, high drug loading, faster drug
absorption and high bioavailability.
CN 105903033A SBE-β-CD Resveratrol SBE-β-CD complex demonstrated
higher water solubility, inclusion rate, less
adverse effects such as renal toxicity and
hemolysis.
CN 1951369A Lecithin, soybean The developed liposomes of resveratrol are
phospholipid, non-toxic, non-immunogenic, biodegradable,
CHOL, chitosan sustained release and enhance stability in vivo
chloride and pharmacological effects.
CN104225612A CMC The CMC conjugate of resveratrol has
amphipathy, and can be self-assembled in water
to form a micelle and can encapsulate a
hydrophobic antitumor drug, so that the water
solubility of drugs is increased. Further the oral
absorption of the in the gastrointestinal tracts
can be increased, and the bioavailability of
drugs can be improved.
Table Abbreviations: PLGA poly(dl-lactide-co-glycolide), CHOL cholesterol, PEG polyethylene
glycol, GMS glyceryl monostearate, CMC carboymethyl chitosan, SBE-β-CD sulfobutyl ether-
beta-­cyclodextrin.
5  Nanocarriers for Resveratrol Delivery 135

as Abraxane (paclitaxel), Lipusu (paclitaxel), Doxil (doxorubicin), DepoCyt (cyta-

rabine), Onco-TCS (vincristine) etc. Moreover, these nanocarriers have been fabri-
cated using GRAS (generally recognized as safe) excipients by FDA. However, in
order to realize the full potential of resveratrol nanoformulations, more comprehen-
sive pre-clinical and clinical evaluations are desired.

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Chapter 6
Potential of Milk Proteins
as Nanoencapsulation Materials in Food
Industry

Amrita Poonia

Abstract  A number of synthetic polymers (e.g. polyacrylamide, polyamides, poly-

phenylesters and polyurethanes) have been used in biomedical and pharmaceutical
sector (Reis et al. 2006). But these polymers cannot be used in food industry that
require food grade that is generally regarded as safe ingredients. The toxicity is
more likely to be associated with synthetic polymers. There have been some con-
cerns about potential limitations on the patentability of nanotechnology, many more
commentators have expressed the opposite concern that there are too many nano-
technology patents that will lead to an overlapping set of patent rights. There is also
a need for regulatory framework capable of managing any risks associated with
implementation of nanoparticles in food technology.
We reviewed that milk proteins possess a number of functional properties that
make them important for conventional and novel dry delivery systems. The major
advances of the past year in harnessing milk proteins for novel health-promoting
delivery applications are mainly in nanosizing, conjugation, crosslinking and target-
ing. The major points are (1) Novel milk-protein nanoparticles were used for solu-
bilizing and protecting hydrophobic nutraceuticals in clear systems, for targeting
gastric tumors, utilizing the natural digestibility of caseins, (2) New cold-gelation
based vehicles for probiotics or protein-drugs were introduced, based on different
crosslinking agents, like rennet, transglutaminase, and genipin, (3) Casein hydro-
gels have a number of favorable properties like high hydrophobicity, good biocom-
patibility in oral delivery application, lack of toxicity and availability of reactive
sites for chemical modifications, (4) Casein floating beads helps to increase the resi-
dence time of drugs in the stomach based on its emulsifying and bubble-forming
properties, (5) Hydrophobically-modified blood serum albumin was introduced as a
new-nanoencapsulator for hydrophobic drugs. In photodynamic cancer therapy
blood serum albumin conjugated magnetic nanoparticles were used. In combination

A. Poonia (*)
Centre of Food Science & Technology, Institute of Agricultural Science, Banaras Hindu
University, Varanasi 221005, Uttar Pradesh, India
e-mail: dramritapoonia@gmail.com; amritapoonia@yahoo.co.in

© Springer International Publishing AG 2017 139

S. Ranjan et al. (eds.), Nanoscience in Food and Agriculture 5, Sustainable
Agriculture Reviews 26, DOI 10.1007/978-3-319-58496-6_6
140 A. Poonia

with lactoferrin, they can be successfully used in challenging targeting tasks, like
crossing the blood-brain-barrier.

Keywords  Caseins • Nanostructures • Whey proteins • Bioavailability • Bioactive

compounds

6.1  Introduction

The use of biodegradable polymers for the administration of pharmaceuticals and

biomedical agents has increased significantly during the past decade. Biodegradable
polymers can be either natural or synthetic. The major advantages of synthetic poly-
mers over natural polymers are that they can be designed to give a wide range of
desirable properties. But the toxicity is more likely to be associated with synthetic
polymers. Therefore, a safer carrier has been demanded. Natural polymers may gen-
erally be considered safer than synthetic polymers. Thus, natural polymers have
certain advantages as drug delivery carriers (Lewis 1990).
Natural polymers have many advantages as drug delivery carriers (Lewis 1990).
Because of their high nutritional value and excellent functional properties, includ-
ing emulsification, gelation, foaming and water binding capacity, food based pro-
teins plays an important role in drug delivery systems. They also have the ability to
interact with a wide range of active compounds via functional groups on their poly-
peptide primary structure, thus offering a variety of possibilities for reversible bind-
ing of active molecules and for protecting them until their release at the desired site
within the body (Chen and Subirade 2008). Proteins are metabolizable; hydrolysis
of food proteins by digestive enzymes generates bioactive peptides that may exert a
number of physiological effects in vivo, for example, on the gastrointestinal, cardio-
vascular, endocrine, immune and nervous systems (Panyam 2003). Proteins also
represent good raw materials due to low toxicity of the degradation end products.
The protein-based nanoparticles are particularly interesting because they are rela-
tively easy to prepare and their size distribution can be monitored (Chen et al. 2006).
Various modifications in the protein matrix allow them to form complexes with
other biopolymers, particularly polysaccharides as a base for several nanoparticles.
Also, protein-based nanoparticles can conjugate nutrients via either primary amino
groups or ionic and hydrophobic binding.
Milk of different species contains 30–36 g/L protein. The amount of milk pro-
teins varies according to the breed, stage of lactation, health of animal and feed of
the animal. Milk proteins are subdivided into two categories i.e. caseins, which
represent approximately 79% of the total proteins and whey proteins ranges approx-
imately 19% of the total protein (Topel 2004). The exact composition of milk pro-
tein is given in (Table 6.1). Milk proteins are structurally and chemically versatile
biopolymers with high nutritional value and safe for consumption. They can also be
used as carriers of hydrophobic molecules or ions and are excellent interfacial agent
6  Potential of Milk Proteins as Nanoencapsulation Materials in Food Industry 141

Table 6.1  Classification and physical- chemical properties of bovine milk proteins (Walstra et al.
1984)
Concentration in milk Proportion of total
Component (g/kg) protein (%)
Total milk protein 32.7 100.0
Caseins 26.0 79.5
αs1-Casein 10.0 30.6
αs2-Casein 2.6 8.0
β-Casein 9.3 28.4
γ -Casein 0.8 2.4
κ-Casein 3.3 10.1
Whey proteins 6.3 19.3
β-Lactoglobulin 3.2 9.8
α-Lactalbumin 1.2 3.7
Blood serum albumin 0.4 1.2
Immunoglobulins 0.7 2.1
Various minor proteins 0.8 2.4
Fat globule membrane proteins 0.4 1.2

used in the formation and stabilization of emulsions containing hydrophobic bioac-

tives. They also have a unique property to form covalent or electrostatic complexes
with molecules of interest to entrap bioactives through the formation of gels. Various
functional properties of milk proteins are listed in Fig. 6.1. This chapter focuses on
the use of milk proteins as agents of encapsulation and for the transport of bioac-
tives. The main objective of this chapter is to highlight that milk proteins occupy a
specific niche among other biopolymers such as alginate, gum, and kappa- carra-
geenan which are frequently used as encapsulating devices.

6.2  Need of Milk Proteins-Based Nano Particles

Milk proteins are natural materials with high nutritional value and excellent func-
tional and sensory properties. In addition, they have many structural features and
functionalities that make them suitable for the construction of nano materials, where
interactions can be controlled in a very precise way to modulate functionality. The
potential of milk proteins as natural nano-vehicles for bioactive compounds has
already received considerable research attention (Radha et al. 2014). Casein micelle
has been designed by nature itself as a self-assembled nano scale system that deliv-
ers calcium and protein in dairy foods. Similarly, whey proteins have been designed
to bind and transport hydrophobic molecules. Milk fat globule membrane material
has been found to be a suitable material for making liposomes (Radha et al. 2014).
Nano-tubes and nano-fibrils can be produced from whey proteins using enzymatic
and heat treatments.
142 A. Poonia

Good
sensory
attributes

High
Self-
nutritional
assembly
value

Functional
Properties
Surface
Gelatin
activity

Binding
Binding
hydrophobic
metal ions
molecules

Fig. 6.1  Functional properties of milk proteins that can be exploited to modify and enhance tex-
tural and sensory characteristics of foods

Nano-particles are the structures with a dense polymeric network in which active
molecules can be dispersed (Dasgupta et al. 2017; Shukla et al. 2017; Walia et al.
2017; Balaji et  al. 2017; Maddinedi et  al. 2017; Sai et  al. 2017; Ranjan and
Chidambaram 2016; Janardan et  al. 2016; Ranjan et  al. 2016; Jain et  al. 2016;
Dasgupta et al. 2016). A number of synthetic polymers (e.g. polyacrylamide, poly-
amides, polyphenylesters and polyurethanes) have been used in biomedical and
pharmaceutical sector (Reis et al. 2006). But these polymers cannot be used in food
industry that require food grade that is generally recognized as safe (GRAS) ingre-
dients. Due to their various functional properties and high nutritive value, proteins
are GRAS foods and widely used in food industry. Recently the various structural
and functional properties of milk proteins have been reviewed (Kimpel and Schmitt
2015). Various properties like the ease in preparation and fractionation on industrial
scale and unique functional properties makes them suitable for use them as a func-
tional protein in formulation of various foods. Milk proteins are used as a delivery
vehicle for bioactive materials also (Guilherme et al. 2014).
6  Potential of Milk Proteins as Nanoencapsulation Materials in Food Industry 143

6.3  M
 ilk Protein Properties Facilitating Their Use
for Delivery Tasks

Milk proteins are widely available, inexpensive, natural and GRAS raw materials
with high nutritional value and good sensory properties. They have many structural
and functional properties which make them highly suitable as vehicles, or as com-
ponents for the construction of vehicles for delivering various bioactives. Caseins
αs1, αs2, and β- naturally bind calcium, as well as calciumphosphate nanoparticles,
via their serine–phosphate residues. Milk proteins also bind hydrophobic molecules
by several mechanisms, mainly hydrophobic interactions, van der Waals attraction
and hydrogen bonds. The amphiphilic structure of most milk proteins confers excel-
lent surface properties. Their ability to adsorb at oil–water interfaces and stabilize
emulsions is influenced by their structure, flexibility, state of aggregation, pH, ionic
strength (particularly calcium ions) and temperature. Some of the major milk pro-
teins are natural self-assemblers, and co-assemblers. Caseins are naturally orga-
nized in micelles, which are spherical clusters of 50–500 nm, held together mainly
by hydrophobic interactions, and by calcium-phosphate nanoclusters, bridging
between their serine–phosphate residues. They have excellent gelation properties
(e.g. acid or rennet curd formation of caseins) and heat induced gelation of whey
proteins or of total milk proteins. Applications of milk proteins as nano- vehicles in
food industry are given in (Table 6.2).
Caseins have apparently evolved as proline-rich proteins to have an open tertiary
structure which is easily accessible to gastric proteases. This may serve as a simple
principle for targeting the stomach, as we have recently proposed for oral drug
delivery for gastric diseases, using β- casein. Milk proteins have ability to interact
with other polymers via covalent conjugation and non-covalent interactions. They
also have shielding and protective properties. The proteins form a shield by adsorb-
ing to the oil–water interface or by binding, entrapping or coating a bioactives,
essential for protecting the encapsulated bioactives. They can also control content
accessibility to digestive enzymes, and consequent bioavailability. Firstly, the struc-
ture or matrix formed by the milk proteins, with or without additional components,
may form a barrier against diffusion and escape of the encapsulated bioactives and
secondly, against inward access of digestive enzymes.

6.3.1  Caseins

Milk is rich in protein and has nine essential amino acids. Casein and whey proteins
are the main proteins which are cheap, non-toxic, easily available and highly stable.
It is GRAS food product and biodegradable in nature. The pH –responsive gel
swelling properties makes it useful for the controlled release. Caseins acts as a
144 A. Poonia

Table 6.2  Techniques and use of milk proteins as a wall materials for encapsulation of food and
drug lipophilic biocomponents
Lipophilic bioactive Techniques of
components encapsulation Wall materials References
Ω-3 fatty acids Oil-in-water Whey protein isolate Salminen et al.
emulsions (2013)
Spray drying Whey protein Umesha et al.
concentrate (2015) and
Gokmen et al.
(2011)
Essential oils Molecular inclusion Whey protein Barros
concentrate -Fernandes et al.
(2014)
Conjugated linoleic acid Spray drying Whey protein Jimenez et al.
concentrate (2008)
Vitamin B12 Hydro-gels Casein Song et al.
(2009)
(−)-Epigallocatechin-3-­ Form nanoparticles of Milk proteins Shpigelman
gallate, the major catchin in diameter smaller than et al. (2012)
green tea 50 nm
Resveratrol Whey protein isolates Liang et al.
(3,5,4¢-trihydroxystilbene), (2010)
a natural polyphenolic
compound found in grapes

Flavor compounds, Binding Whey proteins Diarrassouba

hydrophobic and et al. (2013),
hydrophilic vitamins (Le Maux et al.
(vitamin D3, vitamin E and 2012), Liang
vitamin B9), polyphenols et al. (2011) and
(resveratrol and curcumin, Zorilla et al.
catechins), fatty acids and (2011)
minerals (iron)
Flavor compounds, Bottom – up approach Whey proteins Giroux and
hydrophobic vitamins Britten (2011),
(vitamin E), polyphenols Gong et al.
(curcumin, catechins, (2009),
quercetin, kaempferol and Gulseren et al.
rutin), drugs and minerals (2012a) and
(zinc) Shpigelman
et al. (2012)
Hydrophobic vitamins Hydrogel/hydrogel Whey proteins Betz et al.
(vitamin A, vitamin E), particles (2012), Doherty
flavonoids (anthocyanin), et al. (2011) and
cells (probiotics, yeasts) Liang et al.
and minerals (iron) (2010)
(continued)
6  Potential of Milk Proteins as Nanoencapsulation Materials in Food Industry 145

Table 6.2 (continued)
Lipophilic bioactive Techniques of
components encapsulation Wall materials References
Hydrophobic vitamins Emulsions Whey proteins Hemar et al.
(vitamin A, vitamin D3, (2010), Hong
vitamin E), fish oil, et al. (2012),
essential oils and Liang et al.
polyphenols (resveratrol) (2010) and
Tippetts et al.
(2012)
Flavor compounds, Binding Casein fractions and Anema and de
flavonoids, minerals (iron) casein micelles Kruif (2012),
and other proteins Raouche et al.
(2009), Sahlan
and Pramadewi
(2012) and
Sangeetha and
Philip (2012)
Polyphenols (curcumin, Bottom- up approach Casein fractions and Ma et al. (2012),
tannin), hydrophobic casein micelles Saiz-Abajo et al.
vitamins (vitamin A, (2013), and
vitamin D2, vitamin D3), Shapira et al.
fatty acids and drugs (2012)
Probiotic cells Top-down Hydrogel/ Casein fractions and Heidebach et al.
hydrogel particles casein micelles (2009a, 2009b)
approach
Hydrophobic vitamins Top-down approach Fractions and casein Cornacchia and
(vitamin A, vitamin D3), Emulsion micelles Roos (2011),
fish oil, essential oils and Hemar et al.
polyphenols (resveratrol) (2010),
Matalanis et al.
(2012) ann
Tippetts et al.
(2012)
Thiamine Entrapment Whey protein Bedie et al.
isolates-low (2008)
methoxyl pectin
β-carotene Nano-particles Casein and dextran Pan et al. (2007)
lyophilised and the
freeze-dried
Omega-3 fatty acids Titrating sodium Re-assembled casein Zimet et al.
caseinate solution micelles (2011)
with ethanolic
solution of
docosahexaenoic acid
Hydrophobic nutraceuticals Entrapment β -casein micelles Danino et al.
(2009)
(continued)
146 A. Poonia

Table 6.2 (continued)
Lipophilic bioactive Techniques of
components encapsulation Wall materials References
Hydrophobic bioactive Entrapment in β Hydrophobic Zemit and
materials –lactoglobulin-pectin bioactive materials Livney (2009)
nanoparticles
Carotene Electrospraying Whey Lopez-Rubio
proteinconcentrate and Lagaron
(2012)
β- Carotene and lutein Freeze-dried Whey protein isolate Lim et al.
emulsions as an emulsifier (2014)
Conjugated linoleic acid Spray drying Whey protein Jimenez et al.
concentrate (2008)

shield against ultra violet absorbance properties i.e. 200–300 nm (Korhonen 2003).
The caseins are synthesized exclusively in the mammary glands, suggesting that
one of their functions is to provide amino acids required for the development of the
neonate (Thompson et  al. 2009). Besides this function, caseins allow milk to be
supersaturated in calcium phosphate, due to their capacity to bind divalent and mul-
tivalent ions. Due to this property, casein micelles are natural vehicles for calcium
and phosphate delivery to newly borns (Livney 2010; Thompson et al. 2009). Casein
micelle has been designed by nature itself as a self-assembled nano scale system
that delivers calcium and protein in dairy foods.
Re-assembled casein micelles can be prepared from casein or sodium caseinate.
β- Casein is unstructured amphiphilic protein that self-assemble into micelles.
Linear – β-casein and globular lysozyme have been used to prepare nanoparticles
with simple process. The two proteins form polydisperse electrostatic complex
micelles in the pH range of 3.0–12.0 at a molar ratio of β – casein to lysozyme 0.4
β – casein/lysozyme.
β- Casein is ampiphilc protein and can able to self-assemble into micelles. By
using a simple process β –casein and globular lysozyme have been used to prepare
nano-particles. To form this electrostatic complex micelles these two proteins were
mixed in the ratio of β – Casein to lysozyme 0.4 at the pH range 3.0–12.0 at pH large
particles (300 nm) and at acidic pH small particles (100 nm) (Pan et al. 2007).

6.4  U
 nique Features of Caseins That Claim It to Be Used
in Food Grade Nanoparticles

Caseins are open structured and rich in phospho-proteins. They vary in number and
sequence of amino acids, number of phosphorus atoms, proline and carbohydrate
contents. They also have different hydrophilic and hydrophobic domains which help
6  Potential of Milk Proteins as Nanoencapsulation Materials in Food Industry 147

Excellent substrates for

Rich in
cross linking by
phosphoproteins Varies in number &
transglutaminase
sequence of amino acids, no.
of phosphorous atom
Low level of secondary
and tertiary structures

Different hydrophilic &

hydrophobic domains

Stable under GI
environment
Caseins
Ability of shelf assembly in
to natural simulated

Colloidal inability can Micelles have porous

induced by milk clotting structures that retains
water

Able to withstand the

processing treatments

Fig. 6.2  Milk contains several proteins with unique and diversified functional properties. Unique
features of caseins that claim it to be used in food grade nanoparticles

in conformational changes in solutions. They have ability of shelf-assembly into

natural or artificially simulated miscelles. The formed micelles have porous struc-
ture that retains 2 g water/g protein. Casein micelles can withstand the processing
treatments like heat treatment. Colloidal inability of these micelles can be induced
by using milk clotting enzyme and addition of acids. Casein micelles are stable
under gastrointestinal environment and improve their use as nano-vehicles in food
industry. Caseins have low levels of secondary and tertiary structures and acts as
excellent substrates for cross-linking by transglutaminase. Unique features of
caseins that claim it to be used in food grade nanoparticles has discussed in Fig. 6.2.

6.5  Casein Based Nano-Formulations

The main interest in developing and using casein based nano- formulations in food
industry is the fact that they can exhibit new and improved physical, chemical and
biological properties, phenomena and functionality of food products. The ultra
small size of nanostructures associated with the chemical composition and surface
structure provides not only unique features and huge potential applications but also
potential toxicological properties. Casein nano-formulations are useful in delivery
of nutraceuticals and synthetic drugs via enzymatic crosslinking, graft copolymer-
ization, heat-gelation and polyelectrolyte ionic complexation. It can be concluded
148 A. Poonia

that casein-based formulations are promising materials for controlled drug delivery.
The incorporation of nanostructures into final food products improves different
properties: protection and stability of functional food ingredient, bioavailability and
shelf-life improvement, development of new consumer sensation and efficient deliv-
ery of bioactive substances into biological systems. The most widely applied nano-
carriers consist of natural molecules, such as lipids, proteins or polysaccharides.
The reason for their wide application is based mainly on the excellent biocompati-
bility presented by such carriers. Nevertheless, these vehicles are also able to over-
come the harsh conditions that food products are submitted to during digestion
allowing the release of intact functional ingredients in desired sites.

6.5.1  Casein Nano Films/Coatings

Casein films are of growing interest because they are natural origin and easily bio-
degradable. The main advantage of casein films is that they have high tensile
strength which makes them suitable as coatings for tablets. They are also suitable
for immediate release and found to be a significant factor in controlling drug release.
Casein nano-coatings serves as moisture, lipid and gas barriers as well as carriers of
agents like colors, flavors, antioxidants, nutrients and antimicrobials and could
increase the shelf life of manufactured foods, even after the packaging is opened
(Qureshi et al. 2012). Casein micelles are in effect nano-capsules created by nature
to deliver nutrients, such as calcium, phosphate and protein to the neonate. Re-
assembled casein micelle can provide partial protection against ultra violet light-­
induced degradation to vitamin D2 contained in them. They are useful as
nano-vehicles for entrapment, protection and delivery of sensitive hydrophobic
nutraceuticals within food products. Diak et al. (2007) used casein as a film former
for tablet coating with the help of different water soluble and insoluble plasticizers.
They used diltiazem hydrochloric acid core tablets that were coated with casein
using a pan coater and the efficacy of four different plasticizing agents (glycerol,
triethyl citrate, dibutyl sebacate and oleic acid) in producing a continuous tablet
coat was evaluated. They reported that, only those films formed using oleic acid
were capable of producing a continuous and acceptable coat. So, casein/oleic acid
coatings with no post-coating heat treatment may be suitable for immediate release
coatings whereas the effect of post-coating heat treatment was found to be a signifi-
cant factor in controlling drug release. Due to these properties, casein can be con-
sidered as a potential film former for the coating of pharmaceutical dosage forms.

6.5.2  Casein Nano Composites

Nanocomposites basically provide a highly versatile chemical functionality and

therefore they are used for the development of high barrier properties. They help in
keeping the food products fresh, devoid of any microbial infestation for a
6  Potential of Milk Proteins as Nanoencapsulation Materials in Food Industry 149

sustainable amount of time. They usually act as gas barriers in order to minimize the
leakage of carbon dioxide from the bottles of carbonated beverages. Food manufac-
turing industries can replace expensive cans and heavy glass bottles by using the
nanocomposites to layer their bottles in order to prevent the leakage. In case of food
packaging they not only protect food but also increase shelf life of food products
and solve environmental problems reducing the necessity of using plastics. Most of
packaging materials are not degradable and current biodegradable films have poor
barrier and mechanical properties. So these films can replace traditional plastics and
helps to manage worldwide waste problem. Due to their edibility, milk proteins and
their multiple assemblies constitute ideal drug carriers for an oral-delivery system
and several pharmaceutical projects are already ongoing. Casein drug composites
have more biodegradability then the pure drug. Binding in casein solutions showed
increase in drug solubility then the normal proteins binding. Presence of casein in
drug composites decreases the extent of swelling of matrices and accelerates the
rate of erosion without changing the dissolution medium infiltration rate. Due to the
complex formation between drug and casein, the solubility of the drug can also
enhanced by sodium caseinate. The compressed physical mixtures of ibuprofen
with acid casein resulted in a significant retardation in drug dissolution compared to
the corresponding mixtures with sodium caseinate. Acid casein resulted in more
viscous solutions and more rigid gels at a given concentration than sodium caseinate
thus lowering the effective solubility and diffusivity of the drug. These observations
are consistent with the lower dissolution rate of the acid form of the protein (Gubbins
et al. 2006). The inclusion of casein, either as the acid or sodium salt form, was
found to significantly modify the release of the acidic drug diclofenac from
hydroxypropylmethylcellulose-­based matrices.
Jianzhong Ma et al. (2013) used Transmission Electron Microscopy to determine
the morphology and size distribution of the casein-based latex particles. It could be
seen that the latex particles in the absence of silica Fig. 6.3a was about 60 nm in size
with even distribution However, the particle size of the casein-based silica nano-­
composite particles Fig.  6.3a approximated to 100 nm, which indicated that the

280 5
Elongation at break

260
Tensile strength b
Elongation at break (%)

Tensile strength (MPa)

240 4

220

200
3
180

160
2
4 5 6 7 8 9 10
TEOS content (%)

Fig. 6.3 (a) Morphology of casein-based nano-composite latex particles, (aʹ) casein-based latex
particles in the absence of silica and (b) film properties of casein-based silica nano-composite as a
function of Tetraethyl orthosilicate (TEOS) content (Error bar indicated SD, n = 2). (Jianzhong Ma
et al. 2013)
150 A. Poonia

latexes were successfully encapsulated by the silica outer layer. The composite latex
particles displayed regular sphere in shape with evident core–shell structures, and
the particles were almost uniformly distributed in size.

6.5.3  Casein Hydrogels

Casein hydrogels are highly porous & can easily be tuned by controlling the density
of cross-links in the gel matrix and the affinity of the hydrogels for the aqueous
environment in which they are swollen. Their porosity also permits loading of drugs
into the gel matrix and subsequent drug release. The benefits of hydrogels for drug
delivery may be largely pharmacokinetic – specifically that a depot formulation is
created from which drugs slowly elute, maintaining a high local concentration of
drug in the surrounding tissues over an extended period, although they can also be
used for systemic delivery. Casein hydrogels have a number of favorable properties
like high hydrophobicity, good biocompatibility in oral delivery application, lack of
toxicity and availability of reactive sites for chemical modifications.
Biocompatibility of casein hydrogels is promoted by the high water content of
hydrogels and the physiochemical similarity of hydrogels to the native extracellular
matrix. They are also relatively deformable and can conform to the shape of the
surface to which they are applied. The muco- or bioadhesive properties of some
hydrogels can be advantageous in immobilizing them at the site of application or in
applying them on surfaces that are not horizontal.
Several limitations of these casein based hydrogels have also been reported.
They have low tensile strength which limits their use in load-bearing applications
and can result in the premature dissolution or flow away of the hydrogel from a
targeted local site. This limitation may not be important in many typical drug deliv-
ery applications (e.g. subcutaneous injection). The high water content and large
pore sizes of casein based hydrogels often result in relatively rapid drug release,
over a few hours to a few days. Some hydrogels are sufficiently deformable to be
inject able and these issues significantly restricts the practical use of hydrogel-based
drug delivery therapies in the clinic.

6.5.4  Casein Floating Beads

The emulsifying properties of casein caused acid bubbles incorporation and help in
formation of large holes in the beads. This high porosity of the matrix helps the
beads properties and in drug loading, drug release and floatation. Casein floating
beads are suitable for the inexpensive formation of air reservoirs for floating sys-
tems. They are also able to increase the residence time of drugs in the stomach based
on its emulsifying and bubble-forming properties. Due to its emulsifying properties
casein causes incorporation of air bubbles and formation of large holes in the beads
6  Potential of Milk Proteins as Nanoencapsulation Materials in Food Industry 151

that act as air reservoirs in floating systems and serve as a simple and inexpensive
material used in controlled oral drug delivery systems. Casein floating beads
increases the residence time of drugs in the stomach based on its emulsifying and
bubble-forming properties. Therefore, casein seems to be a material suitable to the
inexpensive formation of an air reservoir for floating systems. (Bulgarelli et  al.
2000) prepared controlled release beads of casein–gelatin by emulsification solvent
extraction method and cross-linked with d, l-glyceraldehyde in an acetone-water
(3:1) mixture (v/v). Casein floating beads were also prepared to enhance the resi-
dence time of drugs in the stomach based on its emulsifying and bubble-forming
properties (Elzoghby et al. 2011).

6.5.5  Casein Nano-Particles

Nanoparticles serve several purposes in the processing of food. They help in improv-
ing the food’s flow property, colour, and stability. They also help in reducing the leak-
age of moisture, keeping the food fresh for a longer time. Nanoparticles that helps in
selective binding and can remove the pathogens and chemicals from food. Casein
microspheres are relatively inexpensive; they have better amphiphilicity and good dis-
persibility in aqueous systems, and they form uniform spherical structures. Particle
amphiphilicity is important for post-synthesis drug loading as well as for easy wetting
and rapid reconstitution in aqueous solutions. Due to long term stability, high drug
payloads, casein microspheres are used as an alternative to albumin as a matrix for
microsphere drug carriers. Huppertz and de Kruif (2008) reported that casein micro-
spheres as inexpensive, with better ampibhicity and good dispensability in aqueous
system. Some advantages of casein nanoparticles are safety and non- cytotoxicity of
co-assembled milk proteins, good alternative for nanoparticles composed of lipids,
which require the use of organic solvents or surfactants for their fabrication, ability to
meet the growing demand for additive-free foods. They can be used as encapsulating
materials in infant formulas, a market with spectacular global growth. The annual
growth of the worldwide production of infant formulas, estimated at 11% from 2010
to 2014, is predicted to increase to over 20% due the very rapid growth of the Asiatic
market (Blanchard et al. 2013). Their reversibility allows controlled disassembly, a
fundamental step for targeted release and cross-linked casein microspheres are also
resistant to proteolytic enzymes and thus stable in the gastrointestinal tract and conse-
quently could be used for sustained release oral preparations.

6.5.6  β-Casein-Based Nanoparticles

Nanoparticles are easily dispersed in oil-based suspensions used in different prod-

ucts such as the delivery of omega-3 from fish oils. Colloidal particles and nano-
emulsions could be used as delivery systems for micronutrients and nutraceuticals
152 A. Poonia

(Chen et  al. 2006). β- Casein is the major milk protein component and is easily
self-assemble into micellar structure by intermolecular hydrophobic interactions
due to its amphiphilic nature, which is a suitable feature for the application as deliv-
ery carriers. (Pan et al. 2007) studied the stabilization of casein nanoparticles by
self-assembly of β- casein and lysozyme and then gelation of lysozyme by heat to
entrap casein in the gel. The nanoparticles thus formed had a spherical shape and
their sizes depended on the pH of the heat treatment (100 nm and 300 nm at pH 10.0
and 5.0, respectively).
Being an edible material, β-casein can be used as a drug carrier for an oral-­
delivery system. Shapira et al. (2012) used some hydrophobic chemotherapeutics
such as mitoxantrone, vinblastine, irinotecan, docetaxel and paclitaxel in β- casein
micelles for target-activated release of drugs for oral delivery application. They
found that with digestion of casein with pepsin, paclitaxel retained its cytotoxic
activity to human N-87 gastric cancer cells, whereas β- casein -paclitaxel nanopar-
ticles were non-cytotoxic without prior simulated gastric digestion. Because of the
gastric digestibility of β- casein, it can be used for targeting stomach tumors.

6.5.7  Nano-Capsules

Nanostructured caseins show promise as active vectors due to their capacity to

release drugs. Their subcellular size allows relatively higher intracellular uptake
than other particulate systems. They can improve the stability of active substances.
They are biocompatible with tissue and cells when synthesized from materials that
are either biocompatible or biodegradable. Other advantages of nanostructured
caseins as active substance carriers include high drug encapsulation efficiency due
to optimized drug solubility in the core, low polymer content compared to other
nanoparticulated systems such as nanospheres, drug polymeric shell protection
against degradation factors like pH and light and the reduction of tissue irritation
due to the polymeric shell. They can mask unpleasant tastes, provide controlled
release properties and protect vulnerable molecules from degradation by external
factors such as light or by enzymatic attack in their transit through the digestive
tract. They can increase the therapeutic efficacy of active molecules because their
bio distribution follows that of the carrier, rather than depending on the physico-
chemical properties of the active molecule itself. Nanoencapsulated systems have a
relatively higher intracellular uptake compared with micro-particles, this behaviour
can be modified depending on nano capsule surface charges and the hydrophilic or
hydrophobic nature of the polymer used in shell formation.
6  Potential of Milk Proteins as Nanoencapsulation Materials in Food Industry 153

6.6  Whey Proteins

Whey proteins are a mixture of globular proteins of variable composition and func-
tional properties. Several whey protein products, for example whey protein concen-
trates and whey protein isolates, in their native form are industrially produced as
food protein ingredients. The functional properties of these products are largely
controlled by the major whey protein β-lactoglobulin. The whey protein and
β-lactoglobulin preparations have been used as a vehicle for the delivery of bioac-
tive compounds. The use of whey proteins and specifically β – lactoglobulin as car-
rier for bioactive compounds is based mainly on the entrapment of these components
in whey protein hydrogels. Hydrogels are water-swollen network that can hold large
amount of water while maintaining a network structure (Qui and Park 2001).
There are two major types of whey proteins. The main whey protein is bovine
milk β – lactoglobulin and α- lactalbumin which are synthesized in the mammary
gland. These proteins provide amino acids to the newly born. The main whey pro-
tein component β – lactoglobulin acts as the gelling agent in hydrogels. Whey pro-
tein gels may be used as pH-sensitive hydrogels for the controlled delivery of
biologically active substances. Due to the presence of hydrophilic groups in the
molecules these hydrogels absorb water. Protein-based hydrogels were found suit-
able for incorporating lipophilic constituents into aqueous foods and beverages and
for controlling digestion and release of lipid foods (McClements and Li 2010).
α-lactalbumin acts as a coenzyme during milk synthesis and helps in synthesis of
lactose. Minor whey proteins i.e. blood serum albumin and lactoferrin are trans-
ferred from blood plasma to milk through the lactating cells. Blood serum albumin
also helps to transport minerals and hydrophobic molecules in blood plasma.
Lactoferrin is an iron binding protein and increase the bioavailability of iron and has
bacteriastatic, antioxidant, anti-inflammatory and immunomodulatory properties
(Thompson et al. 2009).
β – lactoglobulin is a suitable candidate for the preparation of nano delivery sys-
tems for lipophilic bioactive compounds as a stable system and its capability to bind
hydrophobic constituents. Native β – lactoglobulin is stable in acid condition and
quite resistant to digestion by gastric proteases (Wang et al. 1997a). β – lactoglobu-
lin is a lipophilic binding protein similar to retinol-binding protein. However, β –
lactoglobulin showed high affinity to vitamin D2 (ten times higher than retenoids
and some other lipophilic compounds. (Wang et al. 1997b). The structure of β – lac-
toglobulin is characterized by the presence of three possible legend binding sites;
the solvent conical β barrel as the main site, a second site near the a-helix on the
external surface of the β -barrel and the third site at the dimmer interface (Jameson
et al. 2002). However, the bound bioactive compounds are poorly protected because
of the solvent accessibility of the binding sites.
Similarly, whey proteins have been designed to bind and transport hydrophobic
molecules. Milk fat globule membrane material has been found to be a suitable
material for making liposomes.
154 A. Poonia

Nano-tubes and nano-fibrils can be produced from whey proteins using enzy-
matic and heat treatments.

6.7  Binding Properties of Casein

Due to its sponge-like structure consisting of internal cavities connected to each

other and to the porous surface by channels, casein micelles were presumed for a
long time, to protect and transport molecules of interest. The ability of “native”
casein micelles but also isolated casein fractions and caseinates to interact with
hydrophobic molecules and minerals has been the subject of extensive
investigations.
Sahlan and Pramadewi (2012) tested the ability of caseins to encapsulate flavo-
noids, by isolating a casein fraction from cow milk by combining a slight reduction
of pH and a rennet hydrolysis. Casein nanoparticles with a mean diameter of 109 nm
i.e. close to the diameter of native casein micelles, which possesses an encapsula-
tion efficiency of about 42%, corresponding to an encapsulation of almost 1.0 mg
flavonoid per gram of casein. Casein micelles were also tested for their ability to
stabilize minerals in supplemented foods. Raouche et al. (2009) used a reversible
acidification process by carbonation to enhance the iron content in the casein col-
loidal fraction of skimmed milk. For the tested concentrations (2–20 m moles of
iron per liter of milk), the proportion of iron recovered in the casein fraction reached
about 95%. This very high recovered proportion demonstrates the efficiency of the
carbonation process to increase significantly the iron retention in casein micelles.
The process of acidification by carbonation probably reduced competition between
iron and calcium ions for casein phosphoseryl sites. The interaction between cal-
cium and the casein phosphoserine residues is known to be affected by both pH and
ionic strength: increasing ionic strength and decreasing pH reduce the affinity of
casein for calcium. In contrast, the interaction between iron and the casein phospho-
serine residues is less affected by pH change because iron binding involves electro-
static interaction and coordination links. Consequently, calcium was partially
removed from the casein micelles during carbonation, allowing its substitution by
iron atoms. Supplementation with iron modified the properties of the casein micelles
by decreasing the zeta potential, hydration and thermal stability of the casein
micelles; in addition, it slowed down the enzymatic coagulation kinetic of casein
micelles (Raouche et al. 2009).

6.8  Binding Properties of Whey Proteins

β – lactoglobulin has been widely studied for its ability to bind hydrophobic and
amphiphilic compounds such as flavor compounds, vitamins, fatty acids and poly-
phenols. Globally, the interactions between β  – lactoglobulin and bioactives are
6  Potential of Milk Proteins as Nanoencapsulation Materials in Food Industry 155

mainly driven by hydrophobic bonds, although hydrogen bonds are also involved in
the binding of polyphenols and fatty acids (Loch et al. 2013). It has been proposed
that β- lactoglobulin binds hydrophobic compounds preferentially in its internal
calyx, but additional binding sites in the cavity near to the alpha-helix and the exter-
nal surface of the β -barrel have also been described.
Whey proteins except β – lactoglobulin also have ability to bind specific ligands.
Blood serum albumin has two binding sites and has a higher affinity for 2-­nonanone,
a flavor compound, than β – lactoglobulin β or α-lactalbumin, which only possesses
one binding site (Kuhn et al. 2011). After binding to whey proteins, some ligand
properties were improved, including, in a non-exhaustive manner. Firstly, a reduc-
tion of ultra violet radiation induced the photo-degradation of folic acid from 40%
to 60% after 60 min. of treatment, Secondly, an increase in the photo-stability and
solubility of resveratrol and α- tocopherol. Thirdly, an increase in the solubility and
half-life of curcumin. In contrast, a decrease in the antioxidant activity of tea cate-
chins was observed when they formed complexes with β- lactoglobulin (Zorilla
et al. 2011) and blood serum albumin. In some cases, the complexes exhibited unex-
pected new functionalities that were not predictable from those of isolated
molecules.
Le et  al. (2012) evaluated the encapsulation efficiency of β- lactoglobulin
nanoparticles for epigallocatechin- 3-gallate (EGCG) in a wide range of pH (2.5–
7.0), thermal treatment intensity (30–85 °C/20 min), α -lactoglobulin concentration
(1–10 mg/mL) and protein: EGCG molar ratio (1:2–1:32). Nanoparticles were
formed on heating, concomitantly with the encapsulation of EGCG. The four stud-
ied factors affect the nanoparticle characteristics: particle size, zeta potential and
entrapment efficiency. The highest protection of EGCG was observed for heat treat-
ment at 85 °C and a protein: EGCG molar ratio of 1:2 Nanoparticles protect encap-
sulated EGCG via steric hindrance and exhibit antioxidative properties due to the
free thiols of the heat-denatured proteins. Similarly, heat-induced β – lactoglobulin
nanoparticles with a diameter less than 50 nm and a zeta potential of about 40 mV
were produced from 1.0% w/w protein solutions. These nanoparticles showed an
encapsulation efficiency of over 60–70% for EGCG and according to sensory tests,
the bitterness and astringency of EGCG were significantly reduced. The release of
EGCG was limited during simulated gastric digestion, which suggests that the
nanoparticles could be used to protect EGCG in the stomach, allowing a possible
release of the bioactive into the gut (Shpigelman et al. 2012).
Relkin and Shukat (2012) used high-pressure homogenization to produce
nanoparticles from heat-induced aggregates of whey proteins for α -tocopherol
encapsulation. The formed particles exhibited a diameter between 212 and 293 nm,
depending on the pressures employed. Compared to homogenization at 300 bar, a
pressure at 1200 bar induced some protein structural changes that modified the zeta
potential of the produced particles and improved the stability of encapsulated
α-tocopherol during storage. By use of pH-cycling treatment (acidification and neu-
tralization) whey protein nanoparticles with a controlled size can be produced.
Particles with a diameter ranging from 100 to 300  nm were produced through
the  acidification of a low concentrated solution of heat-denatured whey proteins.
156 A. Poonia

The whey proteins were linked by covalent bonds in the nanoparticles after the neu-
tralization step. The particle size varied depending on the pH of acidification (5.0–
6.0), aggregation time (0–75 h) and calcium concentration (0–5.0 mM). Calcium
­concentration also influenced the voluminosity of the particles: increasing the con-
centration of calcium decreased the voluminosity of the particles. This technique
was used to produce particles for entrapping hydrophobic aroma. The retention effi-
ciency was maximum when the aroma molecules were added to the protein disper-
sion before the formation of the particles at pH 5.0 or 5.5 and without added calcium
(Giroux and Britten 2011).
Nanoparticles of blood serum albumin were produced in the presence of the fla-
vonoid quercetin by a desolvation process induced by the addition of 10% dimethyl
sulfoxide. These nanoparticles showed a zeta potential of 12.5 mV and a diameter
close to 10 nm, surprisingly smaller than the diameter measured for native blood
serum albumin and for the nanoparticles produced in the absence of the flavonoid
(Fang et  al. 2010). They reported the highest compaction of the nanoparticles in
complexes with the flavonoid based on the transmission electron microscopy obser-
vations. The antioxidant property of encapsulated flavonoid was not substantially
changed, but its stability under intestinal conditions appeared to increase due to the
formation of both hydrophobic interactions and hydrogen bonds between quercetin
and blood serum albumin during the encapsulation process. Sneharani et al. used
desolvation to produce nanoparticles of β – lactoglobulin for curcumin encapsula-
tion at alkaline pH using acetone. The formed nanoparticles were stabilized using
glutaraldehyde as a cross-linking agent. They reported that spherical particles with
a diameter of 140 nm were formed, which showed a curcumin encapsulation effi-
ciency of about 96%, with a simultaneous increase in curcumin solubility in aque-
ous solution from 0.03 to 620 mM.  It was also reported that the encapsulated
curcumin was slowly released from protein nanoparticles at neutral pH, which lim-
its the use of these nanoparticles as a vehicle for such substances.

6.9  Whey Protein Isolates

Nanoparticles can be prepared by use of whey protein isolate by desolvation using

ethanol. These particles were used for the encapsulation of zinc and demonstrated
entrapment efficiency between 80 and 100%, with a maximum incorporation of zinc
of about 8 mg/g whey protein isolates. These particles remained stable for 30 days
at 22 °C at pH 3.0. Other food-grade technology for the encapsulation of bioactives
based on the supercritical drying of preformed hydrogels to form aerogels was
applied with success to whey protein isolate. Aerogels formed by controlled drying
with supercritical carbon dioxide of whey protein isolate hydrogels exhibit a meso-
porous structure with a high encapsulation capacity of ketoprofen, a hydrophobic
molecule, compared to the macroporous structure found for cryogels formed by
conventional freeze drying techniques. Hence, similar to polysaccharides, protein
aerogels with a high encapsulating efficiency offer new possibilities as an alterna-
tive to aerogels from synthetic polymers.
6  Potential of Milk Proteins as Nanoencapsulation Materials in Food Industry 157

6.10  Protein Nanotubes

α-Lactalbumin Nanotubes  Nano-tubes made of the milk protein α-lactalbumin

are formed by self-assembly of the partially hydrolysed molecule. Certain globular
proteins from milk can be made to self assemble to form nano tubes under appropri-
ate conditions. α- lactalbumin is a milk protein which is beneficially used in the
production of nanotubes. α-lactalbumin nano tubes are formed by self-assembly of
the partially hydrolysed molecule. At neutral pH and in the presence of an appropri-
ate cation, these building blocks self-assemble to form micro meter long tubes with
a diameter of only 20 nm (Otte et al. 2005). These features of the α-lactalbumin
nano tube make it an interesting potential encapsulating agent. Nanotubes of
α-lactalbumin have a cavity diameter of 8 nm which enables the binding of food
components such as vitamins or enzymes (Srinivas et al. 2010). Potential applica-
tions of α –lactalbumin nanotubes are listed in Table 6.3.
Nanotubes made of the milk protein α -lactalbumin are formed by self-assembly of
the partially hydrolysed molecule. Hydrolysis is needed to make the α-lactalbumin
prone to self-assembly. At neutral pH and in presence of an appropriate cation, these
building blocks self-assemble to form micrometre-long tubes with a diameter of
only 20 nm. Figure 6.4 displays a schematic presentation of the self-assembly of
partially hydrolysed α-lactalbumin into nanotubes and a transmission electron
micrograph of the nanotubes. Here, it is clearly visible that the nanotubes are hollow
by the dark stain line in the middle of the structure.

Table 6.3  Overview of unique properties and potential applications of α –lactalbumin nanotubes
with other materials used in food and pharmaceutics
Properties α-lactalbumin nanotubes Conventional materials References
Stability at high They could withstand some Sensitive to high Graveland et al.
temperature important treatments at temperature (2006)
pasteurization temperature
(40 s at 72 °C)
Strength Strong structure is rather Collapse upon
strong and did not collapse freeze-drying
upon freeze-drying
Stability at low The nano-tubes also Cannot withstood a
temperature withstood a freeze-­drying freeze-drying treatment
treatment
Stiffness/hardness The Young’s modulus was Microtubule walls, with Radmacher
determined to be in the a Young’s modulus of (2002)
order of 0.1 GPa. Compared 0.6 GPa. bacteriophage
with Young’s moduli of capsids, 1.8 Gpa.
other (biological) Non-proteinaceous tubes,
structures, the such as carbon
α-lactalbumin nanotubes nanotubes, are
are clearly stiffer than significantly stiffer: their
whole living cells (10 Young’s modulus can be
K4–10 K2 MPa as high as 1 TPa
(continued)
158 A. Poonia

Table 6.3 (continued)
Properties α-lactalbumin nanotubes Conventional materials References
Damage resistant It is possible to cut the They get damaged Doi (1993)
α-lactalbumin nanotubes or
to cut out pieces, without
damaging the complete
structure
Controlled release Controlled disassembly of Non-cross-linked Matsui et al.
the induced by decreasing nanotubes were found (2001) and
the Ca2+ concentration by to disassemble into Raviv et al.
dilution in Ca2+−free buffer. building blocks upon (2005)
By varying the Ca2+ dilution in Ca2+− free
concentration in the solvent buffer, the cross-linked
the disassembly rate can be nanotubes were
controlled resistant to disassembly
for at least 1 day
Formation of gels They can form strong gels Relatively weak at very Doi (1993)
at low weight fractions. The large deformation.
storage modulus of an Random aggregates are
α-lactalbumin nanotubes inefficient as gelating
gel prepared from a 30 g/l. agent: high
α -lactalbumin solution was concentration needed
found to exceed 1 kPa for firm gels
Transparent gels Non-fibrillar aggregate
gels are turbid
Encapsulation Cavity of 8 nm diameter Conventional Gibbs et al.
and a few micrometers in encapsulating agents (1999)
length provides defined mostly have ill-defined
space for specific molecules space for encapsulated
molecules

enzyme Ca2+

α-lactalbumin hydrolysed nanotube

molecules

Fig. 6.4 (Left) Schematic presentation of the self assembly of partially hydrolyzed α-lactalbumin
into nanotubes in presence of Ca2+ (Right) Transmission electron micrograph of negatively stained
α- lactalbumin nanotubes (negative staining performed with 3% uranyl acetate for 1 min)
(Graveland and de Kruif 2006)

6.11  Prerequisite for the Nanpotubes

Concentration of α-Lactalbumin  Minimum concentration to form nanotubes of

α -lactalbumin is 20 g/l (at 50 8C, 75 mM Tris buffer, pH 7.5, 2 mol Ca2C/mol
α-lactalbumin).
6  Potential of Milk Proteins as Nanoencapsulation Materials in Food Industry 159

Concentration of Other Proteins  The presence of low concentration of other pro-

teins, such as β -lactoglobulin, disturbs the process of self assembly into nanotubes.
Already, a 2% protein fraction of β-lactoglobulin (at a protein content of 30 g/l)
induced an increase in random aggregation.
Type of Ions  Various di- and trivalent ions were shown to trigger self-assembly into
nanotubes, namely Ca2+, Mn2+, Zn2+ Cu2+ and Al3+. The specific type of ion that should
be used, nanotubes can only be formed within a rather narrow ion concentration
window. At 30 g/l, α -lactalbumin nanotubes can be formed at molar ion/α -lactalbu-
min ratio between 1 and 3. Below this ratio, the ion concentration is thought to be too
low to produce enough nuclei and as a result, random aggregation also occurs.

6.12  Market

Only few food products containing nano-scale additives are commercially available.
Many companies are conducting research and development on the use of nanotech-
nology to engineer, process, package, and deliver food and nutrients to our shopping
baskets and our plates. In addition to a handful of nanofood products that are already
on the market, over 135 applications of nanotechnology in food industries mainly in
(nutrition and cosmetics) are in various stages of development. Among the 20 most
active companies are 5 that rank among the world’s 10 largest food and beverage
corporations, Australia’s leading Food Corporation, and Japan’s largest seafood
producer and processed food manufacturer. A report produced by Helmut Kaiser
Consultancy, “Nanotechnology in Food and Food Processing Industry Worldwide,”
predicts that the nanofood market will surge from $10 billion today to $30.4 billion
in 2015 of nanotechnology in food industries (Nanoform 2006). Nestle, Altaria,
H.J. Heinz and Unilever are the World’s largest food manufacturing and other small
companies follow these companies.
In Australia, nanocapsules are used to add omega-3 fatty acids to one of the
country’s most popular brands of white bread. According to the manufacturer, nano-
capsules of tuna fish oil added to TipTop Bread provide valuable nutrients, whereas
the encapsulation prevents the bread from tasting fishy. NutraLease, a start-up com-
pany of the Hebrew University of Jerusalem, has developed novel carriers for nutra-
ceuticals in food systems. A joint effort among universities in India and Mexico is
directed at developing nontoxic nanoscale herbicides. Researchers at Tamil Nadu
Agricultural University in India and Monterrey Tech. in Mexico are looking for
ways to attack a weed’s seed coating and prevent it from germinating. More than
400 companies around the world are today active in research and development and
production. USA is the leader, followed by Japan and China. By 2015, Asia, with
more than 50% of the world population, will become the biggest market for the
nanofood, with China in the leading position (Darder Darder 2007). A UK-based
Cientifica estimated that nanotechnologies in the food industry were currently val-
ued at $410 million and would grow to $5.8 billion by 2015 (Ipsen and Otte 2007).
The global market for nanotechnology products was valued at $22.9 billion in 2013
160 A. Poonia

and increased to about $26 billion in 2014. This market is expected to reach about
$64.2 billion by 2019; a compound annual growth rate of 19.8% from 2014 to 2019.
The US market total $2.7 billion in 2013 and is expected to grow nearly $6.3 billion
by 2018, a CAGR of 18.3%. BCC Research expects the European market to reach
$5.3 billion by 2018 from nearly $2.3 billion in 2013, a CAGR of 18.6%. (BCC
research 2011 Report Code: NAN050A). Sales of Nanotools will experience high
growth. This market segment was worth $2613.1 million in 2009 and will increase
at a 3.3% compound annual growth rate to reach a value of $6812.5 million in 2015
(www.bhartbook.com).

6.13  Market Challenges

Sensitive molecules can be entrapped in a form that is physically and chemically

compatible with the food matrix without adverse effects. Also, the use of milk pro-
teins for the targeted delivery of food bioactives or for increasing nutrient bioavail-
ability remains an emerging research area. While going through the advantages and
disadvantages of milk protein based the nano-materials in food products, there are a
number of challenges that need further research are listed in (Box 6.1).

Box 6.1  Market Challenges for Milk Based Nano- Products

Identification of specific targets and targeting mechanisms: Identification
of specific targets and targeting mechanisms for oral delivery of cancer ther-
apy and advancing nanotechnology for food and drug applications is another
major challenge.
Sensitivity to oxidation: While in the field of nutraceuticals, these include
protecting oxidation sensitive hydrophobic and hydrophilic nutraceuticals in
long shelf life food products.
Controlled release: The main technological challenges in this respect are
to control the digestibility, to program the release of the bioactive payload to
occur at the desired target location along the gastrointestinal tract, and to pro-
mote its bioavailability (Livney 2010).
Encapsulation of sensorially challenging nutraceuticals in food
applications.
Need of effective targeted vehicles: Exploring the digestive or systemic
fate of the vehicles developed and their bioactive cargo and applying this
knowledge to the design of smarter, more effective targeted vehicles for both
neutracetical and drugs, as nature remains our main source for inspiration.
Potential Risks: Advancing nanotechnology for food and drug applica-
tions, while critically assessing its potential risks and benefits, with emphasis
on nanoparticle penetration of biological barriers.
6  Potential of Milk Proteins as Nanoencapsulation Materials in Food Industry 161

6.14  Existing Products

In market, energy drinks, nutritional supplements, food storage containers, anti-­

bacterial utensils, cutting boards, plastic wraps, food packaging, Nano-tea, choco-
late and shakes are available. Natural and engineered nanomaterials in the food,
additives and packaging, new flavours and textures, less use of fat, enhanced absorp-
tion of nutrients, blockage of ingredients that contribute to elevated blood choles-
terol are also available. Smart packaging identifying contaminated food, nanoscale
sensors. Identifying the presence of bacteria and releasing chemicals as food spoils.
Nanomaterials preventing adhesion of the microbes to the surfaces and equipment,
nanosilver  – food contact utensils and containers are hitting the market. Current
applications of nanoparticles with their functionality in foods products is mentioned
in (Table 6.4). Friends of the Earth (a Non-Governmental Organization) have also
reported that foods that contain manufactured nanomaterial ingredients are being
sold to consumers in supermarkets (FOE 2008). Examples of foods, food packaging
and agriculture products that now contain nanomaterials are shown in (Table 6.5).

Table 6.4  List of current applications of nanoparticles, their functionality in food and food
processing related nano products with current status and research
Application Status and functionality
Processed nanostructured or -textured A number of nanostructured food ingredients and
food (e.g. less use of fat and additives understood to be in the research and
emulsifiers, better taste development pipeline; e.g. Mayonnaise, Ice-cream and
spread
Nanocarrier systems for delivery of Taste masking of certain/additives, such as fish oils,
nutrients and supplements in the form protection of certain ingredients during processing,
of liposomes or biopolymer-based improved optical appearance, improved bioavailability
nanoencapsulated substances of nutrients and supplements, antimicrobial action,
and other health benefits
Organic nanosized additives for food, Materials range from colors, preservatives, flavorings
supplements and animal feed to supplements and antimicrobials
Inorganic nanosized additives for food, A range of inorganic additives (silver, iron, silica,
health food, and animal feed titanium dioxide, selenium, platinum, calcium,
magnesium) is available for supplements,
nutraceuticals, and food and feed applications
Surface-functionalized nanomaterials Main uses are currently in food packaging; possible
uses emerging in animal feed
Nanosensors for food labelling Research & Development stage
Pills, liquids/capsules Patented “nanodrop” delivery systems, designed to
administer encapsulated materials, such as vitamins,
transmucosally, rather than through conventional
delivery systems such as pills, liquids, or capsules
(continued)
162 A. Poonia

Table 6.4 (continued)
Application Status and functionality
Meat products Nanoencapsulated flavor Enhancers
Nanotubes and nanoparticles as gelation and
viscosifying agents
Nanocapsule infusion of plant based steroids to
replaces meat’s cholesterol
Nanoparticles to selectively bind and remove
chemicals or pathogens from food
Nanoemulsions and particles for better availability and
dispersion of nutrients
Fruit drinks Nanoparticles of carotenoids that can be dispersed in
water, allowing them to be added to fruit drinks
providing improved bioavailability
Lycopene A synthetic lycopene has been affirmed GRAS under
US Food and Drug Administration procedures
Chocolate drink without added sugar A wide range of nanoceutical products containing
or sweeteners nanocages or nanoclusters that act as delivery
vehicles, e.g., a chocolate drink claimed to be
sufficiently sweet without added sugar or sweeteners
Tea Nano-based mineral supplements, e.g., a Chinese
nanotea claimed to improve selenium uptake by one
order of magnitude
Mineral supplements An increasingly large number of mineral supplements
such as nanosilver or nanogold
More details on different applications of nanotechnologies for the food sector can be found in
(Chaudhary and Castle 2011)

6.15  I PR/Patented Products Which Have Potential to Hit

the Market

Nanotechnology is different from many other important fields of invention. Over

the past century in that many of the foundational inventions have been patented at
the outset and in that many of the patents have been issued to universities (Wesley
et al. 2000). By 2012, over 30,000 nanotechnology patents had been granted by the
US Patent & Trademark Office alone (Chen et al. 2006). Patentees generally find
these patents valuable enough to maintain. A 2007 study found that owners had
maintained 54% of pre-1994 patents through three maintenance periods, compared
with 43% of patents generally (Lux Research). While there have been some con-
cerns about potential limitations on the patentability of nanotechnology, many more
commentators have expressed the opposite concern that there are too many nano-
technology patents that will lead to inefficient patent thickets.
6  Potential of Milk Proteins as Nanoencapsulation Materials in Food Industry 163

Table 6.5  Examples of foods and food packaging contain manufactured nanomaterial ingredients
are being sold to consumers in supermarkets now contain nanomaterials (FOE 2008)
Type of Product name and
product manufacturer Nano content Purpose
Beverage Oat Chocolate and Oat 300 nm particles of Nano-sized iron particles
Vanilla Nutritional Drink iron (SunActive Fe) have increased reactivity
Mixes; Toddler Health and bioavailability
Food Aquasol preservative; Nanoscale micelle Nano-encapsulation
additive AquaNova (capsule) of lipophilic increases absorption of
or water insoluble nutritional additives,
Substances increases effectiveness of
preservatives and food
processing aids. Used in
wide range of foods and
beverages
Food Bioral™ Omega-3 Nano-cochleates as Effective means for the
additive nanocochleates; small as 50 nm addition of highly
BioDelivery Sciences bioavailable Omega-3 fatty
International acids to cakes, muffins,
pasta, soups, cookies,
cereals, chips and
confectionery
Food Synthetic lycopene; LycoVit 10% Bright red colour and
additive BASF (<200 nm synthetic potent antioxidant. Sold for
lycopene) use in health supplements,
soft drinks, juices,
margarine, breakfast
cereals, instant soups, salad
dressings, yoghurt, crackers
etc.
Food contact Nano silver cutting Nanoparticles of “99.9% antibacterial”
material board; A-Do Global silver
Food contact Antibacterial Nanoparticles of Ladles, egg flips, serving
material kitchenware; Nano Care silver spoons etc. have increased
Technology/NCT antibacterial properties.
Food Food packaging Nanoparticles of Nanoparticles of silica in
packaging Durethan® KU 2–2601 silica in a polymer-­ the plastic prevent the
plastic wrapping; Bayer based nanocomposite penetration of oxygen and
gas of the wrapping,
extending the product’s
shelf life. To wrap meat,
cheese, long-life juice etc.
Food Nano ZnO Plastic Wrap; Nanoparticles of zinc Antibacterial, ultraviolet
packaging SongSing oxide -protected food wrap
Nanotechnology
164 A. Poonia

6.16  Conclusions

Milk proteins are excellent material to develop nano vehicle for the delivery of bio-
active compounds. Because of their diversified composition and functional proper-
ties, they have advantage of being easy to prepare. The development of milk protein
based nanoparticle drug delivery systems is expected to have a major impact on the
treatment of cancers and other life-threatening diseases. Crosslinked casein micro-
spheres could be promising parenteral biodegradable carriers for sustained delivery
of drugs when administered via intramuscular, intraperitoneal, direct intratumoral
or intra-arterially for embolization in solid tumor deposits. They are also resistant to
proteolytic enzymes, and thus stable in the gastrointestinal tract and consequently
could be used for sustained release oral preparations. Milk protein based nanopar-
ticles are tailored from natural and edible polymers, without the use of exogenous
additives makes them promising as building blocks for encapsulation and versatile
for several innovations and advantages. Therefore, casein appears to be a promising
carrier for the delivery of many orally as well as parenterally administered drugs.
More studies are required to investigate the mechanisms of action of these novel
vehicles that will provide a basis for their further optimization, thus opening more
exciting opportunities for improving the application of these macromolecules.
Secondly, other field to explore is the encapsulating potentialities of spontaneously
co or self- assembled supra molecular structures, native casein micelles,
α-lactalbumin nanotubes, β-globulin fibres and nanospheres from oppositely
charged proteins. The existence of stringent regulatory controls in many countries
provides reassurance that only safe products and applications of nanotechnologies
will be permitted on the market. In world, several countries are active in examining
the appropriateness of their regulatory frameworks for dealing with nanotechnolo-
gies but have applied different approaches to address safety issues of nano-based
products from legally binding provisions to guidance for industry.

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Chapter 7
Uptake and Toxicity of Nanomaterials
in Plants

Atul Dev, Anup K. Srivastava, and Surajit Karmakar

Abstract  Rapid development of nanomaterials has induced their diffusion in our

environment, reaching plants that are the primary link of the food chain. Studies
show that plant behaviour is changing by interaction with nanomaterials, notably
due to their toxicity. Plant physiological barriers are providing some resistance
against nanomaterial-mediated toxicity. Indeed, plant turn on and off machinery to
overcome nanomaterial-mediated stresses, which result in unusual growth patterns.
This article reviews the mechanisms of interaction of nanomaterials with plants,
with focus on uptake, translocation and toxicity behaviour at physiological, pro-
teomic, transcriptomic and metabolomic level. We discuss the toxicity of the fol-
lowing nanomaterials: silver, CeO2, ZnO, cupric oxide, fullerene, nickel oxide, zero
valent iron, gold, aluminium oxide, titania and silica.

Keywords  Nanotoxicity • Translocation • Accumulation • Detoxification pathways

• Natural barriers • Biotransformation • Phenomics • Metabollomics

7.1  Introduction

Plants and nanomaterials interaction is not new, as plants are continuously in direct
exposure to naturally occurring nanoparticles since the evolution. They have survived
and evolved under most disastrous and challenging conditions throughout the life-
cycle and therefore must have a strongest defense mechanism to fight against stresses.
Recently in few years these defense mechanisms has challenged by the generation of
a new kind of synthetic materials at nanoscale. Nanotechnology is creating new
materials day by day that showing the large application in different fields. As these
materials providing new solutions of long persisting problems in the agriculture sec-
tor, causing unforeseen problems too (Dasgupta et al. 2017; Shukla et al. 2017; Walia

A. Dev • A.K. Srivastava • S. Karmakar (*)

Institute of Nano Science and Technology,
Habitat Centre, Phase-10, Mohali 160062, Punjab, India
e-mail: surajit@inst.ac.in

© Springer International Publishing AG 2017 169

S. Ranjan et al. (eds.), Nanoscience in Food and Agriculture 5, Sustainable
Agriculture Reviews 26, DOI 10.1007/978-3-319-58496-6_7
170 A. Dev et al.

et al. 2017; Balaji et al. 2017; Maddinedi et al. 2017; Sai et al. 2017; Ranjan and
Chidambaram 2016; Janardan et  al. 2016; Ranjan et  al. 2016; Jain et  al. 2016;
Dasgupta et al. 2016). Nanomaterial induced toxicity in plants was neither well stud-
ied nor well established. There are still many questions related to nanotoxicity that
needed to be answered. Plants have great tendency of adaptability in unfavorable
condition but there is a knowledge gaps in marking a visible difference in adaptabil-
ity and toxicity. Parameters to clearly define and quantify the toxicity in plants are not
well defined so far. There are literatures available on different detoxification mecha-
nisms that plants utilized against nanoparticles mediated toxicity but none of it estab-
lished a well-defined route that plant take. Nanomaterials are not toxic always as
there are reports that tell about the positive aspects of these materials.
Dramatically the increase in production of synthetic materials at nanoscale and
their interaction with plants has created a buzz in field of toxicological research.
Nanotoxicity and plants is the most emerging subject nowadays as there are so
much concern on environmental issues. We still have very less understanding of the
newly synthesized nano materials, their unusual properties and their interactions
with plants. One nanomaterial interacts so differently with different plant in differ-
ent environments. This interaction allow plants to respond to these materials in
equally different manner but we are still not able to figure out what different
responses plant is giving against them. To understand these responses a thorough
knowledge of plant physiology, biochemistry, and material chemistry is important.
We tried to draw kind attention of readers to the different factors and crucial
issues that are contributing to the toxicity at various stages in the plant system and
to provide a concise knowledge on nanomaterial mediated toxicity.

7.2  Interaction of Nanomaterial with Plants

Nano materials interact physically or chemically with different plants. These inter-
action cause variable changes in plant activity like chemical interactions caused
chemical modification and generation of new molecules which may be harmful to
the plants for e.g. reactive oxygen species (Nel et al. 2006). ROS altered the ion
transport across cell membrane (Auffan et  al. 2008), induced oxidative damage
(Foley et al. 2002), peroxidation of lipids (Kamat et al. 2000). Nanoparticle size,
shape, some surface characteristics like roughness, hydrophobicity or hydrophilic-
ity, effective surface charge (zeta potential), plant species, the environment in which
the plant is growing, etc. are main factors that decide the interaction of nanomaterial
and plants. How plant interacting with the plants decide its uptake in the plants.
There are different routes by which these materials get entry to the plant system.
Synthetic nanomaterials can reach the plants through direct application, accidental
release, contaminated soil/sediments, or atmospheric fallouts. Nanoparticles
(Nanoparticles) enter the plant through the root system and reach the xylem through
the cortex and the pericycle (Dietz and Herth 2011). The first barrier to the entry in
the cell is cell wall it works as a molecular sieve allows only a small range of
nanoparticles to get in. Only those Nanoparticles could effectively cross the cell
7  Uptake and Toxicity of Nanomaterials in Plants 171

wall and reach the plasma membrane that complement the cell wall pore size
(Navarro et al. 2008). Although the smaller Nanoparticles can enter into plant cells
quickly through the root system, the larger Nanoparticles can only penetrate through
the flower stigma, hydathodes, and stomata. As larger nanoparticles have very less
chance to get into the cell, they hardly change the cell metabolic activity (Verano-­
Braga et al. 2014). Following entry into the plant cells, small Nanoparticles after
stabilising inside the cell, behave as reactive metal ions and react with different
functional groups of proteins and alter the protein activity. Increased surface area
allow synthetic nanomaterials to readily adsorb organic molecules and inorganic
ions from the nutrient medium or soil resulting indirect toxicity symptoms which
include chlorosis and wilting (Slomberg and Schoenfisch 2012; Begum and Fugetsu
2012). Nanoparticles interaction with plants causes their uptake or accumulation in
the plants which finally ending up in the transfer across different trophic levels.

7.3  Nanoparticles Uptake by Plants

Plant anatomy is one of the most crucial factors for uptake of the nano scale material.
Shoot surfaces favour the deposition of different air drive nanomaterials, as shoot
surfaces are covered with cuticular waxes, epicuticular structures, such as tubes,
papillae, frequently decrease wettability i.e. Lotus effect (Barthlott and Neinhuis
1997). Nanoparticles are adsorbed onto the plant surfaces and taken up through dif-
ferent plant openings. Nanoparticles can enter plant after passing through the natural
barrier which includes an outermost coating of the cuticle, mucilage and exudates,
pectins, etc. once these barriers are crossed nanomaterial can get into the cells by
binding to different carrier proteins, like through aquaporins, ion channels, or by
creating new pores. Most of the Metal based Nanoparticles that have been reported
are taken up by plants include through specific ion transporters (Hall and Williams
2003). However, the exact mechanisms of why some plant species preferentially take
up several Nanoparticles are still unknown and remain to be explored. There are dif-
ferent anatomical barrier present in the plant system that regulates the uptake of
nanoparticles into the plants. Some of the fascinating barriers are described below:

7.3.1  Cuticle

The cuticle is the very first anatomical boundary that guards the entry of different
types of nanomaterial into the plants. Nanoparticles, such as negatively charged
mesoporous silica nanoparticles (MSN, 20 nm) (Hussain et al. 2013) or neutrally
charged lipid-based liquid crystalline Nanoparticles (150–300 nm) (Nadiminti et al.
2013), were reported to accumulate above the anticlinal cell walls on or in the cuti-
cle. In one case, nano-TiO2 was shown to produce holes in the cuticle (Larue et al.
2014). Larger Nanoparticles can penetrate through some of the cuticle-free areas,
such as hydathodes, the stigma of flowers, etc. Although cuticle cover majority of
172 A. Dev et al.

the plant parts like root periderm, aerial parts including leaves, fruits, etc. there are
still different types of opening such as trichomes, mucilage-covered root hairs and
tips, and hydathodes are left in cuticle which possess different secretory or uptake
functions (Fahn 1982). These openings allow permeation of nanomaterial between
cuticles in the epidermal cells. Intercellular gas space of leaves also permits the
entry of nanomaterial by passage through the stomata. In the presence of the natu-
rally cuticle-free stomata, the pore size was found to be in the size range of 4100
nm, which under-score the importance of the waxy cuticle layer for repellency of
polar solutes (Eichert and Goldbach 2008). Dicot cuticles was found to be more
permeable than those of monocots for lipid-based nanostructured liquid crystalline
nanoparticles.

7.3.2  Suberin

Deep into the soil, plants roots and tubers develop a single or multilayer complex
fatty acid substance suberin as an interface with the soil environment (Schreiber
2010). There are certain loose opening present in plant roots that allow the entry of
nanomaterial to the central cylinder called xylem. The outer exodermis layer prevents
apoplastic bypass flow of solutes and water from the soil to the central cylinder but
the formation of newly lateral roots break the cortical region and allow the rendered
apoplastic bypass flow. These site of lateral root formation allow the entry of nanopar-
ticles into the xylem via the cortex and the central cylinder (Faiyue et al. 2010).

7.3.3  Mucilage and Exudates

Mucilage and exudates of plants are the first barriers for nanomaterial into the
plants. Seed envelops, root hairs and root caps of plants excrete mucilage and exu-
dates into the rhizosphere (Driouich et al. 2013; Hawes et al. 2000; McNear 2013;
Walker et al. 2003; Zhang et al. 2011; Yang et al. 2012). It provides active protection
to the plant cells against different stress and helps protect rhizosphere after provid-
ing the acidic environment. This acidic environment facilitates dissolution of
Nanoparticles for example, Nano-Au, dissolved in the rhizosphere, after getting
oxidised (Taylor et al. 2014).

7.3.4  The Cell Wall and Cell Membrane

Nanoparticles must face the cell wall before entering the intact plant cell and inter-
acting protoplast. The cell wall of plant cells is not continuous it contains different
pores of variable size limit. Different experimental results showed that the maxi-
mum pore size of plant cell walls is usually in the range of nanometers and it varies
7  Uptake and Toxicity of Nanomaterials in Plants 173

tissue to tissue, for example, In root hairs it was found to be 3.5–3.8  nm while
4.5–5.2 nm in palisade parenchyma cells (Carpita et al. 1979) The Same experiment
also has shown that the pore sizes are affected by pH and divalent ions (Fleischer
et al. 1999) and less than 5 nm particles were efficiently able to pass through the cell
wall of undamaged cells (Hischemoller et al. 2009) Tissue- and cell-specific distri-
bution of Alizarin red S-labeled Titanium dioxide (TiO2) nanoparticles (NP) of
approximately 3 nm was found in Arabidopsis seedlings, these nanoparticles were
passed through the cell wall and found in different compartments, including vacu-
oles of epidermal cells (Kurepa et al. 2010).
There is the similar mechanism of nanoparticles uptake in plants cells like ani-
mal cell which include fluid phase endocytosis. Receptor-mediated endocytosis is
the most common mechanism, in which nanoparticles have adhered to the surface
with some specific receptors present on the cell membrane and were invaginated
through a group of vesicle-forming proteins called clathrins. Clathrin-coated vesi-
cles formed in the size range of 70–120 nm in diameter (Samaj 2012), therefore, this
mechanism is limited to Nanoparticles smaller than this magnitude. For example:
when protoplasts of Acer pseudoplatanus (sycamore maple) were exposed to posi-
tively charged Texas Red labelled polystyrene nanospheres of 40 nm these nanopar-
ticles were primarily found in the central vacuoles. The most likely mechanism of
such nanoparticles uptake is receptor-mediated clathrin-dependent fluid-phase
endocytosis (Samaj 2012; Etxeberria et al. 2006; Moscatelli et al. 2007). Nanoparticle
endocytosis can also be clathrin-independent (Onelli et  al. 2008; Samaj 2012;
Etxeberria et al. 2006; Moscatelli et al. 2007). As in clathrin-mediated endocytosis,
this does not require binding of a specific ligand to a receptor; it occurs through
larger vesicles as happen in macro- or micro-pinocytosis in animal cells (Samaj
2012). Neutrally charged polyethylene glycol coated quantum dots 20 nm in diam-
eter sequestered in spherical organelles of less than 120 nm in the cytoplasm (Samaj
2012; Etxeberria et al. 2006).
There are also non-endocytic pathways that facilitate uptake of nanoparticles in a
nonselective manner through gated channels like Aquaporins (water channels) in the
cell membrane (Fitzpatrick and Reid 2009; Rico et al. 2011; Sattelmacher and Horst
2007) with the diameter of 0.2–0.25 nm at the midpoint (Tyerman et al. 2002). Water
and small non-ionic solutes in the size range of greater than 1 nm in diameter are
uptaken by these protein channels. Uptake of insoluble Nanoparticles of less than
1 nm in diameter through these water channels and similar channels (Hu et al. 2010;
Schaller et al. 2013; Wang et al. 2011) is found to be tough. This is not considered
to be as central pathways of uptake of insoluble nanoparticles. Some reports show
the impact of nanoparticles on the expression of these protein channels. Aquaporin
was found to be up-regulated (Khodakovskaya et al. 2012) and sometimes down-
regulated (Lu et al. 2010; Taylor et al. 2014). Although this differential expression
of the aquaporin expression may be a response to the reduced water flow through the
plant as a result of the accumulation of nanoparticles near the roots (Lu et al. 2010;
Asli and Neumann 2009; Ranathunge et  al. 2005). Except aquaporins, there are
some selective ion channels present that allow the uptake of only those nanoparticles
for which elemental specific ion channels is present (Hall and Williams 2003).
174 A. Dev et al.

7.4  T
 ranslocation and Accumulation of Nanoparticles
in Plants

Nanoparticles thought to be more reactive than their bulk counterparts because of

increased surface area to mass ration. It must pass through the cell wall before
reaching the Cell protoplast. Nanoparticles are transported into the plants after
forming different complexes with membrane transporters or root exudates (Kurepa
et al. 2010; Watanabe et al. 2008). Once it reached inside the cells transported apo-
plastically or simplastically in the plant system. Plant cells are interconnected
through plasmodesmata. Therefore, transportation across the cells is easily facili-
tated through it. Nanoparticles translocation and accumulation is a linked process as
one process regulates others. Either the nanoparticles are translocated through the
system or get accumulated near some favourable site or naturally occurring barriers
inside the plants. Translocation and accumulation of nanoparticles depend on many
factors which include size, shape, the chemical composition of nanoparticles, plant
species, plant stage, the environment of nanoparticles, concentration of the nanopar-
ticles, etc. Lipophilic molecules tend to accumulate on the surface of cuticle above
anticlinal cell walls and later translocated along pectins (middle lamellae) through
the apoplast while Hydrophilic compounds pass through particular polar channels
through the cuticle regions (Schreiber 2005; Schreiber et al. 2006). Once nanomate-
rial entered into the plants through this barrier, it gets deposited on the cell walls of
the substomatal cavity or neighboring cells. Some report indicates accumulation of
nanoparticles in necrotic tissues (Uzu et al. 2010) via mucilage entrapment in lysed
cells. Nanoparticles either gets accumulated near root region or minority get into the
system through translocation mechanism.
Translocation of Nanoparticles through central cylinder crucially depends on the
rate of water translocation which is affected by number of factors like the reduced
transpiration, reduced root pressure, some environmental factors like temperature,
humidity, charge-charge interaction between nanoparticles and plants which includes
weak van der Waals forces (Schwab et al. 2011; Zhang et al. 2011; Zhu et al. 2012).
Reduced translocation causes accumulation of Nanoparticles on the root surface
(mucilage). Positively charged nano-Au found consistently accumulated to a greater
extent on the negatively charged root surface then negatively charged nano-Au (Zhu
et al. 2012). Although negatively charged nanoparticles like nano-Au, or quantum
dots exhibit higher translocation rates because of electrostatic repulsion with nega-
tively charged plant surfaces (Wang et al. 2014; Zhu et al. 2012) or sorption hyster-
esis (trapping) by irreversibly diffusing into micro-pores of the mucilage polymers.
There is some exception that doesn’t follow this theory like super paramagnetic iron
oxide nanoparticles (SPIONs) which translocate from roots to shoots regardless of
charge (Ghafariyan et  al. 2013). NP tends to agglomerate extensively because of
excess mucilage production in response to NP exposure (Cherchi et al. 2011; Kadar
et al. 2012; Nielsen et al. 2008; Verneuil et al. 2015). Mucilage in direct contact with
water or soil accumulates large fractions of Nanoparticles, which result in reduced
root–shoot translocation and uptake into cells and finally, nanoparticles start accu-
7  Uptake and Toxicity of Nanomaterials in Plants 175

mulating on the root surfaces. Different factors decide the translocation and accu-
mulation of nanoparticles. These factors and its effect on nanoparticles mediated
toxicity are described in the following section.

7.4.1  Effect of the Dispersion Medium

Dispersion medium of nanoparticles also affects the translocation and uptake of

nanoparticles from the surroundings. (Lin et al. 2009) studied the translocation and
accumulation, of Natural Organic Matter dispersed nanomaterials. Naturally occur-
ring organic matter (NOM) of different organic substances which is considered to
be an important factor affecting nanomaterial transportation to the plants. NOM
suspended fullerene C70 preferably accumulated as black aggregates in rice plants
roots as well as in seed although accumulation in stems and leaves, found negligi-
ble. The presence of aggregates in leaves suggests central cylinder route of water
and nutrients through the xylem. While in the matured plants which have robust
translocation system these aggregates were predominantly found in leaves or near
the stem’s vascular systems and no accumulation was reported in the roots. Fullerene
C70 devoid of NOM were supposed to enter the plant roots through capillary forces,
osmotic pressure, or via the highly regulated symplastic route.

7.4.2  Effect of Surface Characteristics

The impact surface properties of nanomaterial make in translocation across differ-

ent barriers is very interesting. Surface interaction allows fate of translocation of
particles inside the plants. Small size and greater hydrophilicity of the fullerols
C60(OH)20 allowed their permeability through cell walls of Allium cepa (Chen
et al. 2010). Fullerol accumulated in between the cell wall and plasma membrane
showing apoplastic mode of transport in the plant tissues. In comparison to the
hydrophilic fullerols, NOM dissolved hydrophobic fullerene C70, obstructed pores
of the cell wall causing negligible uptake of nanoparticles.

7.4.3  Effect of Size and Concentration of Nanoparticles

Nanoparticle translocation and accumulation also depends on the size and concen-
tration of nanoparticles. Maize with excised roots but intact apexes had not demon-
strated any translocation of Titanium dioxide (TiO2) nanoparticles (Nanoparticles)
(30 nm), probably due to its large size compared to the scale of the root cell wall
pore diameter (6.6 nm) in the maize (Asli and Neumann 2009).
176 A. Dev et al.

Soybean seeds treated with Zinc oxide (ZnO) nanoparticles in the concentration
range of 500–4000 mg L−1. The Zn uptake by the seedlings was found to be signifi-
cantly higher at 500  mg L−1 than at high concentrations (1000–4000  mg L−1)
(Lopez-Moreno et  al. 2010a). Lesser aggregation might be the reason of higher
translocation while high concentration favours the probability for the formation of
agglomerates. This agglomeration ultimately complicated the passage through the
cell pore walls, thereby reducing uptake and accumulation as understood from the
results. Cell-to-cell translocation depends on the size exclusion limit of plasmodes-
mata between adjacent cells. Green Fluorescent Protein (GFP) (27 kDa) which is
nearly 3 nm in size move through the cells. It indicate that Nanoparticles smaller
than 3 nm might also traffic between cells and through the phloem. Carbon-coated
magnetic Nanoparticles injected into pumpkin shoots moved from the site of appli-
cation across, the stem parenchyma tissue and in xylem vessels (Corredor et  al.
2009). When sprayed through leaves, Nanoparticles appeared inside the epidermal
cells of the petiole with the low efficiency translocation.

7.4.4  Effect of Plant Species

Plant species play crucial role in translocation as none of the two plants have exact
same structure. Environment in which the plant are growing also allow plant to
work differently under certain circumstances. Tissue and cell-specific distribution
of an ultrasmall TiO2 (less than 5 nm) nanomaterial complexed with Alizarin red S
nanoconjugate was studied by Kurepa et al. Roots of A. thaliana supposed to release
mucilage that formed a pectin hydrogel. Polysaccharides reported in mucilage
found to adsorb and inactivate the toxic heavy metals in the rhizosphere and
enhanced accumulation in different plant species (Watanabe et al. 2008). The seed-
lings of soybean, alfalfa (Medicago sativa), corn, and tomato (Lycopersicon escul-
entum) accumulated Ce in tissues in concentration gradient manner as corn
accumulated ~300  mg kg−1 while soybean, tomato and alfalfa accumulatd 462,
4000, 6000 mg kg−1 respectively). This variable accumulation could be possible due
to distinct differences in root microstructures and the physical and chemical interac-
tions between the Nanoparticles and root exudates in the rhizosphere. No detectable
translocation was reported in plants when Nanoparticles applied in the irrigation
water. This clearly suggests that the translocation variation of nanoceria might be a
species dependent process (Lopez-Moreno et al. 2010b).
There are some other structures in plants that vary species to species like the pits
in the peripheral primary walls of xylem vessels. It allows perfusion of free dyes
between adjacent vessels. Pit sizes in xylem vessels of other species, such as Abies
nordmanniana, Thuja plicata, Gingko biloba and Eucalyptus regnans, are reported to
be much larger, with values in the μm range (Shane et al. 2000). Movement between
vessels in such species should be easily possible once Nanoparticles reach the xylem
because these vessels constitute open conduits for particle movement that are used by
bacteria to spread within plants. Fluro-Spheres polystyrene microspheres of 1.0 mm
7  Uptake and Toxicity of Nanomaterials in Plants 177

fed to excised vine leaves moved from petioles, via petiole-leaf blade junctions, into
the 1st and 2nd order veins of the leaf blade (Thorne et al. 2006). However, this con-
nectivity can significantly vary between species and pit membranes might restrict the
free movement of larger Nanoparticles through the xylem in other species.
Pumpkin (Cucurbita maxima) plants exposed to 0.5 g L−1 Fe3O4 Nanoparticles
(20 nm) in hydroponics medium translocated 1.3% of the total amount to the leaves,
as determined by vibrating sample magnetometry. Most particles were associated
with the pumpkin root surface. Lima bean plants failed to show any magnetic signal,
therefore no accumulate of any particles reported. This difference reveals significant
variation in particle uptake and translocation among species (Zhu et al. 2008).
Translocation of copper nanoparticles (Cu Nanoparticles) in wheat cultured in
solidified plant growth medium investigated (Lee et  al. 2008). Cu Nanoparticles
found to cross the cell membrane and accumulated in the cells. Plant shows a unique
quality to transform one form of material to another. Reports on this phenomenan
are few therefore it is difficult to believe. Ag(I) ions and Au(III) grown in agar solid
media in alfalfa seedlings were transformed to Au and Ag Nanoparticles (Gardea-­
Torresdey et al. 2002, 2003) so as the Pt(II) ions into Pt Nanoparticles in alfalfa and
mustard seedlings was also reported (Bali et al. 2010). These studies strongly sug-
gest that heavy metals nanoparticles can be formed or accumulated in alfalfa and
mustard seedling but no one have clearly shown how this transformation is pro-
cessed inside the plants and where these transformed materials is accumulating.
Available literature indicated vaguely that Nanoparticles are found in the plant’s
cells and tissues, although one of the above-mentioned studies with Single-Walled
Carbon Nanotubes (SWCNTs) in N. tobacum plant cell suspensions found their fate
in vacuoles (SWNTs_FITC) as well as cytoplasmic strands (SWCNT_DNA)
(Parsons et al. 2010). Ag Nanoparticles found to be accumulated in the stem and on
the surface of root cell organelles in alfalfa (Harris and Bali 2008; Gardea-Torresdey
et al. 2003). Is this conversion is plant species specific or all the plant have tendency
to do this? Do only heavy metals transformed to the nano form? No specific studies
addressing this gap are presently available.

7.5  Transfer to the Next Generation and Trophic Level

Transfer of nanoparticles from one generation to the next generation is possible or

not, the answer to this question seems to be positive. C70 was detected, in the leaf
tissues of second-generation rice plants (Lin et al. 2009). Presence of Nanoparticles
in second-generation plants might cause adaptability of plants which can be lead to
more possible accumulation of the respective Nanoparticles. If these nanoparticles
seem to be accumulating in next generation, what could be the bioavailability for
the next trophic level? This question is still not answered so far. Although there are
studies showing inter trophic and intergeneration transfer of Nanoparticles in algae
and tobacco (Navarro et al. 2008; Judy et al. 2011) but no report of magnification in
higher trophic level is available.
178 A. Dev et al.

7.6  Plant Response to Nanoparticles Toxicity

Plants respond to different types of stresses in various manners, weather the stress
is because of some kind of environmental issues or due to exposure to some toxic
substances. The plant produces reactive oxygen species as a reaction mechanism to
the stresses. There are reports that prove that plant produces reactive oxygen species
(ROS) in response to heavy metals (Sharma et al. 2012) and Nanoparticles (Begurn
et al. 2011; Rico et al. 2013b). ROS is a byproduct of metabolism in plants but as
plant faces stress the generation of ROS increases significantly and result in oxida-
tive damage and cell death in plants. This oxidative stress can be measured by
directly measuring the H2O2 or ROS in plants, by measuring lipid peroxidation or
electrolyte leakage. ROS generation and oxidative damage are believed to cause
toxicity in NP-treated plants but little is known about the mechanism how nanopar-
ticles produce ROS and membrane damage in plants.

7.6.1  P
 roduction of Reactive Oxygen Species in Response
to Nanoparticles

Under normal conditions, ROS are the byproducts of normal metabolic pathways
that localised in different cell organelles like mitochondrion, chloroplasts, and per-
oxisomes (Moller et  al. 2007). Although excessive production of these species
proven lethal to the plants (Fig. 7.1). Plants have mechanisms to counter the produc-
tion of such species in the form of various enzymes and hormones (salicylic acid,
abcisic acid) that came into play once plants signal oxidative stress. Plant hormones
like abcisic acid (ABA) and salicylic acid (SA) turn on different pathways to provide
life support to the plants. Oxidative damage mainly caused by different abiotic and
biotic stresses that suddenly generate huge amounts of ROS (Carocho and Ferreira
2013). Among these ROS some are very common which includes hydrogen peroxide
(H2O2), singlet oxygen (1O2), hydroxyl radical (HO•) and superoxide (O2•−) (Mourato
et al. 2012). Different counter enzyme catalase (CAT), guaiacol peroxidase (GPOX),
ascorbate peroxidase (APOX), superoxide dismutase (SOD), glutathione reductase
(GR), and dehydroascorbate reductase (DHAR) with typical low molecular weight
antioxidants like thiols (GSSG or GSH) and ascorbate helps to avoid oxidative dam-
ages in plants and convert highly toxic ROS species to less toxic species. These spe-
cies like H2O2 was predominantly located in epidermal, parenchyma, and bundle
sheath cells within the leaf tissue (Zhao et al. 2012) and found to initiate further Fe2+
and Cu2+ catalysed Fenton reaction, and generate HO•, highly reactive ROS (hROS),
which cannot be detoxified by any known enzymatic system.
This highly reactive ROS induces irreversible damage to lipids, DNA, and pro-
teins (Mourato et al. 2012; Freinbichler et al. 2011). Metal-based nanoparticles are
one of the leading cause of the production of the hROS but as such there are no
reports on HO• determination so far although levels of hydrogen peroxide (H2O2)
can be readily measured.
7  Uptake and Toxicity of Nanomaterials in Plants 179

Fig. 7.1  Reactive oxygen species (ROS) mediated mechanisms inside the plant cell including cell
organelles and salicylic acid (SA), Glutathione (GSH), Glutathione disulphide(GSSG) mediated
cross talk during stress responses

In a study two rice cultivars Neptune and Cheniere exposed to variable concen-
tration of CeO2 Nanoparticles, showed different H2O2 levels. The H2O2 level in rice
cultivar “Neptune” was three times higher than the control group (Rico et al. 2013a)
whereas cultivar “Cheniere” showed no significant difference upon exposure to the
same concentration of cerium dioxide (CeO2) Nanoparticles (Rico et  al. 2013b).
However when same two groups exposed to the low dose (62.5  mg L−1) showed
H2O2 scavenging. (Rico et al. 2013a, b; Lee et al. 2013c) provided evidence to dem-
onstrate that CeO2 Nanoparticles at lower exposure concentration (50 mg L−1) could
eliminate ROS through a Fenton-type reaction. (Zhao et al. 2012) reported effective
antioxidant defense through CAT and APX activities in corn grown in CeO2
Nanoparticles amended the soil, H2O2 level found to be low in the study as formed
ROS hypothesized to be converted into H2O. Other metal-based Nanoparticles such
as Ag Nanoparticles and ZnO Nanoparticles have been shown to generate excessive
amounts of ROS, which caused cell death, DNA damage, pollen membranes integ-
rity, and chlorophyll content. Significantly higher level of O2•− and H2O2 in onion
was found when exposed to Ag Nanoparticles (Panda et al. 2011; Mukherjee et al.
2014; Speranza et  al. 2013). As mentioned earlier, to defend against oxidative
stresses and nanoparticles mediated stress, plants are capable of converting more
toxic ROS (O2•−) into less toxic species but none of the available antioxidant systems
can successfully transform HO• produced in response to Nanoparticles exposure.
180 A. Dev et al.

7.6.2  Detoxification Pathways in Plants

In plant cells, there are different types of ROS-scavenging pathways that help plant to
overcome stress. It has been found that ROS generation and antioxidant activity may
vary with exposure conditions, Nanoparticles type, and plant species and doses of
nanoparticles. Three types of SOD are reported in plants which include Fe-SOD,
Mn-SOD, and Cu-Zn-SOD. These SOD can rapidly convert O2•− to less toxic H2O2.
Hydrogen peroxide still toxic to plants which further induces three other main anti-
oxidant enzymes pathways that help plants to detoxify this species. The first reaction
involves catalysis of H2O2 to H2O and O2 by CAT. The another reaction is mediated
by APX that converts H2O2 to H2O by ascorbate oxidation into mono dehydroascor-
bate (MDA) and dehydroascorbate (DHA); the third reaction is catalysed by GPX,
which produces the oxidised GSH, which can be subsequently reduced by glutathione
reductase (GR) (Mittler 2002; Mittler et al. 2004; Noctor and Foyer 1998). Also, GSH
is an excellent antioxidant molecule that directly transforms H2O2. CAT and APX
activities have been reported in several studies when plant species were exposed dif-
ferent doses of metal-based Nanoparticles. When rice cultivar “Cheniere” was treated
with 500 mgL−1 CeO2 Nanoparticles the APX activity in the root was unaffected.
While the high activity of GPX was observed at a same concentration of Nanoparticles
although no changes in enzyme levels were noted in the shoots (Rico et al. 2013b).
CAT activity in the root of rice cultivar “Neptune” upon CeO2 Nanoparticles treat-
ment was increased to 62.5 mgL−1 CeO2 Nanoparticles. Interestingly, APX and GPX
response was found to be similar to the “Cheniere” cultivar (Rico et al. 2013a).
Dose-dependent induction of CAT activity in cucumber leaves was reported after
exposing to the TiO2 Nanoparticles while no difference in APX activities was
observed (Servin et al. 2013). Although, in a different study significant induction of
CAT and APX activities in both stems and leaves of ZnO Nanoparticles treated
(4000 mg L−1) velvet mesquite was recorded (Hernandez-Viezcas et al. 2011).
Plant follows multiple antioxidant pathways and can switch from one route to
other depending on the nature of nanoparticles. CAT activity in wheat roots was
significantly elevated when treated with 500 mg kg−1 CuO Nanoparticles, whereas it
get inhibited at 500 mg kg−1 ZnO Nanoparticles treatment, suggesting that one ROS
scavenging pathway is not sufficient to combat ROS (Dimkpa et al. 2012). Information
of other stress-related genes and gene networks is limited that further need great
input to complement the current research problem. Understanding of defense mecha-
nism in plants against abiotic stresses especially nanoparticle-­mediated stresses fur-
ther investigations at genetic, proteomic and the metabolomic level is necessary.

7.6.3  Glutathione Pathway in Detoxification

Glutathione (GSH) is a well-characterized antioxidant and a critical component of

defense response for oxidative stress as a result of heavy metals exposure (Hopkins
and Harris 1929; Cobbett et al. 1998; Dhankher et al. 2002).GSH can scavenge ROS
7  Uptake and Toxicity of Nanomaterials in Plants 181

and itself oxidised to a disulphide form (GSSG), which can then be recycled by
Glutathione reductase. Some components in plant cell machinery chelate heavy
metals for, e.g., Phytochelatins (PC), the downstream products of GSH, chelates
metals ions and help in detoxification of heavy metals (Grill et al. 1989; Cobbett
2000; Mishra et al. 2006).The heavy metal detoxification pathway is well known in
plants that are mediated by biosynthesis of GSH. Li et al. overexpressed γECS gene
in shoots of Arabidopsis and reported significantly higher levels of GSH and PCs
upon arsenic (As) and mercury (Hg) exposure, caused increased metal tolerance in
transgenic plant (Li et al. 2006). Similarly, (Paulose et al. 2010; Zulfiqar et al. 2011)
reported upregulation of GSH biosynthesis and sulphur assimilation in transcripts
of Abyssinian mustard (Crambe abyssinica Hochst. Ex Fries) that were treated with
As and chromium (Cr).
It is unclear that the same mechanism is activated upon Nanoparticles phytotox-
icity or not, although assessment of GSH levels in plants exposed to metal-based
Nanoparticles has reported in some of the studies. Plant gene regulation and GSH
biosynthesis upon metal-based Nanoparticles exposure were first reported in
Arabidopsis exposed to CeO2 and In2O3 Nanoparticles (Ma et al. 2013a). Highly
induced level of a cysteine-rich protein metallothionein (MT), and GSSG was found
in wheat after exposure to Ag Nanoparticles, Ag + ions, and bulk Ag in sand
(Dimkpa et al. 2012). An elevated level of GSSG in wheat shoots and roots grown
in CuO and ZnO Nanoparticles was also found (Dimkpa et al. 2012) but the increase
in the levels of GSSG could not be used directly to show the GSH activity of ROS
conversion into H2O.
GSH supposed to be involved either in detoxification of metal ions released from
Nanoparticles or tackling of ROS generated in response to Nanoparticles exposure
in plants. There is no report except one study (Ma et al. 2013a) on evaluating gene
regulation or antioxidant levels in response to Nanoparticles toxicity. Molecular-­
level understanding of plant responses to nanotoxicity is critical to assess accurately
overall exposure and risk concerns.

7.6.4  Anthocyanin and Heat Shock Proteins

There are some antioxidant compounds like Anthocyanin that are highly distributed
throughout the plant cells like and known to scavenge free radicals and chelate met-
als under the abiotic stresses (Carocho and Ferreira 2013; Mourato et  al. 2012;
Gould 2004). In addition to the antioxidant plants have molecular chaperone such
as HSPs to fight against stresses like heat, drought, salt, and heavy metals (Wang
et al. 2004; Timperio et al. 2008; Bajguz and Hayat 2009). However, what role of
HSPs play in response to Nanoparticles exposure is not known but it is assumed that
it performed the same kind of function as in oxidative stress.
182 A. Dev et al.

7.7  Nanotoxicity at Different Level

Nanotoxicity is a major concern in nowadays since nanomaterial usage increased

significantly in last few years but what impact its making to the plant system is not
very clear. What physiological, biochemical and genetic changes it is making to the
plant is not well understood. It is believed that these changes equally contributing to
the nanotoxicity and cross talk might be the reason of adaptability or toxicity in the
plants (Fig. 7.2). Current section is based on toxicological impact of nanoparticles
at different levels in plants.

7.7.1  Phytotoxicity at Morphological and Physiological Level

Nanoparticles have found to make different effects on seed germination, root elon-
gation and biomass. Fe3O4, TiO2, and carbon Nanoparticles were found to nega-
tively affecting seed germination rate, root elongation, and germination index in
cucumber plants (Mushtaq 2011). The authors found different effects of
Nanoparticles and their counterparts on Cucurbita pepo after treatment of different
Nanoparticles such as multiwalled carbon nanotubes (MWCNTs), Ag, Cu, ZnO,
and Si in suspensions up to 1000 mg/L (Stampoulis et al. 2009). Germination rates
were not affected as such but emerging root length was found to be reduced in Cu
Nanoparticles treatment. Ag Nanoparticles caused a decrease in plant biomass and
transpiration rate. Although this test was not found to be sensitive enough to evalu-
ate and monitor toxicity to terrestrial plants (Stampoulis et al. 2009). Toxicity, dis-
tribution, and biotransformation of the three materials in plant roots was studied and

Fig. 7.2 Nanotoxicity
crosstalk at various levels
in plant cell
7  Uptake and Toxicity of Nanomaterials in Plants 183

found that with the nano-Yb2O3 exposure,YbPO4 deposits were found in the cyto-
plasm of root cells and compared the toxicity of nanoparticulate Yb2O3, bulk Yb2O3,
and YbCl3•6H2O in cucumber plants (Zhang et al. 2012). Effects of rare earth oxide
Nanoparticles (nano-CeO2, nano-La2O3,nano-Gd2O3, and nano-Yb2O3) on root
elongation of higher plant species was evaluated (Ma et al. 2010) and it was found
that different Nanoparticles caused distinct effects on root growth, and these effects
also varied among plant species.
Phytotoxicity is not a single factor driven process there should be different
parameters that are contributing synergistically and causing toxicity. Different
parameters that should be counted while measuring the phytotoxicity are included
in the coming section.

7.7.1.1  Surface Modification of Nanoparticles and Dose Concentration

Surface modification of nanoparticles, doses of nanoparticle treatment and plant

species changes the impact of toxicity to the plant. A recent study reporting the
interaction of SiO2 Nanoparticles with algae showed that alumina coated SiO2
Nanoparticles were less toxic to Pseudokirchneriella subcapitata than bare SiO2
Nanoparticles (Hoecke et  al. 2011). Al2O3 Nanoparticles at concentrations up to
4000 mgL−1 had no significant toxic effects on seed germination, root elongation,
and some leaves of Arabidopsis thaliana (Lee et al. 2010). One study showed that
10–40  mg L−1 of carbon nanotubes increased seed germination and growth of
tomato plants (Khodakovskaya et  al. 2009). This supposed to be due to carbon
nanotubes ability to penetrate the seed coat and enhance the significant water uptake,
although these specific mechanisms were not reported. Nano-TiO2 was also found
to improve energy utilisation and conversion efficiency in D1/D2/Cyt b559 complex
of spinach by enhancing its growth (Su et  al. 2009; Larue et  al. 2011) found no
significant effect of TiO2- Nanoparticles on germination and root elongation of
Triticum aestivum, Brassica napus, and Arabidopsis thaliana.
Toxicity effect of nanomaterials in most of the studies recognised on seed germi-
nation or 15-dayold seedlings (Rico et  al. 2011). Metallic nanoparticles
(MNanoparticles) and metal oxide nanoparticles were shown to be inhibitive at dif-
ferent developmental stages of plants such as seed germination and root elongation
(Lin and Xing 2007; Yang and Watts 2005). Copper nanoparticles reduced growth
rate of mung bean (Phaseolus radiatus) and wheat (Triticum aestivum), which is
one of a symptom of toxicty (Lee et  al. 2008). Very low concentrations of
AgNanoparticles (b1 ppm) found to be toxic to the seedlings of thale cress
(Arabidopsis thaliana), although AgNanoparticles of 20–80 nm clearly stunted the
growth in concentration and particle size dependent. The root tip (cap and colu-
mella) of primary roots turned light brown when exposed to AgNanoparticles, this
might be because of the adsorption of AgNanoparticles alone or after forming a
complex with secondry metabolites of root tips.
184 A. Dev et al.

7.7.1.2  Dissolution of Nanomaterials

Determination of phytotoxicity of metallic nanoparticles and their oxides found to

be very difficult as metallic nanoparticles found to be dissolved into metallic ions.
Dissolution of metal oxide nanoparticles alone cannot be a direct indicative measure
of toxicity as ZnO nanoparticles toxicity to Arabidopsis was found to be much much
stronger than solutions containing the same concentration of soluble Zn (Lee et al.
2010). Phytotoxicity of ZnO nanoparticles in seedlings caused stunt growth, reduced
biomass and root cap deformity. Higher concentration of ZnO nanoparticles caused
shrinkage of root tips high collapsing of epidermal and cortical cells.

7.7.1.3  Physical Interaction of Nanoparticles

Inhibition of plant growth is not the direct measure of toxicity caused by chemical
nature of nanoparticles; instead toxicity may be result of inhibited apoplastic and
symplastic flow caused by blockage of the intercellular spaces, cell wall pores, and
nano-sized plasmodesmata. These may be because of physical interaction of
nanoparticles with the plants (Asli and Neumann 2009). Plant growth and transpira-
tion in maize seedlings (Zea mays L.) was inhibited by bentonite and TiO2 nanopar-
ticles. Studies showed that loss of hydraulic conductivities and reduction in diameter
of maize root cell wall pores from 6.6 nm to 3.0 nm was the main reason of less
transpiration.

7.7.1.4  Solvent Effect and Presence of Stabilisers

Other factors which need to be considered in phytotoxicity study are the solvent
effect and presence of stabilizers in the nanoparticle formation. Most commercial
products contain certain stabilizers that interact with the nanomaterial and change
its property to interact with the plants. The synergetic effects of Nanoparticles and
stabilizers should be taken into consideration in phytotoxicity studies. Different tox-
icity effects of three metallic nanoparticles were studied on lettuce and cucumber
and it was suspected that reported toxicity is could be primarily due to the presence
of stabilizers (Barrena et al. 2009).

7.7.1.5  Method of Nanoparticle Preparation

The information regarding preparation methods is crucial as different sample prepa-

rations resulted in different toxicological properties (Nurmi et al. 2005; Lovern and
Klaper 2006). Different methods of nZVI preparation shown variable properties of
the nanoparticles, as fullerene showed preparation method based toxicological
properties (Oberdorster et al. 2006; Zhu et al. 2006). Another very important param-
eter in the toxicity study is the selection of phytotoxicity indicator so far seed
7  Uptake and Toxicity of Nanomaterials in Plants 185

germination and root elongation are the only two standard indictors of phytotoxicity
suggested by U.S.  Environmental Protection Agency. These indicators are found
least sensitive to monitor toxicity of nanoparticles (Stampoulis et al. 2009). Although
plant biomass and chlorophyll levels shown to be more sensitive but needed stan-
dardization for phytotoxicity studies of nanomaterials.
It is urgent not only to elucidate further the effects of Nanoparticles in plants to
characterize the uptake, phytotoxicity, and accumulation of Nanoparticles, but also
to understand how nanoscale materials can affect food chains and, ultimately, to
human health risk assessment. Moreover, the main question remains, that is, which
are the best standard phytotoxicity tests that may be used in assessing Nanoparticles
toxicity? For example, most of the studies up to moment were based on germination
and root elongation, which are not sensitive enough or appropriate when evaluating
NP toxicity to terrestrial plant species (Rodriguez et al. 2011).

7.7.2  Phytotoxicity at Genetic Level

One of the most questionable aspects is what parameter should be used to detect
genotoxicity as there are not much information on genotoxicity of nanoparticles.
(Atha et al. 2012) reported for the first time that copper oxide Nanoparticles causes
DNA damage in some agricultural and grassland plants (Raphanus sativus, Lolium
perenne, and Lolium rigidum). Comet assay is one of the indicative measures of
DNA damage but it doesn’t tell about the mutation at genetic levels. Another param-
eter includes analysis of the mitotic index (MI), chromosomal aberrations (CA), and
micronuclei induction (MN) which provide evidence for the genotoxicity of
Nanoparticles in plants. In one study of root cells of Allium cepa it was found that
ZnO Nanoparticles exert cytotoxic and genotoxic effects, a decrease in mitotic
index, and increasing of the micronuclei and chromosomal aberration indexes were
reported (Kumari et al. 2011). In a microarray-based gene expression analysis in
Arabidopsis thaliana roots on exposure to ZnO-Nanoparticles, TiO2-Nanoparticles,
it has been found that mechanisms of genotoxicity toxicity are highly specific to the
nanoparticle (Landa et  al. 2012). Gene expression analysis in tomato exposed to
carbon nanotubes (CNTs) revealed up-regulation in the stress related and Aquaporins
gene. In a separate study in maize, selective root growth was reported upon expo-
sure to single-walled carbon nanotubes (SWCNTs). Transcriptional analysis of
roots suggests that SWCNTs and root cell interaction selectively modulates gene
expression of seminal roots, resulting in relative retarded root growth (Yan et al.
2013).
Molecular marker technology is the recently available method that can provide
genotoxicity information at the sequence level. Genotoxicity is supposed to be
mediated by oxidatively modified compounds that tend to accumulate in the nucleus
and created mutagenic DNA lesions and caused inhibition of plant growth. Such
studies indicated the current need of Nanoparticles toxicity measurements in plants
to evaluate the putative genotoxicity of the different Nanoparticles.
186 A. Dev et al.

7.7.3  Phytotoxicity at the Proteome Level

Phytotoxicity of Nanoparticles has been evaluated extensively in various plants.

Plant physiology and biochemistry define its capacity to overcome stresses.
Different types of molecules produced in the plant cell at variable stages which
change the proteome level. Studies that describe such changes is very limited.
Root proteome of Oryza sativa was studied after treatment with Ag-Nanoparticles.
This study revealed that Ag-Nanoparticles-responsive proteins were mainly associ-
ated with detoxification pathway, which includes Ca2+ regulation and cell signaling
(Mirzajani et al. 2014). Elevated levels of defense-related proteins like superoxide
dismutase, L-ascorbate peroxidase, glutathione-S-transferase indicate accelerated
production of ROS under Ag-Nanoparticles treatment. This group hypothesised that
Ag-Nanoparticles or released ions bind to second messenger calcium ion receptors,
calcium ion channels, and Ca2+/Na + −ATPases and slowdown the cell metabo-
lism. Eruca sativa roots exposed to Ag-Nanoparticles and AgNO3 revealed that both
forms of Ag caused disruption in cellular homoeostasis after altering redox regula-
tion related protein (Vannini et al. 2008). Phytotoxicity of Ag-Nanoparticles is pri-
marily due to their characteristic physiochemical properties, and not by releasing
the Ag + because Ag-Nanoparticles were found to be responsible for altering the ER
and vacuolar proteins which indicate these organelles as target sites of
Ag-Nanoparticles. Toxicity mechanisms of Ag-Nanoparticles were also studied on
early-stage-soybean growth under flooding stress (Mustafa et al. 2015).

7.8  Different Nanoparticles and Mediated Toxicity

Significant progress in nanotechnology has directed a considerable interest toward

the application of nanotechnology in agriculture (Mura et al. 2013). As nanoparti-
cles based application in agriculture increasing at a rapid rate so as nanoparticle
mediated toxicological concerns. Some very unusual and catalytic property of
nanomaterials makes them one of a prominent toxic material. Bioactive surface and
their small sizes allow them to pass through the cell membranes and interact with
different cellular structures and biomolecules. The latest studies on phytotoxicity of
different nanomaterials (ZnO, CeO2, TiO2, NiO, CuO, Ag, Au, SiO2, nZVI, fuller-
enes, graphene oxide, carbon nanotubes) is elaborated in the following section.

7.8.1  Silver Nanoparticles

Silver nanoparticles property of agglomeration, to get easily oxidised in water form-

ing a complex with anions and converting to heavy metals makes it hazardous
(Shams et al. 2013). Suspended silver nanopowders of 50 nm in water with different
7  Uptake and Toxicity of Nanomaterials in Plants 187

concentrations and repeatedly sprayed them in different parts of cucumber plant to

monitor their effects. Increasing the concentration of Nanoparticles, increased the
concentration of silver heavy metal and the growth index, and at the same time, the
plant morphological characteristics were improved. Heavy silver accumulates
mainly in roots and decreases in leaf, tissue, and skin of the fruit showing an
improvement of silver heavy metal in various plant organs by increasing the con-
centration of AgNanoparticles in a spray form. This amount is less in fruit, the most
edible part of the plant, but can be dangerous if consumed steadily, for this reason,
it is important to define the concentration limit of the consumed plants (Vannini
et  al. 2013). Treated seedlings of Eruca sativa with different concentrations of
AgNanoparticles to understand the morphological and proteomics changes induced
by Ag in the form of nanoparticles. The results showed that AgNanoparticles caused
oxidative stress and altered specific cellular functions of the plant cell at the molecu-
lar level. (Oukarroum et al. 2013) found AgNanoparticles as a growth inhibitor of
an aquatic plant Lemna gibba, which was exposed to different concentrations of
Nanoparticles. Plant cellular viability was reduced because of the formation intra-
cellular ROS. It was proposed that the stress was produced due to the release of free
Ag inside the plant cells. Colloidal silver (AgNP) Nanoparticles significantly
decreased root elongation at all the concentration tested in tomato plants (Song
et  al. 2013). Smaller hydrodynamic diameters of AgNanoparticles supposed to
induce higher uptake and phytotoxicity. Silver Nanoparticles were taken up into
plant stems, leaves and fruits and lowered chlorophyll contents, elevated superoxide
dismutase activity and decrease fruit productivity. Studies on silver nanotoxicity in
plants have been controversial and centered whether the cause of toxicity is either
the nanosize and shape of the particles or their release as ionic Ag+. All studies,
however, agree that silver nanotoxicity is positively concentration-dependent and
negatively size-dependent (Geisler-Lee et al. 2014).

7.8.2  CeO2 Nanoparticles

CeO2 Nanoparticles have a limited dissolution in soil and plant tissues still these
nanoparticles have found to interact with the plant. CeO2 Nanoparticles affected
plant antioxidant defense system and regulated oxidative stress in germinating rice
seeds grown for 10 days in suspensions of CeO2 Nanoparticles at different concen-
trations (Rico et  al. 2013b). Plants maintain its reactive oxygen species levels
through a different mechanism, but an excess of these species induces oxidative
stress. CeO2 Nanoparticles down-regulated the production of antioxidant enzymes
catalase (CAT) and ascorbate peroxidase (APX) that helps plant to deal with oxida-
tive stress and changed the chemical environment of carbohydrates in shoots, sug-
gesting that these Nanoparticles can change the nutritional properties of cilantro.
Tomato plants were treated with low concentrations of CeO2 Nanoparticles (10
mg/L) in the first generation of their lifecycle but seed quality and the development
of second generation seedlings was affected dramatically (Wang et al. 2013). The
188 A. Dev et al.

results indicated that second-generation seedlings were infertile, grown with smaller
biomass, lower water transpiration rates, and higher ROS content.

7.8.3  ZnO Nanoparticles

ZnO nanoparticles caused a significant reduction in biomass, and growth with a

higher translocation in a medicinal plant Fagopyrumn esculentum (Lee et al. 2013a).
These particles were found to pass through the cell membrane and formed aggre-
gates within the cell producing toxic effect. The different toxic effect was reported
which include shortened and damaged roots with reduced glutathione level.
Increased amount of reactive oxygen species (ROS) was reported which is consid-
ered to be indicative markers of nanotoxicity. High Nanoparticles concentration
stimulated the antioxidant defense system. As a result, the amount of GSH increased
and CAT loosens the scavenging capacity and plant stressed to oxidative damage.
Phytotoxic and genotoxic effects of ZnO on buckwheat seedlings studied and found
that high concentration is genotoxic causing a damaging effect on DNA and altering
gene expression (Lee et al. 2013b).

7.8.4  Cupric Oxide Nanoparticles

Genotoxic and phytotoxic potential of these Nanoparticles in the roots of

Fagopyrumn esculentum seedlings was studied using the RAPD assay (Lee et al.
2013b). It was observed that the seedling growth was affected due to significant
changes in root morphology and root length as nanoparticles were found to be accu-
mulated, in the root epidermis. High doses of CuO Nanoparticles disturbed cellular
homeostatic balance after altering intracellular signalling pathways which ulti-
mately leading to a cascade of genotoxic effects.
In another report behaviour of CuO Nanoparticles was evaluated in Wheat plants
which were treated with these Nanoparticles. These nanoparticles found to be toxic
to wheat causing a reduction in root length (Dimkpa et al. 2013).

7.8.5  Fullerene

Internalisation and accumulation of these compounds in plant roots and seedlings is

well established (Liu et al. 2013). Carboxy-modified fullerenes disrupted the cell
wall and modified the cell membrane of tobacco plants after adsorption to the plant
cell surface. AFM measurements and confocal imaging confirmed the presence of
glycosyl residue on the cell wall of treated plants. The enhanced intracellular ROS
was found in the cell membrane as well as in all the parts of cells. The disruption of
7  Uptake and Toxicity of Nanomaterials in Plants 189

the cell membrane is might be due to the enhanced ROS generation and activation
of the plant defense system. Alteration of cell composition is considered to be the
response of the plant to fight the stress induced by carboxy fullerenes.

7.8.6  Nickel Oxide Nanoparticles

Translocation and phytotoxicity induced by NiO Nanoparticles in tomato seedling

was monitored for different cellular function (Faisal et al. 2013). The result showed
that NiO Nanoparticles caused mitochondrial dysfunction and induced apoptosis in
tomato root cells after triggering the release of caspase-3 proteases from mitochon-
dria. Further, these particles induced oxidative stress by regulating antioxidant
enzymes caused necrosis in tomato seedling roots and finally damage DNA. This
analysis described the potential hazardous impact of these nanoparticles to induce
cell death through the apoptotic and necrotic pathway.

7.8.7  Nanoscale Zero Valent Iron

Nanoscale zero-valent iron (nZVI) toxicity analysis in plant seedlings of cattail and
hybrid poplars was performed (Ma et  al. 2013b). These particles were found to
move into the root cells of poplar plants and can pass through the cell wall and
membrane of poplar roots. These plants were treated with different concentrations
of nanoparticles (0–1000 mg/L) and found that at high concentration nZVI exhib-
ited strong toxic effects. TEM and STEM study confirmed the presence of
Nanoparticles in epidermal cells and accumulation at plant roots surfaces.
Accumulation of nanoparticles formed a black coating on the root surface and
blocks the membrane pores affecting water and nutrient uptake processes. This
black coat might be the direct deposition of nZVI or it can be a combination of ferric
iron oxides and zero-valent iron.

7.8.8  Gold Nanoparticles

Gold nanoparticles toxicity in plants was studied using Allium cepa as a model
plant, because of its stable chromosome number and karyotype. Toxicity of nanopar-
ticles was found to be size- and dose-dependent after evaluating cytogenetic effects
of gold Nanoparticles in Allium cepa bioassay. Gold nanoparticles with three differ-
ent sizes (Au15, Au30, and Au40) and three different concentrations (0.1, 1 and 10
mg/mL) were exposed to the root tip of Allium cepa, and it was found that several
chromosomal aberrations were present when observed under optical microscope.
The mitotic indices in treated root tips showed that impact of Nanoparticles
190 A. Dev et al.

concentration was directly proportional while their size showed inverse relation to
their size. Further analysis revealed that gold Nanoparticles generated various ROS
(reactive oxidant species like superoxide, hydrogen peroxide and hydroxyl) which
caused lipid peroxidation in the cells and contributed to the toxicity. (Rajeshwari
et al. 2016).
Nanoparticles interactions and their trophic transport was studied (Tara Sabo-­
Attwood et al. 2012) using gold nanoparticles in tobacco plants (Nicotiana xanthi).
This study was very crucial to know how this interaction and transport contributed
to nanoparticles toxicity. Tobacco plants were exposed to gold Nanoparticles and
uptake studies, biodistribution studies and toxicity studies were performed using
high-resolution electron microscopy, synchrotron-based X-ray.

Sr. No. Nanoparticles Toxic effects Plant References

1 Silver nanoparticles Accumulation of Aquatic plant Oukarroum
AgNanoparticles, ROS Lemna gibba et al. (2013)
generation
Decrease of root Tomatto Song et al.
length, significant (2013)
decrease of biomass,
higher SODactivity,
lower chlorophyll
content and fruit
productivity
2 CeO2 nanoparticles Downregulation of Cilantro Morales et al.
defensive enzymes; (2013)
change in nutritional
value
Smaller seedlings, Tomatto Wang et al.
weaker and extensive (2013)
root hairs
3 ZnO nanoparticles biomass reduction, Fagopyrum Lee et al.
higher translocation of esculentum (2013a)
Zn, shortened and
damaged root
4 Cupric Oxide Inhibition of root F. esculentum Lee et al.
nanoparticles length, interference in (2013b)
cellular homeostatic
balance, altered
intracellular signaling
pathways, genomic
DNA damaging,
altered gene
expression
5 Fullerene Disruption of the cell Tobacco Liu et al.
wall and membrane, (2013)
inhibition of cell
growth, phytotoxicity,
increased ROS
(continued)
7  Uptake and Toxicity of Nanomaterials in Plants 191

Sr. No. Nanoparticles Toxic effects Plant References

6 Nickel Oxide imbalance in Tomatto Faisal et al.
nanoparticles antioxidant enzymes, (2013)
oxidative stress,
apoptosis, and
necrosis, DNA
damage, Phytotoxicity
7 Nanoscale Zero Valent reduced transpiration Cattail and Ma et al.
Iron and interference with hybrid poplars (2013b)
the water and nutrient
uptake process
8 Gold nanoparticles Chromosomal Allium cepa Rajeshwari
abberations, et al. (2016)
production of various
ROS, lipid
peroxidation
Phytotoxicity, leaf Tobacco Tara Sabo-­
necrosis Attwood et al.
(2012)
9 Aluminium oxide Altered microRNA Tobacco Burklew et al.
nanoparticles expression, decrease in (2012)
leaf count
Lipid peroxidation, Tobacco Poborilova
ROS and NS et al. (2013)
generation
Reduced root length, wheat Yanik and
decrease in protein Vardar (2015).
content, cellular
damage
10 Iron oxide Decreased lipid Peanut Suresh et al.
nanoparticles content, increased (2015).
glycoprotein
Decreased leaf soyabean Burke et al.
phosphorus and (2015)
carbon, retarded
growth
11 Titania nanoparticles Reduced capacity of Ulmus Gao et al.
the plant to fight elongata (2013)
against strong light,
foliar applications
caused decrease in net
photosynthetic rate,
increased leaf
chlorosis and caused
defoliation
Inhibited seed D. magna Zhu et al.
germination and (2010)
reduced root biomass
production
(continued)
192 A. Dev et al.

Sr. No. Nanoparticles Toxic effects Plant References

12 Silica nanoparticles Phytotoxicity Arabidopsis Van Nhan Le
thaliana et al. (2014).
13 Graphene oxide Enhanced release of Faba bean Anjum et al.
different reactive (2013)
oxygen

microanalysis and X-ray absorption near-edge microspectroscopy to localize

AuNanoparticles within plants. These studies revealed that AuNanoparticles entered
plants through the roots in a size dependent manner as 3.5 nm AuNP detected in
plants but 18 nm AuNanoparticles remained agglomerated on the root outer ­surfaces.
Physiological toxicity was observed after 14 days in the form of leaf necrosis.

7.8.9  Aluminium Oxide Nanoparticles

In a Aluminium oxide nanoparticles mediated toxicity study (Burklew et al. 2012)

plants were exposed to the tobacco (Nicotiana tabacum) plants at 0%, 0.1%, 0.5%,
and 1% of concentration and it was found that average root length and biomass was
increased while the leaf count of the tobacco seedlings significantly decreased.
Alteration in different microRNA expression was also reported as some microRNAs
(miR395, miR397, miR398, and miR399) found to be overexpressed during expo-
sure to 1% Al2O3 nanoparticles but none other treatment has shown the similar
behaviour. These overexpressed miRNAs were predicted to play a vital role in plant
stress responses against nanoparticle stress or any other environmental stress.
Toxic effects of aluminium oxide nanoparticles also studied in cell suspension
culture BY-2 of the tobacco plant (Poborilova et  al. 2013). These nanoparticles
showed inhibitory effect on culture growth in both time and concentration-­dependent
manner. Nanoparticles mediated ROS (hydrogen peroxide, superoxide anion radi-
cal) and nitrogen species (nitric oxide) generation has been well-established toxicity
parameter which causes lipid peroxidation and alteration in plasma membrane per-
meability. Besides, the loss of mitochondrial potential and enhancement of the
caspase-­like activity contribute to apoptosis in plants. In the current study alumin-
ium, oxide nanoparticles found to be involved in such cellular changes to induce
apoptosis in plant cells.
Time-dependent (24, 48, 72, 96 h) and dose-dependent (0, 5, 25, 50 mg/ml)
effects of 13-nm-sized Al2O3 Nanoparticles on an agronomic plant wheat (Triticum
aestivum L.) was studied. It was found that Al2O3 Nanoparticles reduced the root
length of wheat by 40.2% in 5 mg/ml, 50.6% in 25 mg/ml, and 54.5% in 50 mg/ml
after 96 h. Histochemical analysis revealed some physiological changes which
include lignin accumulation, callose deposition, and cellular damage in root cortex
cells which correlate the root length inhibition. Nanoparticle caused a decrease in
the total protein content after 96 h of exposure; increase in the peroxidase activity
7  Uptake and Toxicity of Nanomaterials in Plants 193

which is one of the oxidative stress factors. Further studies at DNA level revealed
that Al2O3 Nanoparticles induced DNA fragmentation, and direct exposure of Al2O3
Nanoparticles leads to phytotoxicity causing morphological, cellular, and molecular
alterations in wheat plant (Yanik and Vardar 2015).

7.8.10  Iron Oxide Nanoparticles

The Fe2O3 nanoparticle applied to the peanut seeds by the pre-soaking method at
4000 ppm concentration (Suresh et al. 2015). The Fourier transform infrared spec-
troscopic analysis revealed Fe2O3 mediated stress after calculating the mean ratio of
the peak intensities in various frequency regions. Leaf samples taken for protein
analysis showed a considerable change in glycoprotein content exhibiting 71.45%
increase while lipid content was decreased with total band area of 76.31 ± 0.468.
Toxic effects of positively charged Fe3O4 nanoparticles (Nanoparticles) were
investigated on the growth of soybean plants (Glycine max.) in addition to their
root-associated soil microbes (Burke et al. 2015). Soybean plants were treated with
different concentration of nanoparticles and grown in a greenhouse for 6 weeks.
Plant roots were analyzed for the presence of Arbuscular mycorrhizal (AM) fungi
and nitrogen-fixing bacteria using different culture and DNA techniques. Plant
growth was retarded with the application of Fe3O4 Nanoparticles, leaf phosphorus
and carbon was decrease.
Lemna gibba is an aquatic macrophyte shown to be a sensitive bioindicator of
superparamagnetic iron oxide nanoparticles (SPION). Plants were exposed for 7 days
to different types of SPION which include Fe3O4 (SPION-1), Co0.2Zn0.8Fe2O4
(SPION-2), Co0.5Zn0.5Fe2O4 (SPION-3) at variable concentration of 0, 12.5, 25,
50,100, 200 or 400 Âμg mL−1. SPION shown toxicity in concentration precise man-
ner, at 400 μg mL−1of SPION exposure, chlorophyll content was decreased, functions
of photosystem II (PSII) monitored and change in PSII activity was recorded with a
decrease in performance index by 83, 86, and 79% for SPION-1, SPION-2, and
SPION-3, respectively. These nanoparticles strongly produced reactive oxygen spe-
cies (ROS), which ultimately resulted in growth inhibition. These nanoparticles have
shown complex toxic mechanism in the entire plant system (Barhoumi et al. 2015).

7.8.11  Titania Nanoparticles

Titania nanoparticle potential toxicity to aquatic organisms is still not well known.
This issue is carefully addressed in a comprehensive toxicity study, using Daphnia
magna as a model organism. A toxicity study was performed using modified acute
and chronic toxicity tests. It was found that TiO2 nanoparticles exhibited minimal
toxicity to Daphnia within 48 h exposure time, but this toxicity trend is changing
after further treatment till 72 h. Exposure duration found to be a contributing factor
194 A. Dev et al.

for the NP-mediated toxicity. Further exposure of nanoparticles to the plant caused
reproductive defects, severe growth retardation and at last mortality. Nanoparticles
found accumulated in the plant which supposed to interfere with food intake and
ultimately affect growth and reproduction (Zhu et al. 2010).

7.8.12  Silica Nanoparticles

Toxicity evaluation of silica nanoparticles was performed in cell suspension culture

of Arabidopsis thaliana plant (Cabello-Hurtado et al. 2016). Newly designed mul-
tifunctional silica nanoparticles with an average diameter of 47 nm showed toxic
effects on plant cells, inhibited cell growth, decreased cell viability and photosyn-
thetic efficiency. Silica nanoparticles modified with CMB clusters generated an oxi-
dative stress and caused lipid peroxidation although unmodified silica nanoparticles
have shown no sign of ROS generation and lipid peroxidation. These modified silica
nanoparticles induced enzymatic antioxidant machinery of the plants compared to
control and the other treatments. Electron microscopy revealed internalization of
these nanoparticles which confirm the toxic effect of nanoparticles in the plant.
Phytotoxicity of silica nanoparticles (SiNanoparticles) was evaluated (Slomberg
and Schoenfisch 2012) as a function of its size, surface composition and concentra-
tion of nanoparticles in Arabidopsis thaliana. Plants were grown hydroponically for
3 and 6 weeks in different concentration of variable size and surface composition
nanoparticles. Chlorosis and reduced development were observed for plants exposed
to highly negative SiNanoparticles (−20.3 and −31.9 mV for the 50 and 200 nm
SiNanoparticles, respectively) regardless of particle concentration at alkaline
pH. These phytotoxic effects found to be related to the pH effects and due to the
adsorption of nutrients to the silica surface. Transmission electron microscopy and
inductively coupled plasma-optical emission spectroscopy (ICPOES) revealed
Size-dependent uptake of the nanoparticles in plant roots.
The SiO2 nanoparticles significantly decreased the plant shoot and root bio-
masses in transgenic cotton plants. These nanoparticles also affected the Cu, Mg
contents in shoots and Na content in roots with increase SOD activity and IAA
concentration. Also, TEM analysis revealed translocation of SiO2 nanoparticles
from roots to shoots via xylem sap (Van Nhan Le et al. 2014).

7.9  Conclusion

Current published literature showed that nanoparticles can cause adverse effects on
plants at physiological, cellular and molecular level. Studies on phytotoxicity
caused by nanomaterials revealed that physicochemical property of plant, chemical
and physical nature of nanoparticles determine interaction and fate of nanoparticles
in a plant system. Naturally occurring barriers of plants cells are the first site for
7  Uptake and Toxicity of Nanomaterials in Plants 195

interaction with nanomaterials which regulate the entrance of Nanoparticles, there-

fore, plant structure is a certain measure of differential toxicity of nanomaterials.
Once nanoparticles entered the cells, induce alterations of cell structures and bio-
molecules and produce ROS. Size of the nanoparticle considered to be the primary
factor in determining the type and magnitude of the cellular response. Understanding
of plant defense mechanisms against Nanoparticles-induced oxidative stress is very
critical. The plant faces different biotic and abiotic stresses and protects itself by
using different defense pathways. What different pathways are utilised by the plant
to counter nanoparticle-mediated toxicity is still not clear. To understand this whole
mechanism and key molecules a broad effort is required. To reveal plant mechanism
to overcome nanomaterial-induced stresses we should look through the whole cen-
tral dogma of plant life. A complete pool of information should be collected using
DNA sequencing, transcriptomics, proteomics, metabolomics and most importantly
the phenomics techniques, to establish toxicity measurements in plants. Complete
sets of sensitive assays and experiments must be designed to detect the toxicity at a
very low level.

Acknowledgement  Funding agency UGC is duly acknowledged for providing the fellowship
[22/12/2013(ii) EU-V)] to Mr. Atul Dev.

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Chapter 8
Nanomaterial Impact, Toxicity and Regulation
in Agriculture, Food and Environment

Anubhav Kaphle, Navya PN, Akhela Umapathi, Maulick Chopra,

and Hemant Kumar Daima

Abstract  Development in nanosciences has shown significant impact on all the

areas of natural and applied sciences. It is expected that further advancement will
bring benefits to agriculture, food, environment and medical sectors. Benefits of
nanomaterials are due to their unique physicochemical properties, which make
them significantly different than their bulk counterpart. Still, little is known about
the safety and potential toxicity of nanomaterials in agro-food sector, their long
term impact on environment and biological entities.
In this chapter, we provide a state-of-art snapshot on assorted nanomaterials
including metal or metal oxide nanoparticles, carbon nanotubes, liposomes, nano-
emulsions and dendrimers that are currently being used for plant protection, disease
treatment, packing materials for food security, development of new tastes or tex-
tures or sensations, pathogen detection and delivery systems in agro-food-bio arena.
Furthermore, we discuss scientific concerns that need to be addressed with priority
in order to improve the risk assessment of nanomaterials and potential toxicological
impact on environment and biological entities. This chapter also discusses regula-
tion guidelines, which are urgently required for safe use of nano-products.

A. Kaphle • Navya PN • M. Chopra

Nano-Bio Interfacial Research Laboratory (NBIRL), Department of Biotechnology,
Siddaganga Institute of Technology, B. H. Road, Tumakuru 572103, Karnataka, India
e-mail: anubhavkaphle@gmail.com; navyapn@gmail.com; maulick03@gmail.com
A. Umapathi
Amity Institute of Biotechnology, Amity University Rajasthan,
Kant Kalwar, NH-11C, Jaipur Delhi Highway, Jaipur 303007, Rajasthan, India
e-mail: akhela.aradhya@gmail.com
H.K. Daima (*)
Nano-Bio Interfacial Research Laboratory (NBIRL), Department of Biotechnology,
Siddaganga Institute of Technology, B. H. Road, Tumakuru 572103, Karnataka, India
Amity Institute of Biotechnology, Amity University Rajasthan,
Kant Kalwar, NH-11C, Jaipur Delhi Highway, Jaipur 303007, Rajasthan, India
e-mail: hkdaima@jpr.amity.edu

© Springer International Publishing AG 2017 205

S. Ranjan et al. (eds.), Nanoscience in Food and Agriculture 5, Sustainable
Agriculture Reviews 26, DOI 10.1007/978-3-319-58496-6_8
206 A. Kaphle et al.

Keywords  Nanosciences • Agro-food • Toxicity • Biological • Environment • Risk

assessment • Nanomaterials

8.1  Introduction

Nanomaterials are engineered assemblies with at least one dimension equivalent to

100 nanometers or less and they exhibit different properties compare to their bulk
counterparts as defined by the National Nanotechnology Initiative. These materials
are of significant importance and increasingly being used for commercial purposes
in various sectors, wherein some of the advanced nanomaterials are at the forefront
in biological and pharmaceutical sciences (Astruc et al. 2010; Chrimes et al. 2012;
Daima and Bansal 2015; Daima and Navya 2016; Dubey et al. 2015; Farokhzad and
Langer 2006; Moghimi et al. 2005; Monnappa et al. 2016; Radovic-Moreno et al.
2012; Shankar et al. 2015; Sharma et al. 2014; Zhang et al. 2007a). However, nano-
materials applications to agriculture and food sector are relatively new and it is
anticipated that advanced designer made nanomaterials will revolutionize the field
of agriculture and various food sectors in near future (Dasgupta et al. 2017; Shukla
et al. 2017; Walia et al. 2017; Balaji et al. 2017; Maddinedi et al. 2017; Sai et al.
2017; Ranjan and Chidambaram 2016; Janardan et al. 2016; Ranjan et al. 2016).
In one of the recent reviews, it has been discussed that variety of nanomaterials
have been extensively employed in food sector, wherein these materials are pre-
dominantly used in preservation and packaging. Furthermore, authors have sug-
gested future applications of nanotechnology in food sector and proclaimed that it
can be extended to improve the safety, food quality, shelf life, fortification and bio-
sensors for contaminated or spoiled food and food packaging (Ranjan et al. 2014).
Smart delivery of nutrients, bio-separation of proteins or other biomolecules, rapid
sampling of biochemical contaminants and nano-encapsulation of nutraceuticals,
plant protection / production, disease treatment, packaging materials for food secu-
rity, development of new tastes, textures and sensations, innovative materials for
pathogen detection and delivery systems are some of the emerging research inter-
ests of nanotechnology for food and agriculture as shown in Fig. 8.1.

Fig. 8.1  Schematic representation of central role of nanotechnology in various applications and
potential scopes of nanotechnology in agriculture and food sectors
8  Nanomaterial Impact, Toxicity and Regulation in Agriculture, Food and Environment 207

Furthermore, advances in technologies, such as deoxyribonucleic acid (DNA)

microarrays (DNA chip or biochip), agricultural water quality management, micro-­
electromechanical systems and microfluidics, will enable the realization of the full
potential of nanosciences for food applications (Chaudhry et  al. 2008; Dasgupta
et al. 2015; Kalpana Sastry et al. 2011; Ravichandran 2010). Likewise, production
of agro-food products are of significant importance and it is the primary driving
force of economy (Rashidi and Khosravi-Darani 2011; Raynolds 2004).
Moreover, recent research trends show that nanosciences have potential to
advance agricultural productivity through genetic improvement of plants and ani-
mals, nano-array based gene- technologies for gene expressions in plants and ani-
mals under stress conditions (Kuzma 2007; Scott 2007) and delivery of genes and
drug molecules to specific sites at cellular levels in plants and animals (Maysinger
2007). The potential is increasing with suitable techniques and sensors being identi-
fied for precision agriculture (Day 2005), natural resource management, early
detection of pathogens and contaminants in food products, smart delivery systems
for agrochemicals like fertilizers and pesticides, smart systems integration for food
processing, packaging and other areas like monitoring agricultural and food system
security (Chau et al. 2007).
In addition to above stated scientific developments, nanotechnology is expected
to become the main economic driving forces in the long run and benefit consumers,
producers, farmers, ecosystems and the general society at large. Furthermore, nano-
sciences promise to advance agro-food sector through the enhancement of manage-
ment and conservation of inputs in crops and food products as discussed earlier. In
spite of that toxicological perspectives of nanomaterials are in embryonic stage of
its development. However, nanotoxicity is vital part of nanosciences and nanotech-
nology, which discusses interactions of advanced nanomaterials with biological
systems, environment and agri-food sectors. At the nanoscale level new quantum
effects can alter the chemistry, physics and biology of elements and compounds,
offering exciting new possibilities in various applications in health, food and agri-
culture sectors as discussed. On the other side, nanotoxicity could also pose unprec-
edented risks to health and the environment (Fischer and Chan 2007; Holl 2009;
Mahmoudi et al. 2011; Zhu et al. 2010).
Human skin, lungs and the gastro-intestinal tract are the most likely entry points
for natural or anthropogenic nanomaterials. Due to ultra-small size, nanomaterials
can translocate from these entry portals into the circulatory and lymphatic systems,
and ultimately to body tissues and organs. Few nanomaterials, depending on their
composition and size, can produce irreversible damage to cells by oxidative stress
or/and organelle injury. It is possible that all the nanomaterials do not produce
adverse health effects since the toxicity of nanomaterials depends on various fac-
tors, including their size, aggregation, composition, crystallinity, surface function-
alization etc. (Daima 2013; Daima and Navya 2016; Mirkin and Niemeyer 2007;
Niemeyer and Mirkin 2004; Suh et al. 2009; Yang et al. 2009).
Besides, toxicity of any nanomaterial to an organism is determined by the indi-
vidual’s genetic complement, which provides the biochemical toolbox by which it
can adapt to and fight toxic substances. Diseases associated with inhaled nanomate-
208 A. Kaphle et al.

rials are asthma, bronchitis, emphysema, lung cancer and neurodegenerative dis-
eases such as Parkinson’s and Alzheimer’s diseases. Nanomaterials in the
gastro-intestinal tract have been linked to Crohn’s disease and colon cancer.
Nanomaterials that enter the circulatory system are related to occurrence of arterio-
sclerosis, and blood clots, arrhythmia, heart diseases and ultimately cardiac death.
Translocation to other organs, such as liver or spleen may lead to diseases of these
specific organs as well. Exposure to some nanoparticles is associated with the
occurrence of autoimmune diseases, such as systemic lupus erythematosus, sclero-
derma and rheumatoid arthritis (Bergin and Witzmann 2013; Lefebvre et al. 2015;
Migliore et al. 2015; Nel et al. 2006; Oberdörster et al. 2005; Zhao et al. 2011).
From the above discussion, it is evident that despite of numerous potential appli-
cations, toxicological outlooks of advanced nanomaterials are poorly understood or
rather unclear in agriculture-, food-, environmental- and bio- sectors, which is gain-
ing substantial consideration in terms of nanotoxicology (Daima and Navya 2016;
Garnett and Kallinteri 2006; Krug and Wick 2011; Maynard et al. 2010; Nel et al.
2006; Oberdarster et al. 2007). Therefore, in this chapter, we have abridged assorted
nanomaterials relevant to agro-food-bio sciences along with identifying the out-
standing challenges, wherein special emphasis is given on concomitant nanotoxicity
of advanced materials. We also discuss about the nano-regulation guidelines, which
are urgently required in current scenario for better use of nanotechnology products.

8.2  Current Vehicles Developed by Nanosciences

Public health and availability of nutritious food are the two critical issues that are
currently being encountered around the globe. Additionally, rapidly growing popu-
lation (which is expected to reach over eight billion by 2025 and further increase by
about 30% by the end of 2050 (Sekhon 2014)), climate changes and resource con-
straints are giving rise to unprecedented pressure on both agro-food and water
resources. The decreasing arable land to population ratio has raised a concern
among stakeholders and policy makers. It therefore, calls for a paradigm shift in
contemporary technology to address growing demand of food by increasing the
global productivity as well as improving storage strategies. In this context, nano-
technology have found tremendous potential in revolutionizing agriculture, food
and other allied areas as depicted in Fig. 8.1, and applicability of nanoscience is
only limited by imagination.
As illustrated in Fig. 8.1, nanotechnology plays a central role in the development
of food products of lower calorific value, while still maintaining the taste and texture.
Additionally, it can be used for the effective delivery of bioactive compounds and
nutrients with increased bioavailability (Abbas et  al. 2009; Alfadul and Elneshwy
2010; Miller 2010; Scrinis and Lyons 2007). It also finds application in developing
pathogen and pesticide detecting sensors with very low limit of detection for early
read-out of food-borne diseases and food adulteration (Baruah and Dutta 2009;
Sharon et al. 2010; Xiong and Li 2008; Zhang et al. 2009). It can also be used for
material recycling (Sozer and Kokini 2009), water purification (Qu et  al. 2013;
8  Nanomaterial Impact, Toxicity and Regulation in Agriculture, Food and Environment 209

Savage and Diallo 2005) and for packaging applications to increase shelf life of prod-
ucts (Alfadul and Elneshwy 2010; Duncan 2011; Hatzigrigoriou and Papaspyrides
2011; Sorrentino et  al. 2007). Furthermore, nanotechnology can be employed to
effectively deliver pesticides (Taylor et al. 2005; Tsuji 2001) and fertilizers (Derosa
et al. 2010) in controlled manner so that run-off lost is minimized thereby reducing
contamination, toxicity and other hazards associated with the leakage.
Rapid development in diverse materials and techniques can complement current
technology to solve many burning issues of agro-food sectors. Significant improve-
ments in the development of stable nanomaterials with robust features and proper-
ties applicable in agro-food sectors is increasing the confidence in scientific
community and providing hope to public to bring out the best of technology at an
affordable cost and low risk. In this context, a variety of nano-vehicles have been
designed for their potential employment in agro-food-bio sectors as shown in
Fig. 8.2.

Fig. 8.2  Illustration of range of emerging nanomaterials including metal nanoparticles, metal
oxide nanoparticles, carbon nanotubes, liposomes and dendrimers along with their potential appli-
cations such as carrier, protection and sensing in the field of agro-food sector
210 A. Kaphle et al.

Metal nanoparticles of gold and silver have been extensively used in biomedicine
for diagnostics, therapeutics, antimicrobial and drug delivery applications (Daima
et al. 2011, 2013, 2014a, c; Dubey et al. 2015; Hu et al. 2006; Jain et al. 2009; Lee
and El-Sayed 2006; Luo et al. 2014; Monnappa et al. 2016; Sharma et al. 2014).
Many studies have also shown their potential in food packaging to control microbial
growth and to avoid contamination of pathogens (Duncan 2011; Mohammed Fayaz
et  al. 2009; Sozer and Kokini 2009; Tankhiwale and Bajpai 2009). Interestingly,
metal nanoparticles have been shown to maintain the freshness of food and prevent
microbial contamination that will otherwise result in fouling.
Nanomaterials made-up of metal oxides such as zinc oxide, cerium oxide, tita-
nium dioxide have been constituted into commercial products exploiting their ‘light
activated microbe inactivation’ (Becheri et al. 2008; Ditta et al. 2008; Ranjan et al.
2016). Moreover, metal oxides can be charged by irradiating with precise frequency
of light so that they generate free radicals that can oxidize and avoid spoilage by
killing microorganisms or pathogens. Wherein, carbon nanotubes have been
exploited in water purification unit due to their strong absorption properties (Lu and
Chiu 2006; Qu et al. 2013; Savage and Diallo 2005; Shannon et al. 2008).
On the other hand, polymeric nanoparticles have been used to encapsulate active
ingredients, fertilizers and pesticides for controlled release of chemicals (Chaudhry
et al. 2008; Silvestre et al. 2011). Liposomes have been employed as model mem-
branes of plant organelles to study plant ageing, drying and freeze tolerance against
toxins and pesticides (Taylor et al. 2005). In addition to this, liposomes can also
serve as delivery vehicles to carry plant hormones for controlling metabolism and
growth (Taylor et al. 2005). Similarly, dendrimers can find application in transport
of active agents by improving solubility and reducing enzymatic degradation (Hayes
et al. 2011). Dendrimers also find application in plant gene delivery due to their easy
transit across biological membranes (Samuel et al. 2014).
In the next sections of this chapter, we will discuss about the recent develop-
ments in nanomaterials that are currently being used or can potentially be used in
agro-food-environmental sectors. In the discussion special emphasis will be given
on the unique physicochemical properties of nanomaterials and their applicability in
the contexts of agriculture, food and environmental sectors.

8.3  Applicability of Contemporary Nanomaterials

As discussed in the earlier sections, metal or metal oxide based nanoparticles, car-
bon nanotubes, liposomes and dendrimers find their applications in the field of agro-­
food-­environmental sectors. All these materials have been exploited for their utility
as biomolecule carrier and their controlled release of molecules, packing materials,
protection against pathogen and pesticides detection.
8  Nanomaterial Impact, Toxicity and Regulation in Agriculture, Food and Environment 211

8.3.1  Metallic Nanoparticles

Metal based nanoparticles have distinctive physicochemical properties, which are

governed by their nanoscale size and shape; and facilitate the development of robust
and varied materials. A range of metallic nanoparticles have been constructed and
employed in the sector of agro-food-environment. Among metal nanoparticles, gold
and silver nanoparticles are the most favorite nanomaterials for food packaging,
pathogen and pesticides diagnostics. Interestingly, both gold and silver nanoparti-
cles are equally important and applicable in biomedical sector as well, which makes
them more promising for agro-food field.

8.3.1.1  Gold Nanoparticles

Gold nanoparticles are one of the most desirable materials due to their easy synthesis,
high stability, unique optical properties and easy surface functionalization (Babu
Maddinedi et al. 2015; Daima 2013; Daima et al. 2011, 2013, 2014b; Dubey et al.
2015; Monnappa et al. 2016; Murphy et al. 2008; Shankar et al. 2015; Sharma et al.
2014). Gold nanoparticles can be synthesized as spherical particles or nano-rods of
high aspect ratio or nano-cages with hollow interior and porous wall (Soenen et al.
2011). Gold nanoparticles have unique strong optical signals called surface plasmon
resonance (SPR) that occurs due to the reciprocal movement of electrons on the surface
of material when excited by an appropriate radiation. These signals can be exploited to
develop extremely sensitive sensors (El-Sayed et al. 2005; Melaine et al. 2015).
Likewise, gold nanoparticles based surface enhanced Raman spectroscopy
(SERS) is very promising. The surface plasmon electrons create an electrical field
around it and therefore, it can enhance the Raman scattering cross-section of nearby
molecules that are very unique to the molecules as illustrated in Fig. 8.3. This, in
theory, can facilitate single molecular detection and identification (Haynes et  al.
2005; Kneipp et al. 2005). Tapas et al. developed highly specific and sensitive tryp-
tophan capped popcorn shaped gold particles as SERS probes to detect as low as 5
ppb concentration of Hg(II) ions from aqueous solution in the presence of other
competing analytes (Senapati et  al. 2011). This has very good application in
­detecting heavy metal contamination in food especially sea-foods where these con-
taminations are frequently introduced by industrial wastes.
Gold nanoparticles possess conductive sensing interface and conductivity prop-
erties. Huanshun et al., developed a new sensitive and stable amperometric biosen-
sor for the detection of pesticides such as methyl paraoxon, carbofuran and phoxim
based on immobilization of acetylcholinasterase on gold nanoparticle and silk
fibroin modified platinum electrode (Yin et al. 2009). Here, gold nanoparticles pro-
moted rapid electron transfer reaction at a lower potential and catalyzed the oxida-
tion of thiocholine, which then can be sensed amperomertrically to detect the
presence and amount of those insecticides.
In the recent past, we have shown that tyrosine capped gold nanoparticles pos-
sess intrinsic peroxidase-like activity (Daima et al. 2014c), and it can be expedient
212 A. Kaphle et al.

Fig. 8.3  Gold nanoparticles enhance the Raman signal of analytes due to the electric field of reso-
nating electronic cloud on the surface. The Raman signal can be strengthen, allowing development
of single molecular detection system for pathogen or pesticides in food industries

to detect antibiotic kanamycin using specific aptamers bound to gold nanoparticles

(Sharma et  al. 2014). In this system, in the presence of kanamycin it’s specific
aptamers, designated as Ky2 aptamer, will desorb from the gold nano-spheres
exposing bare surface that can oxidise colorless substrate 3,3,5,5-­tetramethylbenzidine
(TMB) to a purplish-blue product that can be visually or spectrophotometrically
read-out. The same aptamers will not desorb from the surface if there are no kana-
mycin present thus masking the peroxidase activity as reflected in Fig. 8.4. The limit
of detection for the system was measured to be around 4.5 nM of kanamycin
(Sharma et al. 2014). This is an important system as most countries monitor kana-
mycin contamination in food given its serious side effects and would be effective to
sense residual kanamycin as early read-outs instead of using conventional method
of salt precipitation which is time consuming and non-specific.
Functionalized biocompatible gold nanoparticles have also been investigated for
their potential anti-microbial actions due to the presence of specific surface chemis-
try (Huang et al. 2014). Such functional materials can also be employed as food
packaging materials to inhibit microbial contamination of food increasing shelf life
(Thirumurugan et al. 2013). They can also be constituted into composites with poly-
mers and can become barrier materials to prevent moisture exchange and hence
food fouling. Gold particles have also been used for gene delivery applications
(Ghosh et  al. 2008; Han et  al. 2007; Pissuwan et  al. 2011), which can facilitate
transfection of plants and animals with nucleic acids for the production of trans-
genic plants and animals with improved phenotypes.
From the discussion it is apparent that gold nanoparticles can serve as very spe-
cific biosensors units. Also, because of antimicrobial profile, gold nanoparticles
have the potential to be used in food packaging. Gold nanoparticles can also serve
as delivery agents. More research into how gold nanoparticles can be constituted
into efficient systems for wide-spread application in agro-food sectors is necessary
for their sustainable use.
8  Nanomaterial Impact, Toxicity and Regulation in Agriculture, Food and Environment 213

Fig. 8.4  Kanamycin detection system using specific Ky2 aptamers adsorbed on the surface of
gold nanoparticles (GNPs). With aptamers on the surface, peroxidase activity of nanoparticles get
inhibited thus cannot oxidize TMB (Step B). However, if aptamers desorb from the surface to bind
kanamycin, the bare surface can oxidize colorless TMB to purple giving a visual read-out (Step C).
Reproduced from (Sharma et al. 2014)

8.3.1.2  Silver Nanoparticles

Silver nanoparticles have a long history of being used in food and beverage storage
applications as antimicrobial agent and in recent times silver nanoparticles have
emerged as excellent broad spectrum microbicidal agent. Many studies have dem-
onstrated the effectiveness of using silver colloidal solution against many plant
pathogens and bacterial strains (Dasgupta et  al. 2016b; Gajbhiye et  al. 2009;
Mohammed Fayaz et  al. 2009; Velmurugan et  al. 2013). In one of the research,
Gajbhiye and co-worker have reported fungus-mediated synthesis of silver nanopar-
ticles and their application against common plant pathogenic fungi such as Phoma
glomerata, Phoma herbarum and Fusarium semitectum (Gajbhiye et  al. 2009).
They achieved good results when they synergized the effectiveness of silver parti-
cles with anti-fungal drug fluconazole.
Similarly, method for using nano-silver as an additive to prepare antibacterial
wheat flour has been patented (WPI ACC NO: 2006–489,267/200650) under the
application heading “Preparation method antibacterial wheat flour by using silver
nanoparticles” by Park from South Korea (Chaudhry et al. 2008). The great advan-
tage of silver antimicrobials is that silver metal can be easily integrated within
214 A. Kaphle et al.

Fig. 8.5  Schematic representation of gold (Au) and silver (Ag) nanoparticles embedded biopoly-
mer composite to develop sustainable food contact materials for increasing the shelf-life of pack-
aged food items

numerous materials such as textiles, plastics and wares (Gottesman et  al. 2010).
This has an outstanding implication and can be used as disinfectant for a longer
period when traditional antimicrobials would be impractical. Silver nanoparticles
have also been used as food contact materials (FCM) as exemplified in Fig. 8.5 to
prevent food fouling and increase shelf life of foodstuffs.
In addition, silver nanoparticles can also absorb and decompose ethylene gas that
is responsible for ripening and spoilage of fruits and vegetables (Fernández et al.
2010). This property of silver may contribute to its positive effects on the shelf life
of fruits and vegetables. Silver particles / polymer nanocomposite materials have
already been tested with real food systems to evaluate their antimicrobial activity
and their advantage in increasing shelf-life (Kong and Jang 2008; Son et al. 2006;
Tankhiwale and Bajpai 2009).
Mohammad-Fayaz et al. coated sterilized carrots and pears with alginate solu-
tions containing silver nanoparticles, forming edible antibacterial films. They
observed that the treated fruits had less water loss with very good consumer accept-
ability over the experimental period of 10 days (Mohammed Fayaz et  al. 2009).
Similarly, a study on the effects of nanocomposite of polyethylene film with silver
particles showed that the senescence of the Chinese fruit Jujube was delayed to a
8  Nanomaterial Impact, Toxicity and Regulation in Agriculture, Food and Environment 215

great extent of 12 days (Li et al. 2009). Likewise, in another study, a coating of sil-
ver particles and polyvinylpyrrolidone nanocomposites on asparagus samples
showed increased shelf life up to 25 days when stored at 2 °C which acted by
decreasing microbial growth even after many days of storage (An et al. 2008).
From the above discussion, it is evident that silver nanoparticles are essentially
used as anti-microbial agents in most of the applications. However, because of
strong plasmon resonance (SPR) effects, silver nanoparticles can also be used for
bio-sensing applications in agro-food-environment-medicinal sectors like gold
nanoparticles for easy and specific read-out for the presence of analytes (Mcfarland
and Van Duyne 2003). Despite all these advantages, comprehensive studies on
developing combinations of polymer and silver composites for plethora of applica-
tion in barrier materials is still lacking. Thus, much work needs to be done in inno-
vating systems with minimal side-effects and broad spectrum applications in
different sectors.

8.3.2  Metal Oxide Nanomaterials

Metal oxide nanomaterials play a very important role in many areas of pure and
applied sciences. Such materials can adopt diverse range of structural geometries
with electronic structures that can exhibit metallic, semiconductor or insulator char-
acter (Fernández-García and Rodriguez 2011). Metal oxide nanomaterials exhibit
unique physical and chemical properties owing to their small size and a high density
of edge surface site. Due to their unique properties, metal oxide nanomaterials are
increasingly used in fillers, opacifiers, ceramics, coatings, catalysts, semiconduc-
tors, microelectronics, prosthetic implants and drug carriers (Kahru et  al. 2008).
Metal oxide nanomaterials have also been shown to possess antimicrobial effects.
Moreover, metal oxide nanomaterials have very good photocatalytic properties that
can be tuned to work in visible light range. This property can be exploited to syn-
thesize solar-based sterilization coatings or UV-absorption films (Becheri et  al.
2008; Ditta et al. 2008). There are many types of metal oxides nanomaterials that
are being synthesized and have found applications in the area of environmental
remediation, bioengineering, electronics and food packaging technology. Most use-
ful among them are zinc oxide (ZnO), cerium oxide (CeO2) and titanium dioxide
(TiO2) nanoparticles.
ZnO nanoparticles are multifunctional semiconductor materials with a band gap
of ~3.370 eV, and a relatively high excitation binding energy of 60 MeV (Alivov
et al. 2003; Calestani et al. 2010). This confers that properties of ZnO nanoparticles
can be exploited for many applications. ZnO nanoparticles have been used in pho-
tocatalysis (Pare et al. 2008), for excellent piezoelectric applications (Song et al.
2006) and luminescence applications for LED developments (Alivov et al. 2003).
Furthermore, ZnO nanoparticles find application in varistors, transparent conduc-
tors, transparent UV-protection films and chemical sensors for both liquid and gas
phase analytes (Abdelhady 2012; Calestani et al. 2010; Wan et al. 2004).
216 A. Kaphle et al.

In addition to above, many studies confirm anti-microbial properties of ZnO

nanoparticles (Padmavathy and Vijayaraghavan 2016; Zhang et  al. 2007b). ZnO
nanoparticles find their application as food-packaging agents, nano-fertilizer agents
and as solar-assisted disinfectant materials. Narges et al. in their study tested the use
of ZnO nanoparticles as Zn supplement on the farm by coating them on the granular
macronutrients fertilizers, urea and monoammonium phosphate (MAP). They have
also tested the kinetics of the dissolution of Zn from ZnO and compared the data
with bulk ZnO particles from the same materials coated onto same macronutrient
fertilizers. They observed that coated MAP granules showed greater Zn solubility
and faster dissolution rates compared to coated urea granules, which they inferred
may be related to pH differences in the solution surrounding the fertilizer granules.
Thus, the solubility and availability of Zn depends on the chemical nature of the
carrier globules. Surprisingly, the kinetics of Zn dissolution was not observed to be
affected by the size of the ZnO particles applied for coating of either fertilizer type,
probably because the solubility was controlled by formation of the same compounds
irrespective of the original size of the ZnO used for the study (Milani et al. 2012).
In another application of ZnO nanomaterials, Rasika et al. developed ZnO loaded
polyethylene films with starch coating as supporting matrix and assessed their anti-
bacterial properties against Escherichia coli. They showed enhanced activity of Zn
particles against the species and commented on ZnO nanomaterials applicability in
food packaging materials (Tankhiwale and Bajpai 2012).
CeO2 has been used increasingly in various engineering and biological applica-
tions. CeO2 nanoparticles have been used as solid-oxide fuel cells (Stambouli and
Traversa 2002), high-temperature oxidation protection materials (Patil et al. 2002),
catalytic materials (Kašpar et  al. 1999; Trovarelli 1996) and potential pharmaco-
logical agents (Celardo et al. 2011). In recent studies, CeO2 nanoparticles have also
been reported to behave as multi-enzyme mimetics that include superoxide oxidase,
catalase and oxidase like catalytic activities that facilitates development of lucrative
materials for bioanalysis, biomedicine, drug delivery and bio-scaffolding (Xu and
Qu 2014). Much of the applications of CeO2 nanoparticles in agro-food sectors
comprise of using them as anti-microbial agent exploiting light-mediated disinfec-
tion phenomenon. Due to their high specific surface area CeO2 nanoparticles can
promote electron transfer reactions at a lower potential. CeO2 nanoparticles have
thus been applied in the development of chemo-sensors and have also been used as
photo-catalyst for environmental remediation.
Khan and team has developed CeO2 based ethanol sensor with higher sensitivity
and low limit of detection of 0.124 ± 0.010 mM. They have also used these materi-
als to investigate their photo-catalyst behavior by observing the degradation of
amido black and acridine orange dyes. The research team observed that prepared
nanomaterials of CeO2 exhibited different photocatalytic activities towards different
kind of dyes. This behavior, as they mentioned, could be due to the different adsorp-
tion pattern of dyes onto the surface of the material or also may be attributed to the
different structural orientation of molecules so that some orientation are ‘favoured’
for the attack of generated reactive species against other (Khan et al. 2011). CeO2
particles can also be constituted into composites with materials such as graphene or
8  Nanomaterial Impact, Toxicity and Regulation in Agriculture, Food and Environment 217

graphene oxide (GO) (Jiang et al. 2012; Zhang et al. 2013) so that their electron
transfer capacity be enhanced which will open new avenues for the development of
sensors that are applicable in pesticides and pathogen detection.
TiO2 nanomaterial receives much attention from chemist and materials scientist
in the field of photo-catalysis and -sensing owing to its high surface area and very
low band gap energy that can further be brought down to make it operate in visible
light using dopants such as gold, silver or nitrogen (Pearson et al. 2011a, b; Sakthivel
et al. 2004). Also, the crystal structure of TiO2 nanomaterial is more stable against
photo-bleaching which makes it sustainable for routine usage. TiO2 nanoparticles
have also shown to have antimicrobial actions as demonstrated by many studies,
which makes TiO2 nanomaterial applicable in developing food contact material
(Chung et al. 2008; Ditta et al. 2008; Fu et al. 2005; Kubacka et al. 2014; Wang et al.
2010).
In recent past, an attempt was made to analyze the TiO2 nanoparticles-protein
interaction through docking. Interestingly, the docked structures revealed efficient
binding with specific amino acids. Based on the results, authors have suggested that
this approach may be used to explore the in silico nanotoxicology to understand the
mechanism (Ranjan et al. 2015). Siti et al. developed TiO2 nanoparticles loaded low
density polyethylene (LDPE) film and checked their efficacy against model bacte-
rial species Escherichia coli and observed very good performance (Othman et al.
2014). They suggested that this material has potential for food packaging applica-
tion to increase shelf life by preventing microbial spoilage of food products.
Similarly, in another application of TiO2, Chorianopoulos et al. exploited ultravio-
let-­A activated photo-catalytic property of TiO2 and applied it to destroy Listeria
monocytogenes biofilm (Chorianopoulos et al. 2011). The process resulted in the
fastest log-reduction of bacterial biofilm compared to the control test. The use of
TiO2 materials as alternative means of disinfecting surfaces presents a novel
­opportunity for treating biofilm on surfaces of food processing units, which can
enhance food safety and economize time and money.
Higher surface area of TiO2 nanomaterial also provides great advantage for
developing sensors based on electrochemical oxidation. TiO2 nanomaterial can also
be composited with other materials for improved photocatalytic actions, electro-
chemical sensing applications or surface enhanced Raman sensing applications.
Overall, metal oxides particles are very useful for their electronic properties which
can be exploited for developing light-activated disinfectant materials, sensing mate-
rials and anti-microbial films alone or composited with surfaces of graphene for
improved actions.

8.3.3  Carbon Nanotubes

Carbon nanotubes (CNTs) are continuous cylindrical structures made-up of one or

more graphene sheets rolled onto themselves, with open or close ends (Iijima 1991).
All the carbon atoms in perfect carbon nanotubes are bonded in a hexagonal lattice
218 A. Kaphle et al.

except at their ends due to defects that introduce pentagons, heptagons and other
imperfections in the side walls. Lengths of carbon nanotubes range from less than
100 nm to several centimeters with typical diameters of 0.8 to 2 nm for single walled
tubes and 5 to 20  nm for multi-walled nanotubes (De Volder et  al. 2013). Carbon
nanotubes’ strong binding affinity for hydrophobic molecules, their internal tube cav-
ity and higher surface area makes them ideal materials for the development of novel
gas sensors, enzymatic biosensors, voltammetry and DNA probes. Moreover, as
shown by Asensio-Ramos et al., carbon nanotubes can be used as stationary phase
materials for solid-phase extraction of organophosphate pesticides, which can be
applied on a large scale to agricultural, ornamental and forestall soils (Asensio-­Ramos
et al. 2009). This has greater implications in environmental remediation as well.
In a different research setting studying the applicability of carbon nanotubes in
agriculture, researchers have studied the effect of carbon nanotubes on the germina-
tion and growth of plant. Khodakovskaya et al. established the effect of the concen-
tration of carbon nanotubes applied to the seed and measured the germination rate
and time. They found that the addition of carbon nanotubes to agar medium was
found to accelerate the process of seed germination and significantly shorten the
germination time as shown in Fig. 8.6. As shown in the bar chart the germination
time was reduced when carbon nanotubes were added to the nutrient medium. Also,
during the period of 20 days, the % germination of seed was 71% for regular
medium, however when supplemented with carbon nanotubes it rose to 90%. They
also showed that carbon nanotubes were able to penetrate both the seeds as well as
the root systems of the more developed plants. This indicates that carbon nanotubes
can be up taken by seeds and significantly affect their biological activities, may be
by enhancing the amount of water that penetrates inside the seed during the germi-
nation period. However, molecular mechanism of water uptake is still not clear
(Khodakovskaya et al. 2009). Akin results were obtained from the experiments con-
ducted by Anindita and co-workers on mustard plant (Mondal et al. 2011).
Some studies have also advocated antimicrobial property of carbon nanotubes.
Xiuping et al. showed antimicrobial effect of various structures of carbon nanotubes
against copper-resistant Ralstonia solanacearum and compared it with other carbon
based materials such as graphene oxide or fullerenes (C60). Single walled carbon
nanotubes has been shown to have the strongest activity amongst all the tested mate-
rials. Moreover, damage to the cell membrane was observed which led to the release
of cytoplasm materials from the bacterium. Furthermore, carbon nanotubes role has
been described in this research and it was noted that carbon nanotubes have
­important applications in controlling plant bacterial diseases which will increase
crop productivity (Wang et al. 2013).
Carbon nanotubes can also find application in nano-sensors for pathogen detec-
tion in plants and environment. Martín et al. developed electrochemical immuno-­
sensor that promises to be useful and suitable for the detection and quantification of
B. cinerea in apparently healthy apple plant prior to the development of the symp-
toms. Such innovative, rapid and sensitive sensors can be helpful for the early infor-
mation of invading pathogen on the field and can then be rationally analyzed for the
usage of pesticides against them (Fernández-Baldo et al. 2009).
8  Nanomaterial Impact, Toxicity and Regulation in Agriculture, Food and Environment 219

100
90
80
% of germination

70
0 ug/ml
60
10 ug/ml
50
20 ug/ml
40
40 ug/ml
30
20
10
0
3 12 20
Days of germination

Medium with
Standard medium
nanotubes

Fig. 8.6  Influence of carbon nanotubes on the germination period of seeds, wherein decline in
germination period has been shown in the histogram. Also, carbon nanotubes increase the percent-
age of seed germination compare to seeds without carbon nanotubes supplemented medium; which
may be attributed by penetration of carbon nanotubes inside the seed, aiding in water absorption
facilitating seed germination. Adopted from (Khodakovskaya et al. 2009)

8.3.4  Liposomes and Nanoemulsions

Liposomes are lipid vesicles formed from the dispersion of amphiphilic molecules
such as polar lipids in aqueous solvents. The vesicle may consist of one or more
bilayer membranes with internal cavities or space that can incorporate range of
functional molecules. Liposome that contain single bilayer (unilamellar vesicles,
UV) range from <30 nm in size for small vesicles (small unilamellar vesicles-) to
30–100  nm for large layers (larger unilamellar vesicles-) (Taylor et  al. 2005).
Liposomes have been previously used as model systems to study plasma membrane
of cells for degradability and stability mechanisms in various perturbation condi-
tions such as pathogen invasion or endocytosis (Sharma and Sharma 1997; Wilschut
220 A. Kaphle et al.

Fig. 8.7  Schematic diagram showing potential applications of liposomes in food industry and
non-food agriculture sectors. The figure illustrates how liposomes have impact on plants and ani-
mals under non-food agriculture section. The outline also demonstrates utility of liposomes in
nutrient and various functional components encapsulation (Adopted from Taylor et al. 2005)

and Hoekstra 1986). Recent studies have shown that liposomes are suitable for
transporting a range of materials for biological, pharmacological, biochemical and
agricultural interests as schematically outlined in Fig. 8.7. These molecules may be
drugs, pesticides, fertilizers, enzymes or antimicrobials as per the requirement
(Taylor et al. 2005).
Food scientists have begun to realize the potential of liposomes as cargo vehicles
that can provide precise delivery of active agents such as enzymes, vitamins, flavors
in various food constituents. Liposomes have been investigated to study their advan-
tage in food processing and dairy industry. Entrapment of lipases to improve the
production of cheese has been studied recently, which has resulted in decreasing the
inflexibility of Cheddar cheeses while increasing the cohesiveness and elasticity of
such samples (Benech et al. 2002). In addition to usage in food processing, lipo-
somes have also been used to fortify food products with vitamins to increase nutri-
tional values as well as aid in the digestion of constituents in dairy products. In this
context, Banville and co-workers have measured significant difference in the recov-
ery of vitamin D from cheese containing liposomes encapsulated vitamin D com-
pared to commercially produced vitamin D that indicates protective nature of
liposomes encapsulating the vitamins (Banville et al. 2000).
Moreover, researchers have evaluated the potential of liposome in protecting
food components against degradation. Typical example is phosphotidylcholine (PC)
containing liposomes encapsulating stearic acid and α-tocopherol effectively pro-
tected entrapped α-amylase against pepsin attack, cold temperature storage and
extreme pH conditions in one of the study (Hsieh et al. 2002). Similarly, in a kinetic
study, conducted by Rodriguez et  al. of free and phosphotidylcholine liposomes
entrapped glucose oxidase, the Michaelis constant Km for entrapped enzymes versus
free enzyme increased and the maximum velocity Vmax decreased by the factor of
8  Nanomaterial Impact, Toxicity and Regulation in Agriculture, Food and Environment 221

0.35 (Rodriguez-Nogales 2004). The entrapment offered greater proteolysis resis-

tance and thermal stability for the enzyme. Liposome may protect and stabilize
vitamins in food system. Kirby et al. reported stability of phosphotidylcholine lipo-
somes encapsulated ascorbic acid (Vitamin C) and retention of their antioxidant
property by more than 50% even after 50 days of refrigerated storage while free
ascorbic acid lost its activity within 19 days of storage in the equivalent conditions
(Kirby et al. 1991).
All the above discussed studies highlight the potential for liposomes to aid in the
development of effective storage and protection systems for protecting bioactivity
of nutrients as well as fortification of food products with supplements with addi-
tional nutrition values and increased shelf life. There are also a few more reports on
the application of liposomes for the delivery and enhanced efficiency of antimicro-
bial compounds as controlled release formulations (CRF). For example, Bang et al.
used phosphotidylcholine (as amphiphilic compound) and cholesterol (as stabiliz-
ing agent) for the synthesis of nano-sized liposomes to encapsulate the pesticide
etofenprox for controlled release of the molecule (Bang et  al. 2009). The nano-­
liposomes were prepared employing an ultrasonic homogenization technique where
the size of the particles was reduced by optimizing the ratio of lecithin (phosphoti-
dylcholine) and extending homogenization time. Nano-liposome encapsulation pro-
vides great advantage for food scientists as it is flexible for both hydrophilic and
hydrophobic molecules. Hydrophilic molecules are entrapped in the core space
whereas hydrophobic molecules are incorporated into lipid bilayers. This facilitates
multi-pesticides encapsulation to work on a range of agricultural pests.
In addition to above discussed, nanoemulsion is another class of material at nano
scale level which is employed for a range of applications. In general, nanoemulsions
are produced by either high-energy or low-energy approaches and extensively used
in food, agriculture and health sectors. Nanoemulsion is made up of a lipid phase
(dispersed in an aqueous continuous phase), with each oil droplet being covered in
a thin interfacial layer (consisting of emulsifier molecules). Towards gravitational
separation and thermodynamically nanoemulsions are highly stable compared to
conventional emulsions under a range of different conditions (Acosta 2009;
Dasgupta et  al. 2015; Tadros et  al. 2004). Interestingly, the stability of the final
nanoemulsion will fully depend on the specific usage of surfactant in the formula-
tion. Moreover, such designer made nanoemulsions can be suitable to encapsulate
various components (related to food, agriculture and medicine) at oil/water inter-
faces or throughout the continuous phase of the system. Nanoemulsions have also
found their utility in food industry due to their antimicrobial nature for decontami-
nation of food equipment, packaging of food, herbicide and pesticide (Dasgupta
et al. 2015, 2016a; Ranjan et al. 2014; Weiss et al. 2008).
Preparation of emulsions for functional compounds delivery and their encapsula-
tion is one of the most important industrial application of nanoemulsions. This is
possible because nanoemulsions provide better opportunity for encapsulation and
improved bioavailability for living entity. Specific nanoemulsion formulations and
nanoencapsulation are employed for incorporation, absorption and dispersion of
functional food ingredients into nanostructures. Functional compounds such as
222 A. Kaphle et al.

lutein, lycopene, b-carotene, vitamins, phytosterols and isoflavones have been deliv-
ered by encapsulation for improved bioavailability in the human body using nano-
emulsions. Moreover, it has been established that nanoemulsions have potential to
capture flavour and protect it from temperature, oxidation and enzymatic reactions.
Furthermore, nanoemulsions can provide thermodynamic stability to encapsulated
materials at a wide range of pH values. Interestingly, utilization of nanoemulsion
formulations and nanoencapsulation may omit the need of additional stabilizers as
they will protect against breakdown and separation of food (Dasgupta et al. 2015;
Halliday 2011; Silva et al. 2012; Ranjan et al. 2014).

8.3.5  Dendrimers

Dendrimers are branched, synthetic polymers with unique branch topologies that
confer dendrimers properties that are different from linear polymers. Dendrimer
structure consists of a central core and branched, radially emanating identical mono-
meric structures called dendrons as portrayed in Fig. 8.2. The counts of branch point
encountered while moving outward from the core of the dendron to its periphery
gives the definition of its generation. ‘Larger dendrimers are of higher generation
with more branch point radiating out from the core and have more end groups at the
periphery than smaller dendrimers of lower generations (Lee et al. 2005).’ Synthesis
of dendrimers can take place in two fashions - divergent resulting in an exponential
growth or in a convergent way where individual units are synthesized separately and
then joined together with a core (Tomalia et al. 1990). Dendrimers synthesis occurs
in step-wise fashion like synthesis of peptides or oligonucleotides, and it gives a
monodispersed product which overcomes experimental and therapeutic variability
(de Brabander-van den Berg and Meijer 1993; Tomalia et al. 1985).
Higher generation dendrimers, however in practical, deviate from the absolute
mono-dispersity (slightly) due to the current inability in purifying perfect den-
drimers from previous stages. Nature and properties of dendrimers such as solubil-
ity, degradability and biological activity depend on the type of molecules that form
the polymers. Frequently used dendrimers in the areas related to biological applica-
tions are based on polyamidoamines (Tomalia et  al. 1990), polyamines (de
Brabander-van den Berg and Meijer 1993), polyamides (polypeptides) (Sadler and
Tam 2002), poly (aryl ethers) (Hawker and Frechet 1990), polyesters (Grinstaff
2002; Ihre et al. 1996), carbohydrates (Turnbull and Stoddart 2002) and DNA (Li
et al. 2004). The most common dendrimer scaffold that is commercially available is
prepared from polyamidoamine (PAMAM) dendrimers (Lee et al. 2005).
Dendrimers find application as delivery agents that can carry drugs, oligonucle-
otides or other molecules for variety of application in agriculture. A patent has been
filed by Hayes et al. on the method of formulating specific Poly(etherhydroxylamine)
dendrimers for agricultural purposes (Hayes et al. 2011). The dendrimers perform
several functions such as increasing the solubility of active agents; improving adhe-
sion and penetration of the active agents to plant surfaces; improving water-fastness
8  Nanomaterial Impact, Toxicity and Regulation in Agriculture, Food and Environment 223

of the active agents to the plant or seed; increasing soil penetration of the active
agents to reach the plant roots or under soil parts; reducing soil adhesion of the active
agents to reach the plant roots. They can also provide protection against enzymatic
degradation of the active agent by plant or seed or microorganisms present in the soil.
Dendrimers have also been used in plant gene delivery system. Pashupathy et al.
have transfected turfgrass cells with green florescent protein– encoding plasmid
DNA using poly(amidoamine) dendrimers (Pasupathy et al. 2008). The nano-sized
organic chemical nature of dendrimers provides advantage to perform gene delivery
in a noninvasive fashion. Likewise, through dendrimer nanotechnology, Samuel et al.
have developed methods for delivery of biomolecules into plant cells (Samuel et al.
2014). Moreover, in a recent review, possibility of using dendrimers as nitric oxide
(NO) releasing systems in agriculture has also been identified. This characteristic
might be applicable to treat microbial infections in plants with nitric oxide, since
high doses of the gas molecule are known to exert cytotoxic effects against microor-
ganisms such as fungi, virus and bacteria (Seabra et al. 2014). In overall, dendrimers
are potential organic polymers that can serve as carrier molecules for delivery of
active agents, sensory elements, drugs and pesticides for controlled release in agri-
cultural settings. Dendrimers can also provide non-invasive transfection application
to produce transgenic plants and animals with desired or improved traits.

8.4  Insight of Nanoparticles Toxicity

As discussed, compared to other sciences or technologies, nanotechnology is rela-

tively new that has shown enormous potential to solve current critical issues in
numerous sectors. With the availability of versatile nanomaterials, nanotechnology
has captured attention of many agro-food-enviro-health and agrichemical enterprises
as conferred in previous section. However, management and use of engineered nano-
materials necessitate careful understanding of their potential risks and benefits as the
sustainability of this technology depends on the subtle differences between them.
There are some studies that are being carried out to assess eco-­nanotoxicity resulting
from the extensive use of nanomaterials and their exposure to environment.
Researchers are studying potential hazards of engineered nanomaterials by ana-
lyzing the adverse effects incurred when nanoparticles reach at the nano-bio inter-
face. They are also studying transport mechanisms of engineered particles in the
environment, their stability and accumulation, their exposure levels and routes (Chen
et al. 2014). However, much of these studies have focused on short term, high dose
exposure scenarios often conducted in model media. Without much investigation on
a larger scale with systems or models that represent real setting, it will be difficult to
set policies for the guided use of nanomaterials in agriculture or food sector.
In the next section, we shall discuss about potential nanotoxicity posed by vari-
ous nanomaterials as shown by their respective studies, possible mechanisms of
nanotoxicity and some applied mitigation methods for reducing the potential toxic-
ity for better applicability of materials at nano level.
224 A. Kaphle et al.

8.4.1  Metal Nanoparticles Toxicity

As mentioned in previous sections, noble metals like gold and silver nanoparticles
find their use as sensory elements, food packaging materials, anti-microbial agents
etc. Due to their long standing history of usage, researchers have expected them to
be bio-compatible incurring very minimal risks, if any (Pauksch et al. 2014; Shukla
et al. 2005; Wang et al. 2007). However, current studies have identified size, shape,
surface corona and dose dependent toxicity of gold and silver particles in in vitro
and in vivo settings (Albanese et al. 2012; Carlson et al. 2008; Daima 2013; Daima
et al. 2011, 2013; Daima and Navya 2016; El Badawy et al. 2010; Lee et al. 2005).
Increase in levels of reactive oxygen species, depletion in intracellular glutathione
levels and decrease in mitochondrial membrane potentials are important processes
that cause toxicity (Teow et al. 2011).
Yuan Wu et  al. studied effects of silver nanoparticles on Japanese rice fish
(Medaka, Oryzias latipes) by exposing the fish to silver nanoparticles in a different
dose and time dependent manner. The group observed greater toxicity of silver
nanoparticles in Medaka under chronic exposure conditions; oxidative damage and
histological changes resulted from 14 days of exposure. Captivatingly, the highest
bioaccumulation of the particles was found in liver tissue. The study also shows
much decreased activity of lactate dehydrogenase in a dose-dependent manner; sur-
prisingly found so only in liver samples than in gills. The reason for this tissue
dependent activity is, however, not yet fully understood and requires more investi-
gations (Wu and Zhou 2013). In an another toxicological study on silver nanopar-
ticles, Li et al. described size-dependent adsorption, uptake and hemolytic activity
of silver nanoparticles against fish red blood cells (RBCs) (Chen et al. 2015). They
observed that the highest level of adsorption and uptake by the RBCs was for the
middle sized particles compared to smaller or bigger ones. Nevertheless, they
observed higher hemolysis and membrane damage incurred by smallest sized tested
silver particles rather particles of other sizes.
Gold nanoparticles have also been studied for their potential toxic impact. As
shown in Fig. 8.8, Vecchio and team considered mutagenic effects of gold nanopar-
ticles using Drosophila melanogaster (Vecchio et al. 2012). In their first step, they
analyzed different aspects of the reproduction performance of the organism upon
ingestion of 15 nm gold particles at the rate of 3 μg/g per day concentration. They
studied fecundity and fertility of the treated organisms by observing number of eggs
laid and segment of emerged flies. During this study, the research team observed
very less number of eggs laid daily by the organism treated with gold nanoparticles
than that of controls. Also the number of adult individuals developed in the treated
samples was lower than the control. This can be attributed to a combined effect of
developmental disorders induced by the toxicity of gold nanoparticles causing lethal
genetic mutations in the genome. The findings indicate strong evidence of the adverse
effects of gold nanoparticles on organismal development (Vecchio et al. 2012).
In another study conducted by Schaeublin et al., gold nanoparticles showed sur-
face charge dependent cytotoxicity (Schaeublin et al. 2011). They studied the effects
8  Nanomaterial Impact, Toxicity and Regulation in Agriculture, Food and Environment 225

Fig. 8.8  Images of mutant phenotypes observed in the progeny when treated with gold nanopar-
ticles. First column represents wild type for reference. In the different rows, several body impair-
ments are shown, such as deformations of wings (A series), eyes (B) and thorax (C). Furthermore,
schematics describing the flies mating used in these experiments is also illustrated (Adopted from
Vecchio et al. 2012)

of modulating surface charge of 1.5 nm gold particles and observed changes in cel-
lular morphology, mitochondrial function, mitochondrial membrane potential,
intracellular calcium levels, DNA damage-related gene expression and of p53 and
caspase-3 expression levels upon exposing human keratinocyte cell line (HaCaT) to
the particles. Surface charged gold nanoparticles were found to cause significant
mitochondrial stress whereas neutral particles did not cause significant changes.
Also increased nuclear localization of p53 and increased caspase-3 expression was
observed in the cells with surface charged nanoparticles. Surface charged particles
induced cell death through apoptosis; whereas, neutral nanoparticles led to necrosis.
Such differential cytotoxicity need to be considered while dictating toxicity for
nanoparticles and need to be investigated systematically (Schaeublin et al. 2011).
Metal nanoparticles can readily transform in the environment, which modifies
their stability, uptake, transport, fate and toxicity. It is thus equally important to
consider such transformation of particles to evaluate their toxicity. For example, in
a recent review Sharma (Sharma 2013) writes that the high molecular weight com-
pounds like humic and fulvic acids in soil provide stability, till months, to silver
nanoparticles thus are likely to be transported to various locations and may have
ecological risk associated with them. On the contrary, silver binds strongly to sulfur
(organic or inorganic form) in natural or wastewater treatment plants, where silver
nanoparticles are expected to accumulate and release in particulate or ionic (Ag+)
form. Furthermore, it has been reported that the strong affinity towards sulfur results
in sulfidation of silver to form insoluble silver sulfide that cause lower toxicity of
original particles (Levard et  al. 2012). Hence, along with other physicochemical
properties nanoparticles chemistry in the environment plays significant role in caus-
ing toxicity to organisms and need to be investigated thoroughly prior to their
application.
226 A. Kaphle et al.

8.4.2  Metal Oxide Nanoparticles

The worldwide annual production of TiO2 nanoparticles is estimated to be ~3000

tons, ZnO is produced in the volume of ~550 tons annually and CeO2 nanoparticles
are produced in ~55 tons annually (Piccinno et al. 2012). The extensive usage of
metal oxide nanomaterials for a variety of applications ranging from electronics,
cosmetics to agriculture without assessing their potential impact on the end users
and customers has shocked policy makers and scholars in the field.
As discussed in previous section, typically ZnO and TiO2 nanoparticles are broad
spectrum antibacterial and antifungal agents. Studies are performed to assess their
potential in inhibiting pathogen bacteria, such as Escherichia coli O157:H7 (Jin
et al. 2009; Ma et al. 2013), Salmonella (Jin et al. 2009) and Listeria monocytogenes
(Jin et al. 2009). Though, from an ecological perspective, due to the nature of non-­
selective “killing” of microorganisms, understanding toxicity of these metal oxide
nanoparticles to environmentally relevant bacterial species is of great importance.
Often, this fact has been neglected, if not, overlooked, which is gaining significant
attention. Microorganisms, especially bacterial species are essential decomposers of
organic matter and are the base of many aquatic and terrestrial food webs (Ma et al.
2013). Thus, the non-selective broad spectrum nature of metal oxide nanoparticles
can potentially destroy useful species of microorganisms creating an imbalance in
the microcosm of soil. This hampers processes like nitrogen fixation and might result
in altering nutritional values of agricultural soil, which will have long term impact.
Likewise, there are reports that discuss about the toxicity of ZnO nanoparticles
to microalgae attributing the toxicity to solubilized Zn2+ release from the nanopar-
ticles. Furthermore, it has been established that eventually such nanoparticles can
inhibit photosynthetic activity of cyanobacteria instigating cell death (Ma et  al.
2013). Similarly, studies on higher plant species have shown toxicity of zinc parti-
cles to affect seed germination and root elongation. The toxicity resulted both from
the nanoparticles dissolution to Zn2+ ions and nanoparticle-dependent effect. In
addition to above reports, ZnO nanoparticles have also been found to be bioavail-
able and cause toxicity to earthworms. The nanoparticles encourage significant
response from antioxidant system and lead to DNA damage within the organism
(Hu et al. 2010; Unrine et al. 2010).
Moreover, CeO2 nanoparticles have been shown to cause oxidative stress and
membrane damage in rice plants as discussed by Rico et al. (2013a). In the study,
plants treated with 125 mg nCeO2 L−1 showed reduced antioxidant enzyme activi-
ties and high fatty acids content, resulting in increased membrane damage. However,
it was surprising to observe that 500  mg nCeO2 L−1 exhibited enhanced enzyme
activities with low fatty acids content besides low membrane damage. Translocation
into the vascular tissues of rice seedling roots and alteration in the biomolecular
components of the xylem was also found after Ce treatment. However, this altera-
tion of molecular content requires further studies to assess any negative impact on
the plant as suggested by the authors (Rico et al. 2013a). Similarly, in another study,
it has been established that nano-ceria can modify nutritional value of rice grains,
8  Nanomaterial Impact, Toxicity and Regulation in Agriculture, Food and Environment 227

which they suggested may have long term effect on the food quality (Rico et al.
2013b). Jose et al., in an independent study also obtained similar results of reducing
nutrition content of soybean plants caused by nano ceria (Peralta-Videa et al. 2014).
Besides, TiO2 has been studied for its toxicity to freshwater fish, cladocerans and
green algae that are low-level organisms in fresh water and marine food chains (Hall
et al. 2009). Scott et al. observed greater sensitivity of green algae towards TiO2
with IC25 value of 1–2 mg/l. However, organisms such as Ceriodaphnia dubia had
great resistance to the exposure with IC25 ranging from 9.4–26.4 mg/l, and fathead
minnow with IC25 values over 340 mg/l. Therefore, it has been suggested to consider
specific organism dependent toxicity and water quality parameters to evaluate TiO2
hazard in the ecosystem. In another study conducted by Seeger et al., unexpectedly,
found that woody plant species such as willow tree used in study were not sensitive
towards TiO2 materials and revealed no significant damage when compared to the
exposure to ZnO particles (Seeger et al. 2009). These studies contradict potential
risks of nanoparticles. However, many are preliminary results and should be con-
firmed with numerous studies, with different organisms taking care of surrounding
effect of the particles such as soil conditions and pH, when assessing agricultural
effects. Also, studies involving longer duration with gradually increasing exposure
concentration should be initiated before a final conclusion in this issue can be made.

8.4.3  Carbon Nanotubes

With increased carbon nanotube production, risk of environmental release and level
of exposure is increasing than ever. It is therefore necessary to evaluate their routes
of release, distribution and potential risks to biota. Toxicity of carbon nanotube
depends on numerous physiochemical factors such as particle size, shape, surface
charge, chemical composition, coating and surface roughness of nanotubes as dis-
cussed earlier. Larger surface area of carbon nanotubes have frequent chances for
cells contact. Smaller sized and functionalized carbon nanotubes have exhibited
enhanced ability to penetrate into wide range of cells and translocate through cel-
lular barriers (Kostarelos et al. 2007). However, as discussed by Fraczek et al. small
particles consisting of single walled carbon nanotubes were easily phagocytosed by
macrophages and transported to local lymph nodes (Fraczek et  al. 2008). Larger
particles can aggregate and accumulate in the organs during long-term toxicity stud-
ies. Surface charge of carbon nanotubes can affect the translocation of particles by
forming ion layers providing them hydrodynamic mobility. Carbon nanotube’s sur-
face can be cationic, anionic or neutral in nature, wherein cationic surfaces are
believed to be more toxic than other surfaces (Du et al. 2013).
In this context, it has been testified that acid-functionalized single-walled carbon
nanotubes cause considerably higher embryo toxicity and cytotoxicity compared to
neutral tubes (Saxena et  al. 2007). Similarly, in studies that compared effects of
cationic and anionic surfaces of carbon nanotube, it was found that cationic particles
induced stronger toxicity than the anionic particles (Sadiq et al. 2009). Comparatively,
there are very few reports on studies of carbon nanotubes toxicity with wild terres-
228 A. Kaphle et al.

trial species. Laboratory rodent studies with inhalation route and injection exposure
are available. In a study involving female Fisher rats, an oral dose of 0.64 mg/kg
single walled carbon nanotubes in saline or in corn oil displayed amplified levels of
oxidative damage to DNA in liver and lung tissue. From this report, it can be estab-
lished that carbon nanotube ingestion thus can be genotoxic to terrestrial mammals,
however further investigations are imperative (Folkmann et al. 2009).
It is interesting to state that the soil is expected to be the ultimate sink for carbon
nanotubes; therefore, their effects and bio-distribution in plants should be carefully
established. Few studies on phytotoxicity contradict effects caused by carbon nano-
tubes on terrestrial plants. In one of a recent study, seeds of six plant species (radish,
rapeseed, ryegrass, lettuce, corn and cucumber) were soaked in 2000 mg/L of multi-­
walled carbon nanotubes and incubated for 5 days for germination. In this study, no
difference in germination and root growth was witnessed (Lin and Xing 2007).
However, researchers observed reactive oxygen species induced phytotoxicity in
spinach when new types of multi-walled carbon nanotubes were employed (Begum
and Fugetsu 2012). On the other hand, it is surprising that some of the studies have
even revealed enhanced seed germination when carbon nanotubes were applied in
the media (Khodakovskaya et al. 2009).

8.4.4  Liposomes

Liposomes are the first nanomaterial preparations that can serve as very good deliv-
ery agents and can carry virtually any type of molecules. However, we need to be
careful in their usages. There are reports available that discuss about potential toxic-
ity of liposomes as inflammation, myelosupression, proliferation and carcinogene-
sis inducing agents (Lotem et al. 2000; Lyass et al. 2000). Commonly used neutral
lipids, phosphatidylcholine and cholesterol for preparing liposomes appear to be
non-toxic whereas charged liposomes, particularly the cationic ones have shown
potential toxicity. Hussain et al. (Hussain et al. 2007) studied 125 nm cationic lipo-
somes with an anticancer oligonucleotide coated with PEG designed to target cell-­
adhesion molecule exclusively expressed on solid tumors. Cell culture study
indicated the sensitiveness of the liposome loaded drug. Liposome alone contrib-
uted to nearly half of the sensitization following the investigation that focused on
the liposome effect only (Jian et al. 2012).
Similarly, Gokhale et al. (2002) assessed the toxicity of 467 nm sized cationic
liposomes coating the raf antisense oligonucleotide and empty liposome alone
using multiple assays in multiple species. It has been found that liposome could
increase neutrophil counts in dose-dependent manner with no effects on WBC
count, it can also alter enzymes amount in mice and swifts in complement activity
in monkeys. Toxicity of a nanomaterial is a function of its size, shape, surface
corona, charges and transformations that occur when they are present in the envi-
ronment. Therefore, these parameters must be considered while dictating toxicity of
any kind of material at nanoscale level.
8  Nanomaterial Impact, Toxicity and Regulation in Agriculture, Food and Environment 229

8.4.5  Dendrimers Nanotoxicity

Unarguably, dendrimers are great materials for delivery of active agents, for devel-
oping multiplexed sensory units, as their smaller size allow them to interact effec-
tively and specifically with the components of cell such as plasma membranes or cell
organelles. However, potential toxicity associated due to their terminal -NH2 groups
and multiple cationic charges might limit their prospects in applications. Dendrimers
having cationic surfaces exert significant in vitro cytotoxicity (Agashe et al. 2006).
However, coated or PEGylated dendrimers showed reduced effects thus providing
an opportunity to rationally design materials to avoid possible side-effects.
Studies carried out by Jevprasesphant et al. (Jevprasesphant et al. 2003) on inves-
tigating cytotoxic potential of PAMAM dendrimers in Caco-2 cell lines showed a
significant toxicity associated with the use of the dendrimer as shown in Fig. 8.9.
The observed cytotoxicity might be attributed to the presence of free primary amine
groups and the positive charge associated with them that shed off from the den-
drimer structure. Similarly, many studies confirm hemolytic, hematological and
immunological effects associated with dendrimers. Albertazzi et al. observed sur-
face chemistry dependent in vivo distribution and toxicity of G4 PAMAM and C12
lipid moieties added PAMAM dendrimers in the central nervous system. They have
observed high penetration of C12 particles due to their lipophilic nature and induced
apoptotic cell death of primary neurons even at nano-molar concentrations, whereas
G4 type dendrimers were reported to cause necrosis due to rapid cell damage
(Albertazzi et al. 2012).
Soledad Gonzalo et  al. studied amine- and hydroxyl- terminated poly (amido-
amine) (PAMAM) dendrimer internalization in microorganisms of environmental
relevance namely a cyanobacterium of the genus Anabaena and the green alga
Chlamydomonas reinhardtii (Gonzalo et al. 2015). They used PAMAM ethylenedi-
amine core dendrimers from generations G2 to G4 having cationic surface measured
as ζ-potential. They observed clear relationship between dendrimer generation and
toxicity, with higher toxicity for higher generations. Cationic and G4 generation
dendrimers considerably accelerated the formation of reactive oxygen species in
both organisms. Reporting for the first time about the quick and large internalization
of cationic PAMAM dendrimers by microorganisms, authors recommended further
investigations prior to their wide-spread use as such dendrimers may pose significant
risk for the environment, particularly for primary producers of natural ecosystems.

8.5  Risk Management and Regulatory Issues

As discussed in earlier sections, due to the presence of unique physicochemfical

properties nanomaterials are important for a range of beneficial technologies includ-
ing biological and therapeutic employability. However, sometimes because of addi-
tional important intervention, nanomaterials may also lead to adverse effects causing
230 A. Kaphle et al.

120 G2 G2.5 G3 G3.5 G4

100

80
%Viability.

60

40

20

0
Control

50
100
150
200
400
700
1000

50
100
150
200
400
700
1000

10
15
20
25
80
100

50
100
150
200
400
700
1000

2
5
10
30
80
100
Concentration (µM)

Fig. 8.9  Influence of dendrimer generation and concentration on the survival of Caco-2 cells
(mean ± S.D., n = 5) exposed to balanced salt solution (control), cationic (G2, G3, G4) and anionic
(G2.5, G3.5) PAMAM dendrimers (Opted from Jevprasesphant et al. 2003)

serious issues to health, plants and environment. In recent past, regulatory bodies
around the globe have realized the risk associated with the usage of nanomaterials.
It is imperative to fine-regulate balance between the efficacy and toxicity of nano-
materials before employing such materials (Thorley and Tetley 2013). In one of the
recent critical reviews, it has been discussed in detail that such nanomaterials that
are intended to be used in food products and medicinal purposes must be investi-
gated thoroughly by in silico, in vitro and in vivo toxicity analysis (Jain et al. 2016).
Various governmental agencies like The Royal Academy of Engineering, The
Royal society, The United States Environmental Protection Agency, The European
Commission‘s Scientific Committee and non-governmental organizations such as
Friends of the Earth and Xpert Arena are actively working on potential toxicity and
risk assessment of nanomaterials (Jain et  al. 2016). A few important regulations
have been established by the European Union for providing specific provisions for
nanomaterials usages directly or indirectly, as illustrated in Table 8.1. However, pre-
scribed specific guidelines for employing assorted nanomaterials for marketing and
use of nano-derived industrial products have not been prepared, which can be
accepted uniformly. Taking above discussion into account, it can be concluded that
only a few regulations providing specific provisions for nanomaterials have been
formulated which opens new opportunities for debate toward the nano-regulation
guidelines. Such regulatory guidelines are urgently required in current scenario for
better use of nanotechnology products in day to day life.
8  Nanomaterial Impact, Toxicity and Regulation in Agriculture, Food and Environment 231

Table 8.1  List for some of the important regulations established by the European Union for
providing specific provisions for nanomaterials usage directly or indirectly
Name of regulation and
specific features Particulars
Regulation (EC) no States that a food additive already authorized but obtained
1333/2008 nanotechnology requires an evaluation before marketing
For food additives
Regulation (EC) no States that a food enzyme already included in the community list but
1332/2008 prepared by different methods or using different starting materials
For food enzymes from those included in the risk assessment of authority, should be
submitted for re-evaluation
Regulation (EC) Though nanomaterials are not directly stated, there is a direct
450/2009a reference to “substances deliberately engineered to particle size
Active and intelligent which exhibit functional physical and chemical properties that
materials and articles significantly differ from those at a larger scale”; therefore, a
intended to come in case-by-case analysis has to be followed for active and intelligent
contact with food materials and articles containing nanomaterials
Regulation (EU) no States that substances with nanomaterial must be only used if stated
10/2011a in annex I of the regulation
Plastic materials and
articles intended to be
used to come in contact
with food material
This table has been adopted from Jain et al. (2016)
It can be noted that both regulation 450/2009 and 10/2011 state the functional barrier concept
a

which means that it is not directly applicable to nanomaterials

8.6  Conclusions

Nanosciences have brought a range of beneficiary changes to the agriculture, food,

environment and biological sciences and currently being reconnoitered extensively.
In this context, a variety of nanomaterials including metal nanoparticles, metal-­
oxide nanomaterials, carbon nanotubes, dendrimers, nanoemulsion and liposomes
are at forefront and advancing rapidly. Nevertheless, care needs to be taken prior to
using these materials as some of the reports are dubious about the safety of these
materials and investigating potential toxicity of nanomaterials. Moreover, long term
impact on environment and biological entities is unknown or rather unclear that
needs to be addressed urgently for safer and broad use of emerging nanomaterials,
wherein rationally designing of nanomaterials is imperative for providing additional
opportunities by avoiding possible side-effects. Furthermore, experiments control-
ling all the parameters that influence nanomaterials toxicity are difficult to establish;
however a model system representing most of these variables can give us a fair idea
of toxicity for a given material prior to its application in agriculture, food, environ-
ment and medicine, and such models need to be recognized urgently. Moreover,
strong regulatory guidelines are urgently required to utilize full potential of nano-
technology in agriculture, food, environment and biological sciences.
232 A. Kaphle et al.

Competing Interests  The authors declare that they have no competing interests.

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Chapter 9
Nanomaterial Toxicity in Microbes, Plants
and Animals

Babita Kaundal, Swayamprava Dalai, and Subhasree Roy Choudhury

Abstract  Nanotechnology has gained public interest due to its extensive use in
commercial products including industry, electronic components, agriculture, sports,
sunscreens, medicine and biomedical field. As a consequence there is an unprece-
dented growth of research in medicine for nanotoxicity following inhalation, inges-
tion and skin contact. This review presents the toxicity, fate, behavior and mechanism
of action of nanomaterials. It includes the effect of nanomaterials on microbes,
plant, animal and human. Factors controlling toxicity are nanoparticle size, shape,
surface charge, composition, ionic concentration and other physicochemical prop-
erties. We also list the market-available nanoproducts having toxic effects. We
describe the tests for detection of cytotoxity and genotoxicity. Risk management,
rules and regulations for marketed nanomaterials are also highlighted.

Keywords Nanoparticles • Nanotoxicology • Cytotoxicity • Genotoxicity •

Oxidative stress

9.1  Introduction

As per the definition adopted by British Standards Institution, the American Society
for Testing Materials and the Scientific Committee on Emerging and Newly
Identified Health Risks, a nanomaterial is a material with at least one dimension
under 100 nm (Bowman et al. 2010). Within this group, a nanoparticle) is defined as
materials with at least two dimensions under 100 nm (Buzea et al. 2007).
Nanotechnology Consumer Products Inventory estimated over 1800 publicly
available nanotech products from 622 companies in 32 countries (Vance et al. 2015).
Most of the products are from the health and fitness category containing 762, or
42% of the total, silver nanomaterials being the most frequently used (Vance et al.
2015). The study also shows that the majority (nearly 71%) of the consumer prod-

B. Kaundal • S. Dalai • S.R. Choudhury (*)

Institute of Nano Science and Technology,
Habitat Centre, Phase-10, Mohali, Punjab 160062, India
e-mail: subhasreerc@inst.ac.in

© Springer International Publishing AG 2017 243

S. Ranjan et al. (eds.), Nanoscience in Food and Agriculture 5, Sustainable
Agriculture Reviews 26, DOI 10.1007/978-3-319-58496-6_9
244 B. Kaundal et al.

ucts fail to disclose sufficient information about the usage of nanomaterials in them.
The project listed all the products contributing to the modern society, in an online
database. The engineered nanoparticles are having a variety of consumer and indus-
trial applications, such as devices used for energy, such as solar cells, fuel cells and
batteries; real-time diagnosis, high sensitive biomedical imaging in health sector
and as carriers of active pharmaceutical drugs in targeted delivery applications.
Titanium di-oxide (TiO2) nanoparticles in sunscreen, surface coatings, paints, cos-
metics, and food products (Chen et al. 2009); Silver in food packaging, disinfec-
tants, clothing and other home appliances (Silvestre et al. 2011; Duncan 2011); Zinc
oxide in cosmetics, paints (Wiesenthal et al. 2011; Lorenz et al. 2010), and CeO2 as
the fuel catalyst (Yu and Xi 2012) have designated Nanotechnology as one of the
fastest growing sectors of the high-tech economy. The unique properties of nanoma-
terials has instigated on the technological innovations to shape our world, as nano-
materials are bridge between bulk materials and atomic or molecular structures.
Also, nanomaterials offer ample opportunities for building novel compounds in
various areas of scientific research. Recent years have witnessed a tremendous
expansion of research and potential applications of nanotechnology.
Though the nanoparticles are having a very productive usage, we cannot ignore
the fact that these particles have a very soaring chance of getting released to the
environment, bearing a potential risk for human health. Each new nanomaterial
must be thoroughly analyzed to evaluate its advantages over the risks  (Dasgupta
et al. 2017; Shukla et al. 2017; Walia et al. 2017; Balaji et al. 2017; Maddinedi et al.
2017; Sai et al. 2017; Ranjan and Chidambaram 2016; Janardan et al. 2016; Ranjan
et al. 2016; Jain et al. 2016; Dasgupta et al. 2016). Nanotoxicology is defined as the
study and application of toxicity of nanomaterials. The nanomaterials exposure on
human body can be intentional (engineered nanoparticles used in consumer and
industrial products) or unintentional such as inhalation of fumes, powdered nano-
materials released from gas or wood furnaces (Dikio and Bixa 2011), pyrolysis of
acetylene and carbonization of synthetic polymers (Dikio 2011). Intense production
of carbon nanotubes has been reported from a low power soldering unit.
These facts have compelled a need for a preemptive analysis of fate and transport
of nanomaterials in the environment as well as the human exposure pathways. The
fate in the environment is largely determined by physicochemical and electronic
properties of nanomaterials such as thermodynamic properties, solubility, hydro-
phobic- hydrophilic balance etc. Moreover, the activity, fate and transport of nano-
materials in an environmental scenario also depend on the soil or water
physico-chemical properties and biota. The surface properties of nanomaterials also
contribute to toxic activity. Pristine nanoparticles aggregate faster than the surface
functionalized nanoparticles (Jiménez and Madson 2003). There is a wealth of stud-
ies in recent years, on the potential of nanoparticles to react with the biological
entities in a natural environment. The escalating applications of nanomaterials in
modern science require a thorough perceptive of their in vitro and in vivo activities
(O’Brien and Cummins 2010). Understanding the behavior of nanoparticles, such
as absorption, circulation, metabolism and excretion in  vivo, could bring better
insight into the toxicological aspects of these nanoparticles. The intentional and
9  Nanomaterial Toxicity in Microbes, Plants and Animals 245

Cell− Viability
Nanoparticle
interaction
Toxic

Intentional
NANOTOXICITY Non toxic
Unintentional
Changes in
Exposure Cellular
Function

Oxidative No
stress
Mechanism
Inflammation Yes

Genotoxicity

Fig. 9.1  Nanoparticle toxicity flow diagram. Exposure (intentional and unintentional) of nanopar-
ticles to the cell can lead to loss of cellular viability and change in cellular function. The major
mechanism of cell-nanoparticle interaction can be oxidative stress, inflammation and Genotoxicity

unintentional exposure of NP in an environment results in cell-nanoparticle interac-

tion. The viability of the cells will decide the extent of toxicity of these nanoparti-
cles as a preliminary evaluation technique of nanoparticle toxicity such as
[3-(4,5-Dimethylthiazol-2-yl)-2,5-Diphenyltetrazolium Bromide] assay. However,
the viable cells will face a change in cellular function if the nanoparticle toxicity has
sufficiently affected the cellular activities. The mechanism of nanoparticle toxicity
leading to disturbed cellular function/ viability, are generation of oxidative stress,
inflammation of cellular membrane and membrane of internal organs, and
Genotoxicity (Fig. 9.1). These nanomaterials may also get transported across a food
chain leading to bioaccumulation and biomagnifications posing greater health haz-
ard to the environment and human race. The unique properties of nanoparticles,
such as high specific surface area, abundant surface reactive sites, charge, shape,
and mobility, could potentially lead to unexpected health or environmental hazards.
Nanoparticle toxicity has been reported for mammalian cell lines (Sambale et al.
2015; Mukherjee et al. 2012; Song et al. 2014; Chueh et al. 2014), plants (Chichiricco
and Poma 2015; Ma et al. 2010), crustaceans (Ivask et al. 2014; Blinova et al. 2013;
Becaro et al. 2015), fish (Kovrižnych et al. 2013; Yue et al. 2015; Sohn et al. 2015)
and mice (Park et al. 2010; Xu et al. 2013; Faedmaleki et al. 2014). Nanoparticles
also present potential risks to human health because they have been shown to be
toxic to human lung cells (Sambale et al. 2015) and red blood cells (Shang et al.
2014).
246 B. Kaundal et al.

9.2  Nanotoxicology Research

The risk associated with nanomaterial exposure demands rapid and accurate strate-
gies to assess the potential unintended consequences of these materials. Oxide
nanoparticles are the most widely produced and used nanomaterials. Aluminum
oxide (Al2O3), silicon dioxide (SiO2), titanium dioxide (TiO2), and zinc oxide (ZnO)
are among the most frequently used industrial additives with various applications.
Aluminum oxide, since it has good dielectric and abrasive properties, is widely used
as an abrasive agent or insulator. TiO2 is an opacifier which has been used in paints,
papers, toothpastes, plastics, sunscreen, and many cosmetic products. SiO2 in crys-
talline form is widely used in electronics as a semiconductor. ZnO, which has
ceramic properties, has applications in semiconductors and pigments (Adams et al.
2006), beauty products and textiles. Nano metal oxides have greater surface area
and reactivity than bulk counterparts, hence providing superior performance, but
they may also bring higher environmental and health risks. Different market avail-
able nanoproducts made up of nanomaterials having toxicity are listed below
(Table 9.1).

9.2.1  Studies on Microbes

Microorganisms form the base of the food web and are indispensable agents in
maintaining biogeochemical cycles. Since commercial nanoparticles, eventually
enter the water-bodies, their interaction with aquatic microorganisms is of primary
consideration. The microbial processes also influence the distribution of metals in a
water body (Rajendran et al. 2003). Any damage to the microbes may disturb the
geochemical cycles. Hence, the negative impact of nanoparticles, released to the
environment, on microbes needs to be assessed.
Several studies in recent past have demonstrated the toxicity of organic and inor-
ganic nanoparticles towards bacterial cells. Carbon-based nanoparticles, oxide
nanoparticles (Adams et al. 2006; Brayner et al. 2006; Thill et al. 2006) and metal
nanoparticles (Choi et al. 2008) are all reported to have microbial cytotoxicity. The
unusual death of bacteria caused by nanoparticles may affect the normal biological,
chemical and nutrient cycles in the ecosystem, and may cause further detrimental
impacts on other organisms.
TiO2 nanoparticles exhibited potential cytotoxicity as well as membrane damage
potential with reactive oxygen species playing a major role (Kumar et al. 2011; Kim
et al. 2011; Adams et al. 2006). Lopes et al. (2012) studied the toxicity and genotox-
icity of two organic (vesicles composed of SDS or DDAB and of monoolein and
sodium oleate) and four inorganic nanoparticless (TiO2, TiSiO4, Lumidot-CdSe/ZnS
and Gold nanorods) to the bacteria Vibrio fischeri and Salmonella typhimurium.
Thill et al. (2006) studied the impact of a model water dispersion of nanoparticles
9  Nanomaterial Toxicity in Microbes, Plants and Animals 247

Table 9.1  Market available nano-products having toxic nanomaterials

Nanomaterials Applications Exposure Possible Risks References
Carbon Sporting goods, Inhalation, Pulmonary Oberdorster
nanomaterials, filtration and Skin contact inflammation, et al. (2002)
silica nanoparticle storage devices, granulomas and Kim et al.
OLEDs, computer fibrosis (2015)
RAM, cosmetics,
computer
hardware, Paints,
cleaning products,
cosmetics, food
supplements
Silver and gold Socks, hairbrushes, Skin, Central nervous Marin et al.
nanomaterials plasters, food ingestion system and other (2015)
packaging, food organ toxicity Coradeghini
supplements et al. (2013)
Cosmetics,
personal care
products, fuel
catalysts, food
supplements
Titanium dioxide Paints, sunscreens, Skin, Cytotoxic effects Armand et al.
antibacterial Ingestion on digestive (2016)
coatings, cleaning system, lung
products injury, liver
damage, intestinal
dysfunction and
damage
Zinc Oxide Sunscreen Skin, Digestive system Pati et al. (2016)
Ingestion toxicity,
Genotoxicity,
renal injury and
anemia
Fullerenes Sporting goods, Inhalation Cytotoxicity and Dönmez
filtration and DNA damage Güngüneş et al.
storage devices, (2016)
OLEDs, computer
RAM, cosmetics,
computer
hardware,
Photodynamic,
drug delivery
Iron Oxide Targeting and Inhalation Cytotoxicity and Dönmez
cancer diagnostics DNA damage Güngüneş et al.
(2016)
Quantum dots Intracellular skin Epidermis Ryman-­
imaging penetration Rasmussen
et al. (2006)
Carbon Nanotubes Cytotoxicity Skin Epidermis Tavares et al.
Inhalation inflammation, (2014)
Lung membrane
inflammation,
Genotoxicity
248 B. Kaundal et al.

(7  nm CeO2) on Gram-negative bacteria (Escherichia coli). These nanoparticles

were positively charged at neutral pH and thus displayed a strong electrostatic
attraction toward bacterial outer membranes. The small particle size, large surface
area of nanoparticles and their ability to produce reactive oxygen species are con-
sidered to be related to nanoparticle toxicity (Nowack and Bucheli 2007).
Another problem is that when bacteria are exposed to nanoparticles, it may enter
the food web through bacteria. Bacteria are essential links in both the aquatic and
soil food webs. In the aquatic food web, bacteria are the main food of protozoa,
which will be fed on by fish. In the soil food web, bacteria are food of protozoa,
nematodes, arthropods, which will feed birds and animals. Thus, the uptake and
adhesion of nanoparticles to bacteria will place nanoparticles in food webs, poten-
tially affecting human food safety.

9.2.2  Studies on Plants

Plants play a key role in the flow of energy from the sun to other organisms and are
thus fundamental for any terrestrial ecosystem. In anthropized environments the
tissue surfaces are exposed to pollutants on a daily basis, the aerial ones providing
a huge landing field for airborne particles and the subterranean ones a kind of drain
for pollutants absorbed by the soil.
A number of studies draw particular attention to the susceptibility of animals and
plants to nanomaterials, but the internalization of nanomaterials in plants and the
related toxicity mechanisms are still poorly understood (Miralles et al. 2012; Poma
et al. 2014; Husen and Siddiqi 2014). The protective layer of plant surfaces, restrict
the entry of foreign particles. However, the small size of nanomaterials may help in
effective penetration, resulting in harmful effects. Positively charged nanogold has
been used as probes to understand the mechanism of NP internalization through the
plasma membrane in plant cells (Chichiricco and Poma 2015). Eichert et al. (2008)
reported penetration of 43 nm polymeric nanoparticles in the stomatal leaf pores of
Vicia faba, whereas 1.1 μm particles did not penetrate. Kurepa et al. (2010) treated
the seedlings of Arabidopsis thaliana with TiO2 nanoconjugates having ~3 nm size,
in an agar media and reported the ability of these nanoparticles to penetrate into the
epidermis. Studied the phytotoxicological behavior of silver and zinc oxide
­nanoparticles on four different plants, i.e., Allium cepa and seeds of Zea mays
(maize), Cucumis sativus (cucumber) and Lycopersicum esculentum (tomato),
reporting the toxicity of nanoparticles. Ma et al. (2010) studied the impact of engi-
neered nanoparticles in relation to the composition, size, shape and other important
physicochemical properties in a plant model. Oukarroum et al. (2013) correlated the
generation of reactive oxygen species (ROS) in silver NP toxicity with the growth
and cellular viability of the aquatic plant Lemna gibba.
A number of studies in the recent past have elucidated the cytotoxicity potential
of TiO2 nanoparticles towards algae (Mohammed Sadiq et al. 2011). Though, uses
of freshwater and marine microalgae in wastewater treatment and heavy metal bio-
9  Nanomaterial Toxicity in Microbes, Plants and Animals 249

remediation are well established (Saunders et al. 2013), only a handful of reports
discussed NP detoxification potential of algae. Since, TiO2 nanoparticles are abun-
dantly used in the commercial products, studying their detoxification in the fresh-
water system becomes highly imperative.

9.2.3  Studies on Animals

Daphnia sp. is an important standard test organism in aquatic ecotoxicity testing

(Baun et  al. 2008). Studying the relationship between the accumulation and the
transportation of nanoparticles within this organism and their chronic toxicity will
offer valuable insights into the broad impact of nanoparticles in aquatic environ-
ments (Zhu et al. 2010).
The studies of TiO2 nanoparticles effect on aquatic organisms have mostly been
done on water flea (Daphnia magna, Daphnia pulex, Ceriodaphnia dubia etc.), and
the 48 h mortality or EC50 (EC50 that is defined by the concentration of an agonist
that produces 50% of the maximal possible effect of that agonist) was noted to be
more than 100 mg/L (Warheit et al. 2007; Zhu et al. 2010; Marcone et al. 2012).
Since, there are evidences showing free radical generation by TiO2 nanoparticles
under visible light and dark conditions, cytotoxicity under these circumstances
needs to be evaluated.
The profound use of nanoparticles offered a threat to the vertebrates in the
aquatic system. Studies evidenced that ZnO nanoparticles were toxic to zebrafish
embryos at different extents. To retard the oxidation and photocatalytic activity of
the ZnO nanoparticles, it was coated with different agents like zinc aluminate
(Fangli et al. 2003), aluminium hydroxide (Al [OH]3), polymers and inert oxides of
silica, anti-oxidant compounds like vitamins (A, E, C) (Tran and Salmon 2010).
However, the biological acceptability of such coated nanoparticles has not been
studied. To isolate a lower toxic species of ZnO, with a higher efficacy to attenuate
UV light is thus warranted.
The spleen is an important immune organ and a constituting part of the reticulo-
endothelial system. The toxicity of various doses of S-multiwallcarbon nanotubes
was examined by carbon clearance measurement, oxidative stress assay, histopatho-
logic and electron-microscopic examination. Compared with the control group,
phagocytic activity of reticuloendothelial system, activity of reduced glutathione,
superoxide dismutase and malondialdehyde in splenic homogenate did not change
significantly in 2 months. The histopathologic examination showed no observable
sign of damage in spleen; however, the accumulated S-MWCNTs gradually trans-
ferred from the red pulp to the white pulp over the exposure time and might initiate
the adaptive immune response of spleen.
250 B. Kaundal et al.

9.2.4  Studies on Human

The Royal Society identifies the potential for nanoparticles to penetrate the skin and
recommends that the use of nanoparticles in cosmetics be conditional upon a favor-
able assessment by the relevant European Commission safety advisory committee.
Recent investigations reported the toxicity of nanoparticles in various mammalian
cell lines. Sambale et al. (2015) studied the toxic effect of silver nanoparticles on
fibroblasts, human lung adenocarcinoma epithelial cell line and on human hepato-
cellular carcinoma cell line. Song et al. (2014) reported the effect of Cu nanoparti-
cles on liver cell lines. Carbon nanotubes are known for their microscopic size and
incredible tensile strength. A recent study shows that the carbon nanotubes may lead
to pleural abnormalities such as mesothelioma (cancer of the lining of the lungs)
(Donaldson et al. 2013). Considering these risks, rigorous regulation has been indis-
pensable ensuring their safe handling and disposal.
The potential workplace exposure of nanoparticles demands strict regulation.
According to Royal Society Report (2004), there is deep concern regarding the
inhalation of large quantities of nanomaterials by workers during the manufacturing
process. The possible health risks associated with NP exposure on human body has
been shown in Fig.  9.2. The exposure of nanoparticles at workplace has been
reported to be associated with diseases like asthma, bronchitis, heart diseases, neu-
rological disorders, asbestosis etc. nanoparticles may also affect kidney and liver
resulting in diseases of unknown etiology. To address such concerns, a study was
conducted by the Swedish Karolinska Institute (2008) on various NP effects on
human lung epithelial cells. According to it, iron oxide nanoparticle were found to
be less toxic, but they showed little DNA damage. ZnO and TiO2 nanoparticles were
reported to be highly detrimental. CNTs caused higher DNA degradation even at
lower concentration. Copper oxide nanoparticles were found to be highly detrimen-
tal at work place.
Nanoparticles form transient complexes with certain proteins (Radic 2015).
Polystyrene nanoparticles bind to several apolipoproteins form human plasma by
travelling through intestine wall and entering the blood stream, influencing fat
metabolism (Hellstrand et al. 2009).
The extremely small size of nanomaterials also means that they much more read-
ily gain entry into the human body than larger sized particles. How these nanopar-
ticles behave inside the body is still a major question that needs to be resolved. The
behavior of nanoparticles is a function of their size, shape and surface reactivity
with the surrounding tissue. In principle, a large number of particles could overload
the body’sphagocytes, cells that ingest and destroy foreign matter, thereby trigger-
ing stress reactions that lead to inflammation and weaken the body’s defense against
other pathogens. In addition to questions about what happens if non-degradable or
9  Nanomaterial Toxicity in Microbes, Plants and Animals 251

Fig. 9.2  Disease Associated with nanoparticle inhalation/ingestion. Nanoparticle mediated toxic-
ity related pathophysiological conditions of brain, heart, gastro-intestinal system, skin, lymphatic
system, lungs, kidney, liver and circulatory systems

slowly degradable nanoparticles accumulate in bodily organs, another concern is

their potential interaction or interference with biological processes inside the body.
Because of their large surface area, nanoparticles will, on exposure to tissue and
fluids, immediately adsorb onto their surface some of the macromolecules they
encounter. This may, for instance, affect the regulatory mechanisms of enzymes and
other proteins.
Nanomaterials are able to cross biological membranes and access cells, tissues,
and organs that larger-sized particles normally cannot (Holsapple et  al. 2005).
Nanomaterials can gain access to the blood stream via inhalation or ingestion. At
least some nanomaterials can penetrate the skin (Ryman-Rasmussen 2006); even
larger microparticles may penetrate the skin when it is flexed (Tinkle et al. 2003).
Broken skin is an ineffective particle barrier, suggesting that acne, eczema, shaving
wounds or severe sunburn may accelerate skin uptake of nanomaterials. Then, once
in the blood stream, nanomaterials can be transported around the body and be taken
up by organs and tissues, including the brain, heart, liver, kidneys, spleen, bone mar-
row and nervous system. According to a report by American Technion Society
252 B. Kaundal et al.

(2015), a team of researchers showed that exposure of nanoparticles (SiO2) can con-
tribute to cardiovascular diseases when the NP cross cellular and tissue barriers and
reach the circulatory system (Petrick et al. 2014). Researchers at Helmholtz Zentrum
Muenchen and the Technische Universitaet Muenchen (TUM) found that some com-
monly used engineered nanoparticles negatively affected the heart rate, rhythm and
ECG values of a test heart (Stampfl et  al. 2011). Kidney cells are also affected
severely with NP exposure. A study on silver NP toxicity suggested potential cyto-
toxicity and Genotoxicity of mammalian kindey cells (Milić et al. 2015). Indiana
University-Purdue University Indianapolis examined the effect of low concentra-
tions of carbon NP (CNP) exposure on renal epithelial cells, fullerenes (C60), single-
walled carbon nanotubes (SWNT), and multi-walled carbon nanotubes (MWNT) on
renal cells. The findings suggested that the nanoparticles can damage a kidney cell
which is a very appalling sign; because damage to kidney cells could result in toxic
waste products meant to be expelled from the body in urine could end up back in the
bloodstream or vice versa (Blazer-Yost et al. 2011). The toxic effect of ZrO2 nanopar-
ticles on the liver and kidney tissues as well as the activities in liver and kidney
enzymes has been investigated (Arefian et al. 2015). Upon NP exposure significant
increase in Malondialdehyde (MDA) levels in liver while significant decreases were
observed in Glutathione Peroxidase Enzyme Activity (GPX), Catalase Enzyme
activity (CAT) and Superoxide Dismutase Enzyme activity (SOD). When exposed to
high dosage of nanoparticles, the liver enzyme concentration was significantly
increased. The obtained results revealed the significant role of ZrO2 as an increasing
ROS generation agent and the ROS have induced the development of free radicals.
Nanomaterials have proved toxic to human tissue and cell cultures, resulting in
increased oxidative stress, inflammatory cytokineproduction and cell death
(Oberdörster et al. 2005). Unlike larger particles, nanomaterials may be taken up by
cell mitochondria and the cell nucleus (Porter et al. 2007). Studies demonstrate the
potential for nanomaterials to cause DNA mutation (Geiser et al. 2005) and induce
major structural damage to mitochondria, even resulting in cell death (Radoslav
et al. 2003).

9.3  Mechanism of Toxicity

Nanotoxicology is a sub-specialty of particle toxicology. It addresses the toxicology

of nanoparticles (particles <100 nm diameter) which appear to have toxicity effects
that are unusual and not seen with larger particles. Nanoparticles can be divided into
combustion-derived nanoparticles (like diesel soot), manufactured Nanoparticles
like carbon nanotubes and naturally occurring nanoparticles from volcanic erup-
tions, atmospheric chemistry etc. Typical nanoparticles that have been studied are
titanium dioxide, alumina, zinc oxide, carbon black, and carbon nanotubes, and
“nano-C60”. Nanoparticles have a much larger surface area to unit mass ratios
which in some cases may lead to greater pro-inflammatory effects (in, for example,
lung tissue). In addition, some nanoparticles seem to be able to translocate from
9  Nanomaterial Toxicity in Microbes, Plants and Animals 253

Table 9.2  Recent reports on Mechanism of Metal/ Metal Oxide Nanoparticle toxicity
Nanoparticles Mechanism of Toxicity References
Copper oxide Oxidative damage, genotoxicity, Ahamed et al. (2010), Fahmy and
cytotoxicity, nephrotoxicity Cormier (2009), Karlsson et al.
(2009) and Lei et al. (2008)
Cerium oxide Inflammation, apoptosis, p38-Nrf2 Kumar et al. (2011), Ma et al. (2011)
signaling, membrane damage and Eom and Choi (2009)
TiO2 Reactive oxygen species Dalai et al. (2014), Yoo et al. (2012)
Zinc oxide Mitochondrial dysfunction, apoptosis, Alarifi et al. (2013), Guo et al.
necrosis, inflammation (2013), Sharma et al. (2012),
Ahamed et al. (2011a, b), Xia et al.
(2008)
Iron oxide Necrosis, apoptosis, acute toxicity, Sohaebuddin et al. (2010),
endothelial permeability, and Raghunathan et al. (2013)
inflammation
Aluminum Mitochondria-mediated oxidative Pakrashi et al. (2011), Asharani et al.
oxide stress and cytotoxicity in human (2011)
mesenchymal stem cells, Aberration
Nickel oxide Lipid peroxidation and apoptosis Siddiqui et al. (2012) and Ahamed
et al. (2011a, b)
Ag-NP Mitochondrial damage and Gulati and Gupta (2012),
genotoxicity in human lung fibroblast Papageorgiou et al. (2007), Li et al.
cells (IMR-90) and human (2002)
glioblastoma cells (U251)
Gold Lipid peroxidation and autophagy Chairuangkitti et al. (2013) and Li
in vitro in MRC-5 lung fibroblasts et al. (2010)

their site of deposition to distant sites such as the blood and the brain. This has
resulted in a sea-change in how particle toxicology is viewed- instead of being con-
fined to the lungs, NP toxicologists study the brain, blood, liver, skin, and gut. The
reported mechanism of toxicity of few metal and metal oxide nanoparticles has been
briefed in Table 9.2.
For some types of particles, the smaller they are, the greater their surface area to
volume ratio and the higher their chemical reactivity and biological activity. The
greater chemical reactivity of nanomaterials can result in increased production of
reactive oxygen species (ROS), including free radicals (Manke et al. 2013). ROS
production has been found in a diverse range of nanomaterials including carbon
fullerenes, carbon nanotubes, and NP metal oxides. ROS and free radical produc-
tion is one of the primary mechanisms of NP toxicity; it may result in oxidative
stress, inflammation, and consequent damage to proteins, membranes, and DNA
(Nel 2006).
The bioavailability of Nanoparticles is an important factor in a natural environ-
ment. Once exposed in the environment, the Nanoparticles will not remain pristine.
Instead the particles with combine with various dissolved/ natural organic matter or
sediments in the environment which will play a major determining factor for decid-
ing the toxic activities of nanoparticles (Fig. 9.3). Hence the fate of the nanoparti-
cles in an environmental condition is highly dependent on several biotic and abiotic
254 B. Kaundal et al.

Dissolved organic
Whole Organism
matter Nanoparticles
Natural organic Bioavailability Uptake Cell or Tissue
particulates

Membrane
Sediments

Environmental Fate Effects at Molecular Level

Necrosis DNA Membrane toxicity

Growth Lethality Defence Reproduction Impairment

Effects at Individual Level

Fig. 9.3  Mechanism of nanoparticle toxicity: The cell-nanoparticle interaction depends on the
nanoparticle bioavailability. After cellular or tissue uptake, nanoparticles exhibit effects like necro-
sis, DNA damage and membrane toxicity at molecular level and reduced growth, lethality, reduced
self defence, reproduction and impairment at individual level

factors. On the contrary, these factors also contribute to the nanoparticle uptake by
membrane, tissue or whole organisms. The nanoparticle uptake may lead to necrosis
of the cell structure, contributing majorly towards membrane damage and DNA
degradation. The effects at individual level will be retarded growth, lethality, loss of
bodies self defence, loss of viable offsrings and impairment of normal cellular
function.

9.4  Cytotoxicity of Nanoparticles

A primary marker for the damaging effects of nanoparticles has been cell viability
as determined by state and exposed surface area of the cell membrane. Cells exposed
to metallic nanoparticles such as copper oxide, had up to 60% of their cells rendered
unviable (Seabra and Durán 2015). When diluted, the positively charged metal ions
often experience an electrostatic attraction to the cell membrane preventing it from
transportation and communication, rendering the cells inactive.
Along with existing and emerging use of nanoscale materials, i.e., metals such as
Ag, Au, metal oxides such as TiO2, ZnO, Fe3O4, Al2O3 and CrO3 and nonmetals such
as CNT, grapheme, growing concerns have arisen about their unintentional health
and environmental impact. Cellular morphology, mitochondrial function, mem-
brane leakage of lactate dehydrogenase (LDH), the permeability of plasma mem-
brane, and apoptosis are being assessed under controlled conditions (2 to 72 h of
exposure). The microscopic studies demonstrate the change in morphology of cells,
9  Nanomaterial Toxicity in Microbes, Plants and Animals 255

displaying cellular shrinkage, and membrane damage (Pakrashi et al. 2011; Dalai
et al. 2014). Mitochondria function, LDH release are several parameters that decide
the damage to cells. More cells became necrotic as the concentration of nanoparti-
cles increases. Proteins and organic substances increase the dissolution rates of par-
ticles of ZnO, CdSe, iron oxides, aluminium oxides and oxyhydroxides through at
least two mechanisms: aqueous complexation (that is, aqueous species complexing
free ions released from the material’s surface) and ligandenhanced dissolution (that
is, adsorbed natural organic material and organic acids extracting surface metal
atoms from NP surfaces).

9.5  Genotoxicity of Nanoparticles

Many methods ranging from comet assay to the HPRT gene mutation test have
found that metal-based Nanoparticles disrupt DNA and its replication process in a
variety of cells. In a study examining the effects of nanosilveron DNA, Ag
Nanoparticles were introduced to lymphocyte cell DNA which was then examined
for abnormalities. The exposure of the Nanoparticles correlated to a significant
increase in micronuclei indicative of genetic fragmentation (Huk et al. 2015). Metal
Oxides such as copper oxide, uraninite, and cobalt oxide have also been found to
exert significant stress on exposed DNA (Seabra and Durán 2015). The damage
done to the DNA will often result in mutated cells and colonies as found with the
HPRT gene test.

9.6  Immunogenicity of Nanoparticles

Very little attention has been directed towards the potential immunogenicity of
nanostructures. Nanostructures can activate the immune system, induce inflamma-
tion, immune responses, allergy, or even affect the immune cells in a deleterious or
beneficial way (immunosuppression in autoimmune diseases, improving immune
responses in vaccines). More studies are needed in order to know the potential del-
eterious or beneficial effects of nanostructures in the immune system. In compari-
son to conventional pharmaceutical agents, nanostructures have very large sizes,
and immune cells, especially phagocytic cells, recognize and try to destroy these
nanoparticles. Immunosuppression may be either inadvertent or desirable. Although
traditional toxicology studies focused on the undesirable consequences of immuno-
suppression (Descotes 2004), such studies are sparse for nanoparticles. To date,
most studies focused on the inflammatory properties of nanoparticles. One of the
few studies on immunosuppression has demonstrated that inhalation of CNTs sup-
presses B cell function and that the TGF-β produced by alveolar macrophages is a
key element in the mechanism of the observed immunosuppression (Mitchell et al.
2009).
256 B. Kaundal et al.

9.7  Risk Management of Nanoparticles

Major challenges related to the diversified actions of nanomaterials and nanoparticles

are to be addressed for their potential as commercial applications. Technical reports
such as ISO/TR12855 and ISO/TR13121 for providing framework related to risk
assessment related to nanomaterials has been established by International Organization
for Standardization (ISO) (ISO/TR 12885. Nanotechnologies-Health and Safety
Practices in Occupational Settings Relevant to Nanotechnologies 2008; ISO/TR
13121. Nanotechnologies-Nanomaterial Risk Evaluation, 1st ed.; the International
Organization for Standardization, 2011). Technical reports deliver framework for
systematic risk characterization, hazard identification, risk evaluation and assessment
of synthesized nanomaterials in order to provide safety to environment and popula-
tions, protect health including general public, consumers and workers.
Risk management framework related to nanomaterial can be divided into fol-
lowing steps;
Identification of hazard- Description of nanomaterial profiles, applications,
physicochemical properties, exposure and hazards profiles are documented.
Risk Evaluation- Depending upon identification of hazards and its exposure
potential risk associated and its severity are assessed.
Control Risk- Level 1 includes elimination of hazard, Level 2 includes substitu-
tion to a safer materials or products e.g., by using exhausted ventilation with
efficient filters such as HEPA.
Implementation of administrative control for developing safety data sheets.
Usage of personal protective measures including gloves, eye goggles, respira-
tory protector etc.
Decision, documentation and act- Decision of whether or in appropriate quan-
tity of production and development of nanomaterials to be determined.
Sharing information with the stakeholders taken in account depending above
the results of previous risk assessments frameworks.
Review- Update of the risk assessment process through regular review and spe-
cific events.
Conventional toxicity assays may include misleading results leading to technical
limitations such as nanoparticles due to their high surface area and hydrophobicity
have been observed to adsorb vital dyes, micronutirents of cell culture or cytokines
(Bakand and Hayes 2016). To overcome these limitations using systemic approaches
by taking control and standard, assessment of nanoparticles to interfere with the
assays, particle dispersion should be highly monitored and interpreted. Currently
for Nanomaterials size distribution, morphology and structure characterization
scanning electron microscopy (SEM) and transmission electron microscopy (TEM)
serve as efficient tools (Drobne 2007). Interdisciplinary research teams of nanotoxi-
cologists, chemists, engineers, and material scientists are required to collaborate,
investigate and understand the structural, analytical properties of nanomaterials and
their biological interactions.
9  Nanomaterial Toxicity in Microbes, Plants and Animals 257

Coating nanoparticles may be used for minimizing toxicity with desirable sur-
face properties. Uncoated TiO2 have been found to induce phototoxicity while coat-
ing the same with hydrophobic stabilisers used in sunscreen formulations has been
reported to show no cytotoxicity (Schilling et al. 2010). Covalent functionalization
with carboxyl groups have been reported to decrease the toxicity of carbon based
nanotubes (Sasidharan et al. 2011). The diverse therapeutic implications of AgNP
including dentistry, cancer treatment, and virucidal applications to biosensors in
diagnosis and imaging have been reported while a dose-dependent cytotoxicity of
AgNPs and Ag+ in A549 human lung-derived cells, have been significantly decreased
following pre-treatment with the antioxidant N-acetyl-cysteine (Shenava et  al.
2015).
Toxicity of AgNPs have also been reduced by its incorporation in collagen
hydrogels by tethering Nps to thio-modified LL37 peptide (Alarcon et al. 2016).
Very limited toxicological data are available regarding airborne contaminants,
also data related to standards for environment and workplace exposure are scanty,
thereby proper guidelines for exposure of nanoparticles to be established. Strategies
considering human health safety, environment protection, minimizing unintentional
occupational health hazards following exposure to nanoparticles should be evalu-
ated and accordingly control measures need to be implemented.
Two technical specifications on occupational health safety measures and use of
control banding for occupational risk management related to nanomaterials have
been implemented by ISO.
Control banding includes categories or bands of health hazards related to expo-
sure to engineered nanomaterials to predict the risk level. This control measures will
determine the level of risks involved. A practical guidance has been recommended
for industrial hygienists for understanding, management of occupational risk asso-
ciated with engineered nanomaterials accounting methods of monitoring and
describing criteria for risk management options (Ramachandran et al. 2011).
Rules and Regulations for Marketed Toxic Nanomaterials
Nanomaterials due to their miniscule size and large surface area have shown prom-
ises to potentially improve mechanical, optical, electrical, and catalytic features and
have been incorporated into wide variety of consumers and health goods, animal
feeds, food packaging and chemical fertilizers. However, little is currently known
about the possible effects of nanotechnology on human, animal or environmental
health. What we do know is that nanoparticles have a tremendous ability to pene-
trate cells and DNA structures. With increased use of nanoparticles, There are grow-
ing concerns about the possible toxic issues may be related with them on humans,
other living organisms and environment. Current laws monitoring nanomaterials
safety and risks are highly insufficient. The Toxic Substances Control Act (TSCA)
was also established to assess the risk associated with nanomaterials and to provide
authority to the Environmental Protection Agency (EPA) in regulating them.
Legislation governing the use of nanoparticles is limited around the world
(Table 9.3).
258 B. Kaundal et al.

Table 9.3  Legislation being followed in some countries regulating use of nanoparticles
Country Authorization/Organization Legislation
1. Europe EC(258/97) (European Food Safety Novel food/feed
Authority guidelines)
(EC) 1333/2008 Food additives
(EC) 1332/2008 Enzymes
(EC) 1334/2008 Flavourings
(EC) 1831/2003 Feed additives
(EC) No 1107/2009 Agricultural pesticides
(EC) 20/2011 Plastic food contact
materials
(EU) No 528/2013 Biocides
2. U.S US Food and drug administration (FDA) Federal food, drug and
cosmetic act
Environmental Protection Agency (EPA) (FFDCA) Federal
Insecticide, Fungicide
and Rodenticide Act
(FIFRA)
3. Australia/New Food Standards Australia New Zealand Australia New Zealand
Zealand (FSANZ) Food
Standards Code
4. Canada Canada Canadian Food Inspection Food and Drugs Act
Agency (CFIA)
5. Switzerland Switzerland Swiss Federal Office of
Public Health (FOPH)
Federal Office for the Environment
(FOEN)
6. China Ministry of Agriculture Food Safety Law of
Ministry of Health China, 2009
National Institute of Metrology
7. India Food Safety Standard Authority of India Food Safety and
(FSSAI) Standards Act, 2006
8. Japan Ministry of Health, Labour and Welfare Food Sanitation Law
9. Korea Ministry of Food and Drug Safety Food Sanitation Act
(MFDS)
Korean food and Drug Administration
(KFDA)
Korean Agency for Technology and
Science (KATS)
10. Russia The Federal Service for the Protection of Sanitary Rules and
Consumer Regulations (“SanPiN”)
Rights and Human Well-Being of the
Ministry of Health and Social Development
(Rospotrebnadzor)
11. Thailand Food and Drug Administration of the Food Act B.E.2522
Ministry of Public Health
12. Antarctica Antarctica (Environmental Protection) Waste disposal
Act
9  Nanomaterial Toxicity in Microbes, Plants and Animals 259

9.8  Future Aspects

Though the nano-product industries are on an exponential rise, the concern for the
potential ill effects of NP toxicity on the environment and on human health is also
increasing day by day. The unique properties of nanoparticles have distinguished
them from their bulk counterparts in quite a lot of applications. NP toxicity assess-
ment is currently a major research area, the focus being nanoparticle interaction
with biological systems.
Most of the toxicological assessments have utilized a cost-effective in vitro sys-
tem. However, in an in vitro system only specific biological pathways can be tested
under controlled conditions. Performing toxicological evaluation in an in vivo sys-
tem is difficult, costly and incorporates many challenges.
NP adsorption onto the cell membrane and internalization has been reported sev-
eral times. However, limited information is available suggesting the relation between
nanoparticle physiochemical factors and their intracellular distribution. Also, the
molecular targets for nanoparticles on the cell membranes and cellular organelles,
has not been fully explored. To develop a foolproof protocol for nanoparticle toxic-
ity assessment, through knowledge on particle adsorption, cellular uptake and inter-
nalization of nanoparticles contributing to altered biological responses, is need of
the time.
Intensive research is in demand to understand the link between nanoparticle
physiochemical properties (size, shape, surface charge, surface area, roughness,
composition, catalytic properties) and biological responses. Furthermore, stipulated
studies are called for (i) assessing the role of nanoparticle internalization on its tox-
icity, (ii) studying the molecular markers on the cell membrane and organelles
involved in nanoparticletoxicity response, (iii) assessing the underlying mechanism
of action of nanoparticles towards a biological entity, i.e., oxidative stress, mem-
brane aberration, lipid peroxidation and genotoxicity.

9.9  Conclusion

The concern regarding potential nanoparticle toxicity in the environment is need of

the moment. Stringent, unprejudiced assessment of current regulatory policies of
nanomaterial safe handling and disposal is in demand. Also the potential workplace
exposure of nanoparticles demands strict regulation. On the other hand, the current
lab based toxicity evaluation methods should be revisited. Current toxicity evalua-
tion methods mostly focus on in vitro investigations, whereas, in vivo studies will
give proper insight to the nanomaterial fate and behavior in a human body.

Acknowledgement  We kindly acknowledge SERB DST Funding (YSS/2015/001706) to Dr.

Subhasree Roy Choudhury.
260 B. Kaundal et al.

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Chapter 10
Nanofertilizers for Sustainable Soil
Management

Santosh Kumar Sanivada, Venkata Smitha Pandurangi,
and Murali Mohan Challa

Abstract  New fertilizers utilizing nanotechnology are a solution to upgrade the

worldwide farming productions. Advancement of dependable and eco-friendly
methodology for amalgamation of nano-particles is an imperative stage in the field
of farming. This article reviews the impact of engineered nanomaterials on soils.
This article then proposes risk assessment strategies to address the situation. The
major topics are nanofertilizers for future agriculture; effects of engineered nano-
materials on soil health and biodiversity; sustainable soil management; validation of
fertilizer potential; mechanism of action of nanomaterials as fertilizers; nanofertil-
izers, agricultural productivity and greenhouse gas emissions; engineered nanoma-
terials in ‘biosolids’ used to fertilize agricultural fields; exploring the efficacy of
commercially available engineered nanomaterials on a soil microbes; nanotechnol-
ogy regulation; nanofertilizers applications; and the future of nanofertilizer market
sector.

Keywords  Nanotechnology • Ecofriendly • Engineered nanomaterials • Agriculture

• Fertilizers • Soil health • Biodiversity • Soil management • Green house gas emis-
sions • Regulation

S.K. Sanivada (*)

Department of Microbiology and Food Science & Technology, GITAM Institute of Science,
GITAM University, Beach Road, Gandhi Nagar, Rushikonda, Visakhapatnam 530045,
Andhrapradesh, India
e-mail: santoo.sanivada9@gmail.com
V.S. Pandurangi
Department of Biochemistry, GITAM Institute of Science, GITAM University,
Visakhapatnam, Andhrapradesh, India
e-mail: venkatasmitha_pv@yahoo.co.in
M.M. Challa
Department of Biotechnology, GITAM Institute of Technology, GITAM University,
Visakhapatnam, Andrapradesh, India
e-mail: mmchalla@gmail.com

© Springer International Publishing AG 2017 267

S. Ranjan et al. (eds.), Nanoscience in Food and Agriculture 5, Sustainable
Agriculture Reviews 26, DOI 10.1007/978-3-319-58496-6_10
268 S.K. Sanivada et al.

10.1  I ntroduction to Need of Nanofertilizers for Future

Agriculture

Upheaval of world population in the previous decade has constrained the agricul-
tural area to build crop profitability to fulfill the needs of billions of individuals
particularly in developing nations. Broad presence of mineral insufficiency in soils
has brought about extraordinary monetary loss for farming community and critical
reductions in wholesome quality and general amount of grains for individuals and
domesticated animals. Agrochemicals characterize chiefly by fertilizers and pesti-
cides are indispensable inputs for agriculture production. At times, the application
surpasses two times the ideal amount, implying that other undesired outcomes tune
in, for example, ecological tainting or generation of green house gasses. An impres-
sive experimental exertion has been made to create feasible frameworks for the
controlled or moderate conveyance of agrochemicals, with a specific end goal to
alter the mineral accessibility in soil to insignificant dosages needed for pest control
or to levels required by plants (Pereira et al. 2015). Utilization of large scale use of
chemical fertilizers to build the yield profitability is not a suitable choice for long
run since the fact that the chemical fertilizers are considered as twofold edged
swords, which from one perspective build the yield generation however then again
aggravate the soil nutrient balance, diminishing soil fertility and even more on the
evolved ways of life crosswise over biological systems prompting heritable changes
in future eras of consumers (Solanki et al. 2015).
The field of nanotechnology has seen remarkable development over the past
decade can possibly give answers for crucial agricultural issues brought on by con-
ventional fertilizer and pesticide administration (Mastronardi et al. 2015). A nano-
meter (nm) is one billionth of a meter, and an engineered nano material (ENM),
customarily characterized, has not less than one size measured at less than 100 nm.
A bacterium measures about 25,000 nm or 2.5 small scale meters in length (Auffan
et al. 2009). Regularly used fertilizers can be refined down to around ten microns,
with a micron being one millionth of a meter. Given the heterogeneity of engineered
nanomaterials and the novel properties connected with their size, shape and differ-
ent viewpoints, a formal and extensive administrative meaning of “nanomaterial”,
which is versatile to new logical discoveries, is hard to focus. Then again, the rou-
tine definition is of a material measuring 1–100 nm that can be designed, envisaged
and controlled (Subramanian et al. 2015; Hendren et al. 2013).
Headway in nanotechnology has enhanced courses for substantial scale creation
of nanoparticles of physiologically vital metals, which are currently used to enhance
fertilizer formulations for improved uptake in plant cells and by minimizing mineral
loss. Nanoparticles have high surface area, sorption limit, controlled-discharge
energy to focus on targeted sites making them smart delivery system (Solanki et al.
2015). They could accurately discharge their active ingredients in reacting to eco-
logical triggers and natural demands. In latest laboratory examinations, it has been
found that nano-fertilizers can enhance crop profitability by improving the rate of
seed germination, seedling development, photosynthetic movement, nitrogen
10  Nanofertilizers for Sustainable Soil Management 269

NANO FERTILIZERS NANO PESTICIDES NANO CARRIERS

INCREASING
AGRONOMIC TOXICITY TO SOIL
PRODUCTIONS AGRICULTURAL MICROORGANISMS
APPLICATIONS OF
NANOTECHNOLOGY
ENHANCED POTENTIAL PLANT
FERTILIZERS IN CROP AND HUMAN
FERTILIZATION HEALTH IMPACTS

PLANT-GROWTH Benefits Potential ETHICAL AND

STIMULATION risks SAFETY ISSUES

UPGRADING THE
BIOAVAILABILITY OF LOW LEVEL OF
MICRONUTRIENTS PUBLIC AWARENESS

POSSIBLE REMEDIES

REASSESMENT OF NEED OF PUBLIC POLICY TO

INCENTIVES ARE NEEDED
ECOTOXICOLOGY AND ESTABLISH ENVIRONMENTAL
FOR PROMOTING SMART
SYSTEMATIC ANALYSIS OF SAFE FATE OF AGRI-NANO
SOLUTIONS
DISPOSAL TECHNOLOGY APPLICATIONS

Fig. 10.1  Agricultural applications of nanotechnology, their benefits, potential risks and possible
remedies

metabolism, and carbohydrate and protein synthesis. In any case, similar to a new-
born innovation, the moral and security issues encompassing the utilization of
nanoparticles in plant efficiency are boundless and must be precisely assessed
before adjusting the utilization of the nano-fertilizers in crop fields (Solanki et al.
2015) (Fig. 10.1).
Microbial decay of crops is connected with tremendous conservative losses, and
the use of nanoformulated antimicrobial substances emerges as an intriguing dis-
tinct option for face the risk brought about by such microorganisms. Antimicrobial
nanoparticles can discover a few applications in farming and the viability of metal-
lic nanoparticles including silver, nickel, iron, and zinc oxides has been exhibited in
numerous frameworks. Likewise, the capture of antimicrobial substances in diverse
nanostructures may speak to an option for conveyance of these mixes. A differing
quality of nanovesicles has been created for exemplification of antimicrobial sub-
stances, including both normal and manufactured polymers as epitomizing material
(Brandelli 2015).
However, the utilization of nanomaterial containing fertilizers and other agricul-
tural commodities additionally conveys natural and health risks, for example, the
collection of nanomaterial residues in edible tissues, which prompts potential phy-
totoxicity to farming harvests and unsettling influence to the biological community.
These natural and wellbeing risks should be surely known before the utilization of
nanotechnology in agriculture can be completely grasped (Ma and Gao 2015).
270 S.K. Sanivada et al.

Fig. 10.2  Nanotechnology offers answers for different issues in agriculture including lessening
the utilization of fertilizer, pesticide and water. Soil could be a significant sink of nano particles
contrast with air and water biological community consequently, there is an attention to assess the
risks associated to engineered nanoparticles in soils

(Fig.10.1). Toxic effects of nanoparticles have been seen in various in vitro studies
specifically, numerous nano particles, for example, silver-, copper-, or zinc oxides-
nanoparticles, are known for their antimicrobial properties (Dinesh et  al. 2012;
Dasgupta and Chidambaram 2016). The toxicity quality component frequently said
is an oxidative stress created by the generation of responsive oxygen species from
nanoparticles in contact with microbial films, bringing on disturbance of layers,
oxidation of proteins, or interference of vitality transduction (Klaine et  al. 2008;
Neal 2008; Xia et al. 2008).
Amid the diverse periods of their life cycle, from generation to transfer, engi-
neered nanomaterials can be discharged to the earth either directly or indirectly,
raising incredible worries about potential biological risks. Direct estimation of engi-
neered nanomaterials fixation in nature stays troublesome because of current spe-
cialized confinements (Cornelis et al. 2014). As of now, the best way to get data on
existing levels of nano particles in nature is to model anticipated ecological focuses
(Sun et al. 2014). Presentation demonstrating unequivocally recommends that soil
could be a noteworthy sink of nano particles compared with air and water biological
communities (Sun et  al. 2014). Subsequently, there is an interest to evaluate the
risks related to engineered nanomaterials in soils, keeping in mind the end goal to
protect the soil ability to satisfy vital environment administrations (Naja et al. 2009)
(Fig. 10.2).

10.2  E
 ffects of Engineered Nanomaterials on Soil Health
and Biodiversity

Indeed, even the exceptionally hopeful market allocation is estimated to be between

$50 billion and $1 trillion in worldwide estimation of engineered nanomaterials
and nanotechnology-empowered good sales (World Economic Forum 2015), is
10  Nanofertilizers for Sustainable Soil Management 271

overshadowed by the evaluated monetary estimation of the biological system ben-

efits that rely on upon soil biodiversity. Such appraisals are liable to the situation
suspicions of econometrics. On the other hand, considering even a wide level of
methodological mistake, even the fractional the loss of the financial estimation of
soil because of the misapplication of engineered nanomaterials in fertilizers and
soil small scale supplements, for example, zinc, accommodates more than ade-
quate defense for the safety oriented methodology taken by testing the impacts of
engineered nanomaterials on soil-like media in the research facility. Amid the pre-
vious decade, soil science examination has reacquired arrangement and budgetary
conspicuousness, demanding that “soils are back on the worldwide schema”
(Pascual et al. 2015). The generally low universal profile of soil strength and bio-
diversity exploration will turn out to be steadily applicable to the innovation evalu-
ations of agri-nanotechnologies (Nanowerk 2015). Conversely, till date, no
enactment or law exists that is particularly focused at soil biodiversity, whether at
worldwide, national or provincial level. This reveals the absence of consciousness
for soil biodiversity and its worth, and in addition the unpredictability of the sub-
ject. A few territories of arrangement specifically influence and could address soil
biodiversity, including soil, water, atmosphere, rural and nature approaches (Boer
and Hannam 2015).
European Commission analysts and soil researchers have arranged database for
lawmakers and different policymakers to consider in drafting such obligatory law
(Nanowerk 2013). The analysts have portrayed in incredible details of how soil
attempts to feed biological system, not the slightest among them crop production.
Keeping in mind the end goal to bring up issues for an innovation appraisal on the
connection of micronsized (1000 nanometers) fertilizer particles and engineered
nanomaterials with soil, it is important to give a brief portrayal of the genuine soil
environment that is extraordinarily disentangled when researchers test the impacts
of engineered nanomaterials in lab tests. While it is hard to picture the intricacy of
the trophic (feeding) connections that deliver soil. The disintegration of plant matter
by microscopic organisms and parasites, and the trophic cycle of mega and micro-
fauna that joins with the mineral pool, atmosphere and fertilizers, both characteris-
tic and substance, speak to the unpredictability of soil health. As indicated by
International Soil Reference and Information Centre (ISRIC)  - World Soil
Information project report, misuse of the soil has a worldwide financial and produc-
tivity loss estimation of about $66 billion USD per annum (Bai et al. 2012; Conijn
et al. 2013).
Not all engineered nanomaterials utilized as a part of soil added substances
will influence these aspects in the soil/plant food chain, yet for our intent, the vital
trophic connections give off an impression of being the way the soil mineral pool,
amplified by fertilizer particles of nitrogen (N), phosphorus (P) and potash (K)
and engineered nanomaterials soil supplements, amplified with the soil organic
group. This group incorporates the micron-sized organisms and microbes that are
the initiate of the feeding chain for the earthworms and other fauna that would
deplete the engineered nanomaterials. The assurance of the biological controllers,
272 S.K. Sanivada et al.

biological community and chemical researchers would be a need for any commit-
ment of the revamping of worldwide soil health to feasible improvement. In the
event that engineered nanomaterials are to be added to agronomical soil, whether
purposefully or not, an innovation evaluation of agri-nanotechnologies will need
to consider exploration on soil deprivation and soil health. The utilization of the
microorganisms and growths by the mites and nematodes and their utilization was
accomplished by the termites, ants and earthworms is not just a nutritious rela-
tionship that engineered nanomaterials could upset (Hagerbaumer et  al. 2015).
The soil governing and fabricating roles of each of these primary life forms would
likewise be influenced. As talked about beneath, researchers are as of now testing
for the impact of engineered nanomaterials on earthworms and single isolates of
soil microorganisms. As imperative as these analyses seem to be, they don’t claim
to start to test for the impact of engineered nanomaterials on the trophic and pro-
vincial connections among the living beings of the soil natural group (Smita et al.
2012).
At the point when, for instance, carbon nanotubes are added to soil in research
examinations to figure out if the nanotubes will boost seed germination rates
(Khodakovskaya et al. 2009; Tripathi et al. 2011; Mondal et al. 2011; Srinivasan and
Saraswathi 2010; Smirnova et al. 2011; Wang et al. 2012). An innovation evaluation
about such examinations needs to explore additionally how those carbon nanotubes
will influence the different soil organic and synthetic controllers. While it is reason-
able that researchers pick the earthworm for testing toxicity in soil, subsequent to
the earthworm is close to the end of the soil feeding chain (Hayashi and Engelmann
2013).
It is inescapable that, along with their utilization, designed nanoparticles will be
discharged into soils and waters. Along these lines increasing worry over the poten-
tial effects of engineered nanoparticles in the soil environment and on human well-
being. However accessible information shows that present risks of engineered
nanoparticles in the earth and human wellbeing were still limited. Therefore a
requirement with work to increase an understanding of the exposure levels for engi-
neered nanoparticles in natural frameworks and to begin to investigate the outcomes
of these levels in terms of the ecosystem and human health. This will require
research in a range of areas, including detection and characterization, environmen-
tal fate and transport, ecotoxicology and toxicology.

10.3  Sustainable Soil Management in Agricultural Systems

Merchandising farmers are encouraged to certify their soil health yearly. Farmers
may supervise the soil health by testing on the diverse soil groups and yield zones
of their fields utilizing monetarily accessible units or sending soil tests to research
10  Nanofertilizers for Sustainable Soil Management 273

facilities to determine the status of the organic, physical and chemical measure-
ments. The outcome of the chemical investigation helps to figure out what rebalanc-
ing of NPK and other soil added substances ought to be purchased to plant one year
from now’s harvest. Conversely, for settling the natural and physical issues of the
soil are not all that fast as that of applying another blend of compost to compensate
for NPK deficiencies or disproportion (AGWEB 2013).
Soil health exhibited as an integrative property that mirrors capacity of soil to
react to nanotechnologic agricultural intervention, so that it maintains to sustain
both the farming production and the provision of other ecosystem functions. The
significant challenge within sustainable soil management is to conserve ecosys-
tem function while optimizing agricultural yields. It is suggested that soil health
is dependent on the safeguarding of four noteworthy functions: carbon conver-
sions; nutrient cycles; soil constitution safeguarding; and pest and disease regu-
lation. Each of these functions is showed as total of a variety of biological
processes provided by a diversity of interacting soil organisms under the influ-
ence of the abiotic soil environment. Examination of current models of the soil
community under the contact of nanotechnologic agricultural interventions
affirms the profoundly integrative prototype of associations inside of each of
these functions and prompts to the conclusion that measurement of individual
groups of organisms, processes or soil properties does not be sufficient to specify
the soil health state.

10.4  Validation of Fertilizer Potential

The fate of fertilizers is estimated to depend on nanotechnology applications.

Mukhopadhyay (2014) endeavored to gauge this future as far as items or procedures
reported in patents conceded. While it might be difficult to guess what future part
nanotechnology will play in the improvement of fertilizers, there is an unmistakable
sign that the business is heading in this order (Box 10.1). This reasonable course is
archived by the many patents petitioned for nano-sizing and once in a while consoli-
dating into fertilizers with added substances, for example, nano–metal oxides that
would target pathogenic soil microorganisms (Mastronardi et al. 2015). Still, orga-
nizations appear to be extremely hesitant to promote those arrangements. The
micro-scaling of fertilizers is a worldwide business practice, but a few organizations
have started to publicize their fertilizers as nano-sized “Smart nano-fertilizer” has
been proposed with nanosized biosensors suspended in a biopolymer that coats
micronsized fertilizer particles (Solanki et al. 2015).
274 S.K. Sanivada et al.

Box 10.1 Possibility of Engineered Nanomaterials as Fertilizers for

Increasing Agricultural Productions (Liu and Lal 2015)
Macronutrients as nano fertilizers for increasing agronomic productions:
Plant macronutrients, particularly nitrogen and phosphorus are essentially
critical as far as agronomic creation, sustenance security, and natural insur-
ance in examination with different nutrients. In this manner, research, devel-
opment and use of nanofertilizers with high productivity (low leaching rate,
low immobilization rate by soil, and high plant-uptake rate) and low natural
risks (low eutrophication potential and low nitrogen leaching rate to the
groundwater) are important and a high research concern.
Application of micronutrients as nanofertilizers in soil-plant systems:
Micronutrient research ought to concentrate on upgrading the bioavailability
(plant-uptake rate) of these fertilizers to address the molybdenum leaching or
soil fixation issues like iron, zinc or copper connected with the traditional
micronutrient fertilizers. All the more essentially, research is expected to look
at the valuable impacts of these micronutrient nanofertilizers with industrially
accessible micronutrient partners (e.g., Iron nanoparticles versus ferric chlo-
ride or iron ethylenediaminetetraacetic acid (EDTA) as iron sources) under
the field condition.
Potential of nanomaterial-enhanced fertilizers in crop fertilization:
Zeolites are still a promising nanomaterial in diminishing nitrogen leaching
and expanding effective utilization of nitrogen. Extra research needs to ana-
lyze the yield and ecological advantages of nitrogen-stacked zeolite fertilizers
with the additional expenses from zeolite acquirement and the nitrogen-­
stacking procedure. It is likewise critical to look into and create different sorts
of nutrient augmented nanoparticles, for example, silica-nanoparticles, iron
oxide-nanoparticles, and carbon nanotubes.
Effects of engineered nanomaterials on plant-growth stimulation:
Recent research findings on utilizing titanium dioxide-nanoparticles or car-
bon nanotubes as a plant development stimulant can altogether build agro-
nomic yields. Indeed, Carbon nano tubes application can dramatically
multiply the tomato yield over that of the controls (Khodakovskaya et  al.
2013), which is an amazingly high reaping improvement when interpreted
into ranch generation scale. Be that as it may, this constrained information
depended on research center or nursery concentrates just, extra proof, espe-
cially field confirmation, is expected to accept such considerable yield genera-
tion upgrades

The nano-biosensors discharge the fundamental fertilizer supplements in

response of plant needs, as conveyed by root framework particle signals (Monreal
et al. 2015). According to one review of agri-nanotechnology writing, “the utiliza-
tion of nanoparticles in agribusiness is in its early stages, with hardly any research
10  Nanofertilizers for Sustainable Soil Management 275

articles compared to medicinal field” (Dimkpa et al. 2012a). On the other hand as it
may in it infancy, sustained by both private and government grants, is budding fast
“Exploratory patents and research articles on nanomaterials in fertilizers or plant
safety have expanded exponentially since the thousand years shift” (Mastronardi
et al. 2015; Gogos et al. 2012).

10.5  Mechanism of Action of Nanomaterials as Fertilizers

There is an urgent need to develop smart materials that can systematically release
chemicals to specific targeted sites in plants which could be beneficial in controlling
nutrition deficiency in agriculture. “Smart delivery system” means combination of
specifically targeted, highly controlled, remotely regulated, and multifunctional
characteristic to avoid biological barriers for successful targeting (Nair et al. 2010).
Advancement in technology has improved ways for large-scale production of
nanoparticles of physiologically important metals, which are now used as “smart
delivery systems” in order to improve fertilizer formulation by minimizing nutrient
loss and increased uptake in plant cell (Naderi and Danesh-Shahraki 2013). These
“nano-fertilizers” have high surface area, sorption capacity, and controlled-release
kinetics to targeted sites attributing them as smart delivery system.
Different kinds of nanomaterials, including those manufactured from elements
not traditionally classified as nutrients (e.g. titanium, silicon, silver) and nano forms
of micronutrients such as Zn, Fe and Mn, have been demonstrated as being able to
improve crop growth and content of these elements (Larue et al. 2012; Wang et al.
2013a, b, c; Siddique and Al-Whaibi 2014; Servin et al. 2015). Often, the positive
effects of nanoparticles on crop growth occur to a greater extent than with the equiv-
alent dose of the same mineral nutrient presented in ionic (salt) form (Alidoust and
Isoda 2013; Pradhan et  al. 2013; Zhao et  al. 2013; Kim et  al. 2014), and when
applied at the same concentration at relatively high doses, the concentration at
which toxicity occurs is lower with ions than with nanoparticles (Dimkpa et  al.
2012a; Pradhan et al. 2013; Kim et al. 2014). The enhanced beneficial effects of
nanoparticles are due likely to the fact that unlike ionic fertlizers where a significant
portion of the nutrients could be lost due to the formation of phosphate and carbon-
ate precipitates or other soil factors, exposure to nanoparticles is potentially con-
trolled by the sustained but low release of the functional ions from the particles
which serve as reservoirs of ions (Dimkpa et  al. 2012b), with plant-adequate
amounts then likely taken up to offset losses due to interaction of the released ions
with soil factors. Moreover, ions from the immediately soluble salts are readily
available to the roots and could rapidly reach undesirable doses, subject to interac-
tions with soil factors.
Corradini et al. (2010) evaluated the interaction and stability of chitosan nanopar-
ticles suspensions containing N, P, and K fertilizers which can be useful for agricul-
tural applications. Similarly, Kottegoda et  al. (2011) synthesized urea modified
hydroxyapatite-nanoparticles for gradual release of nitrogen with the crop growth.
276 S.K. Sanivada et al.

These nano-fertilizers showed initially burst and subsequently slow release of nitro-
gen up to 60 days of plant growth compared to commercial fertilizer which shows
release only up to 30 days. The large surface area of hydroxyapatite facilitates the
large amount of urea attachment on its surface. Strong interaction between
hydroxyapatite-­nanoparticles and urea contributes to the slow and controlled release
of urea. Similarly, polymer-based mesoporous nanoparticles can also provide effi-
cient carrier system to agrochemical compounds which improves the efficiency and
economical utilization.
Nanoparticles can possibly convey supplements to particular target destinations
in living frameworks. The stacking of supplements on the nanoparticles is normally
done by ingestion on nanoparticles, connection on nanoparticles interceded by
ligands, encapsulation in nano particulate polymeric shell, entrapment of polymeric
nanoparticles, and amalgamation of nanoparticles made out of the supplement itself
(Solanki et al. 2015). Nano-fertilizers can decisively discharge their dynamic ingre-
dients in reacting to ecological triggers and natural demands. Both in  vitro and
in  vivo strategies can be utilized for nanofertilizer conveyance to the plants.
Although, the uptake, translocation, and destiny of nanoparticles in plant frame-
work are to a great extent incomprehensible bringing about the ascent of different
moral and security issues encompassing the utilization of nano-fertilizers in plant
efficiency. An efficient and exhaustive quantitative investigation in regards to the
potential wellbeing ecological approval, and secured dumping of nanomaterials can
guide to upgrading in manipulating further uses of nano-fertilizers.

10.6  Nano-Fertilizers, Agricultural Productivity

and Greenhouse Gas Emissions

Among the advancements whose promoters case to raise farming harvest yields
while diminishing the ecological harm of horticultural undertaking, maybe no case
is more engaging than changing and lessening the utilization of concoction compost
inputs through nanotechnology. Greenhouse gas emissions and hypoxia are only
two of the negative ecological results of the huge utilization of chemical fertilizers
for chief commercial crops (Park et  al. 2012; PHYS.ORG 2015). For example,
United States has the third most elevated utilization of crop nutrients and is the
world second biggest shipper of crop nutrients. Nutrient utilization in 2013 was
11.9, 3.9 and 4.3 million metric tons for nitrogen, phosphate and potash separately.
In 2013, crop protection sales were $7.4 billion and seed deals were over $12.6 bil-
lion. The US has more than 382 million sections of land of arable area with 95 mil-
lion sections of land planted for corn producing 14.0 billion bushels in 2013 (Agrium
2015). Hypoxia is the investigative term for a “no man’s land” region in a waterway,
about denied of oxygen as the after effect of agrarian water overflow conveying
nitrates and phosphorus from fertilizer, e.g., the 6–7000 square mile no man’s land
in the Gulf of Mexico (NOAA 2015). Unduly idealistic assessments about the
10  Nanofertilizers for Sustainable Soil Management 277

versatility of agribusiness to environmental change, in light of 1990s presumptions

and information about farming alleviation potential, are quick offering route to a
much more tightly timetable for more noteworthy decreases in commercial agricul-
tural outflows (Hansen and Sato 2016). Total fertilizer nutrient (nitrogen, potash and
phosphate) utilization is projected at 183200000 tones in 2013 and is forecast to
reach 186,900,000 tones in 2014. With a consecutive growth of 1.8 percent per year,
it is likely to reach 200,500,000 tones by the end of 2018 (FAO 2015). If the busi-
ness prominence is right, the negative ecological results of fertilizers utilization will
probably amplify. To this amplification ought to be included the tremendous meth-
ane discharges from the water driven cracking strategies used to create the charac-
teristic gas needed for engineered nitrogen fertilizer fabrication (Mother Jones
2013).
Couldn’t the embodiment of engineered nanomaterials into synthetic fertilizers
in to hike of nitrogen use proficiency empower product yield increments of 70 per-
cent to “booster the world” of 2050 without further harming water quality and esca-
lation of green house gasses. Moreover, wouldn’t the nano-scaling or micron-scaling
of fertilizers and miniaturized scale nutrients empower a more practical utilization
of accessible fertilizer and other supplements, since a much little volume of fertil-
izer would deliver bigger yields? In reality, among the worldwide association pro-
moters of fast escalation in fertilizer use, nano-empowered fertilizers and the
nano-scaling of inputs may be viewed for expanding fertilizer deals and product
yields while securing or notwithstanding upgrading rural natural deposits. Among
the yield-related traits of nano-fertilizer guaranteed in patents are controlled supple-
ment discharge and raised water maintenance in soil (Liu and Lal 2015). (http://
www.fao.org/docrep/015/an177e/an177e00.pdf).

10.7  E
 ngineered Nanomaterials in Biosolids Used to Fertilize
Plant Growth

Some experimental examination into the engineered nanomaterials vicinity in agri-

cultural soil and plants expect that such vicinity is unavoidable. Along these lines, a
recent study states, “a huge fraction of engineered nanomaterials in consumer and
commercial items will accomplish natural environments” (Colman et al. 2013). The
fraction of that big portion which comes as silver (Ag) nano-particles in biosolids
will have experienced a procedure of sulfidation that “significantly modifies the
properties of Ag nano particles, including their surface charge, the capacity to dis-
charge Ag nano particles and toxicity” (Mitrano et al. 2015). In an article on the
mind boggling procedure needed to distinguish nano-zinc oxide and nano-cerium
dioxide (nano-cerium) particles in soybean which are fit for human consumption,
the scientists found that “With the amplified utilization of engineered nanomateri-
als, for example, ZnO and CeO2, these nanomaterials will definitely be discharged
into the earth with incomprehensible results” (Hernandez-Viezcas et al. 2013). The
278 S.K. Sanivada et al.

in all likelihood type of discharge would be zinc and cerium engineered nanomateri-
als in biosolids lawfully affirmed to field fertilization (FSC 2008). Chemicals in
pre-nano biosolids have been recognized as known or suspected. Cancer-causing
agents and hormonal endocrine disruptors, prompting bunch human health troubles
(Venkatesan and Halden 2015). The analysts note, such arrival of engineered nano-
materials “can make them go into food chain and the following plant era” (AZO
NANO 2015). Their tests discovered that just nano-cerium, utilized as a part of
interior ignition forms, sunscreens, gas sensors and nonessential creams, was distin-
guished in the edible plants (Schwabe et al. 2015). Carbon nanotubes could be in
biosolids, has numerous measurements, including the administrative practice that
permits the utilization of biosolids to agricultural soil as “protected.” Current risk
examination procedures would oblige convincing and disaggregated confirmation
to demonstrate that the lethality and introduction of soil microorganisms and micro-
fauna to engineered nanomaterials and nothing else in the biosolids was unsafe to
soil health and maybe to human health (Kwak and An 2015).
It is in no way, shape or form sure that setting up maximum residue levels for
fertilizer engineered nanomaterials to secure soil microorganisms and microfauna
are technically viable. However, preceding putting resources into the exploration
that would give hazard investigation confirmation to setting up such maximum resi-
due levels, it is reasonable to inquire about whether there are less costly and danger-
ous means than nano-empowered fertilizers to accomplish the specialized
destinations of yield improvement and lessened environment hazards from agricul-
tural yield. Testing the impacts of economically accessible engineered nanomateri-
als on a soil microorganism regarding plant development is essential.

10.8  E
 fficacy of Commercially-Available Engineered
Nanomaterials on a Soil Microbe

Engineered nanomaterials toxicity towards microorganisms has been demonstrated

in various in vitro examines yet, the evaluation of engineered nanomaterials eco-
logical effect is still in its initial stages. This amalgamation on the impacts of engi-
neered nanomaterials on soil microbial groups bolsters distinctive conclusions. It
has been shown utilizing diverse procedures, diverse markers, and common soils,
which engineered nanomaterials could have an effect on microbial exercises, pleni-
tudes and differences. Table 10.1 lists the studies on nanotoxicity of plants and soil
dwelling organisms. Researches on the effect of nanotoxicity on soil often used
natural or artificial soil, aqueous suspensions as media. Nanotoxicity studies on soil
have been conducted with various species and nanoparticles (Juganson et al. 2015).
On the other hand the toxic impacts of engineered nanomaterials on microbial group
are exceedingly reliant on both the engineered nanomaterials considered and the
soil properties (Terekhova and Gladkova 2013; Simon-Deckers et al. 2009; Jiang
et al. 2009).
Table 10.1  Toxicity of nano particles to soil: an overview
Nano Diameter Test duration
a
particles (nm) Test organism Test media (h or days) Test endpoint Outcomes References
Multiwall 40–70 Rice Rice germination buffer 2 weeks exposure to Effect on seed EC10 = 400 mg/L; Lin et al.
carbon nanoparticles in setting; decrease in EC11 = 400 mg/L; (2009)
nanotubes media and transfer to seed weight
soil containing no Translocation of NOEC = 800 mg/L
nanoparticles multiwall carbon
nanotubes to
stems and leaves
Double-­ 10–30 Eisenia veneta Loamy sand soil with a pH of 28 days Mortality NOEC = 495 mg/kg Scott-­
walled 5.5, total organic carbon 2.3%, Growth EC10 = 94 ± 45 mg/ Fordsmand
carbon clay 5%, silt 13%, sand 82% kg et al. (2008)
nanotubes and a C:N of 0.4% and 41.5%, EC50= > 500 mg/kg
respectively. The earthworms
Cocoon production EC10 = 37 ± 73 mg/
were fed with dried cow-dung,
kg;
pH of 8.5
EC50 = 176 ± 150
10  Nanofertilizers for Sustainable Soil Management

mg/kg
Hatchability EC10= > 500 mg/kg
C70 – Rice Rice germination buffer 2 weeks exposure to – C70 were easily Lin et al.
fullerene nanoparticles in translocated from (2009)
media and transfer to roots to leaves and
no nanoparticles rest of plant
containing soil
C60 11 Eisenia veneta Loamy sand soil with a pH of 28 days Survival NOEC = 1000 mg/ Scott-­
fullerene 5.5, total organic carbon 2.3%, kg Fordsmand
clay 5%, silt 13%, sand 82% Growth EC20 = 1000 mg/kg et al. (2008)
and a C:N of 0.4% and 41.5%, Cocoon production EC78 = 1000 mg/kg
respectively. Earthworms were
Hatchability NOEC = 1000 mg/
fed with dried cow-dung, pH of
kg
8.5
279

(continued)
Table 10.1 (continued)
280

Nano Diameter Test duration

a
particles (nm) Test organism Test media (h or days) Test endpoint Outcomes References
C60 – Lumbricus Clean soil with 4.3% organic 4 weeks Adult mortality NOEC = 154 mg/kg Van der
fullerene rubellus matter, moisture content of Ploeg et al.
17.2% and soil pH was 5.0 Adult growth NOEC = 154 mg/kg (2011)
Cocoon production EC40 = 154 mg/kg
326 days Offspring mortality EC40 = 154 mg/kg
Offspring growth NOEC = 154 mg/kg
C60 11 Eisenia fetida Artificial soil: 10% Sphagnum 28 days Mortality NOEC = 50,000 Li and
fullerene peat moss, 20% kaolin clay, mg/kg Alvarez
and 70% quartz sand. pH in the Growth NOEC = 50,000 (2011)
range of 6.5–7.5 mg/kg
Cocoon production NOEC = 10,000
mg/kg
EC60 = 50,000 mg/kg
Zinc 10–20 Eisenia fetida Artificial soil (10% finely 7 days Mortality NOEC = 5 g/kg Hu et al.
oxide ground sphagnum peat, 20% (2010)
kaolin clay, 70% industrial
sand, pH was adjusted to 6.0 ±
0.5 by adding calcium
carbonate), water content 35%
(w/w)
Zinc < 100 Lepidium Standard artificial soil 72 h Seed germination NOEC = 230 mg Manzo et al.
oxide sativum (sphagnum peat 10%, kaolin Zn/kg (2011)
clay 20%, quartz sand 70%) Root elongation EC25 = 230 mg Zn/
kg
Zinc < 100 Vicia faba Standard artificial soil 96 h Micronucleus 5.2 micronuclei Manzo et al.
oxide (sphagnum peat 10%, kaolin frequency 1000/cell = 230 mg (2011)
clay 20%, quartz sand 70%) Zn/kg
S.K. Sanivada et al.
Nano Diameter Test duration
a
particles (nm) Test organism Test media (h or days) Test endpoint Outcomes References
Zinc < 100 Heterocypris Standard artificial soil 6 days Mortality EC100 = 230 mg Manzo et al.
oxide incongruens (sphagnum peat 10%, kaolin Zn/kg (2011)
clay 20%, quartz sand 70%)
Zinc < 100 Folsomia Standard artificial soil 28 days Reproduction test NOEC = 230 mg Manzo et al.
oxide candida (sphagnum peat 10%, kaolin Zn/kg (2011)
clay 20%, quartz sand 70%) Avoidance test EC16 = 230 mg Zn/
kg
Zinc 40–100 Eisenia fetida Artificial soil (10% sphagnum 4 weeks Reproductive EC33 = 100 mg/kg Canas et al.
oxide peat, 20% kaolin clay, 69% fine toxicity, cocoon (2011)
sand, 1% finely ground cow production
manure) and 2% cow manure, Reproductive EC100 = 1000 mg/
soil moisture 35% (w/w) toxicity, cocoon kg
production
Zinc 20 Soil bacteria Mineral pasture soil (Typic 2h Growth inhibition EC50 = 64 mmol/g Rousk et al.
oxide Dystrochrept, organic-C = 40 (2012)
mg/g, total-N = 3.3 mg/g, pH
(H2O) = 5.0.
10  Nanofertilizers for Sustainable Soil Management

Zinc 20 Soil bacteria Organic pasutre soil (Typic 2h Growth inhibition EC50 = 185 m Rousk et al.
oxide Fragiochrept, organic-C = mol/g (2012)
154 mg g21, total-N = 9.3 mg
g21, pH(H2O) = 6.6)
Zinc <50 Fagopyrum Microcosm (aged natural soil 2 weeks and 5 days seedling growth EC24 = 1000 mg/kg Lee et al.
oxide esculentum with actice soil bacteria) reduction (2012)
Zinc <50 Fagopyrum Natural soil without active soil 2 weeks and 5 days seedling growth EC31.5 = 1000 mg/ Lee et al.
oxide esculentum bacteria reduction kg (2012)
Zinc 30 Folsomia Loamy sand soil (LUFA- 4 weeks survival NOEC = 6400 mg Waalewijn-­
oxide candida Speyer 2.2, Sp 2121, Germany, Zn/kg Kool et al.
2009), pH 5.5 (2012)
(continued)
281
Table 10.1 (continued)
282

Nano Diameter Test duration

a
particles (nm) Test organism Test media (h or days) Test endpoint Outcomes References
Zinc 30 Folsomia Loamy sand soil (LUFA- 4 weeks reduction of EC10 = 2559 Waalewijn-­
oxide candida Speyer 2.2, Sp 2121, Germany, reproduction (133–5502) mg Zn/ Kool et al.
2009), pH 5.5, ZnO added as a kg (2012)
dry powder EC50 = 3159
(126–5502) mg Zn/kg
Zinc 30 Folsomia Loamy sand soil (LUFA- 4 weeks reduction of EC50 = 3593 Waalewijn-­
oxide candida Speyer 2.2, Sp 2121, Germany, reproduction (122–5684) mg Zn/ Kool et al.
2009), pH 5.5, ZnO added as a kg (2012)
suspension
Zinc <100 Lepidium Hydrated standard OECD soil 3 days Root growth NOEC = 10 mg/kg Josko and
oxide sativum (MicroBioTests Inc., inhibition EC7 = 100 mg/kg Oleszczuk
Mariakerke, Belgium): 70% EC37 = 1000 mg/kg (2014)
fine quartz sand (50% particles,
NOEC = 100 mg/kg
0.05–0.2 mm), 20% kaolin clay
(kaolinite content preferably EC55 = 1000 mg/kg
above 30%) and finely ground
Sphagnum peat; filter paper
Zinc 58.40 ± Eisenia fetida Soil from an untreated 28 days Survival NOEC = 1000 mg/ García-
oxide 30.13 grassland area located 10 km kg Gómez et al.
northeast of Madrid: pH 7.8, (2014)
Sand (%) 73.4, Silt (%) 18.8,
Clay (%) 7.8, EC (μS/cm) 390,
Oxidizable organic C (%) 1.9,
Cd (mg/kg) 0.2, Cu (mg/kg) 27,
Pb (mg/kg) 31, Zn (mg/kg) 53
S.K. Sanivada et al.
Nano Diameter Test duration
a
particles (nm) Test organism Test media (h or days) Test endpoint Outcomes References
Zinc 58.40 ± Eisenia fetida Sewage sludge treated soil: pH 28 days Survival NOEC = 1000 mg/ García-
oxide 30.13 7.8, EC (μS/cm) 2550, Organic kg Gómez et al.
matter (%) 59.80, Oxidizable (2014)
organic C (%) 31.21, Total P
(%) 7.34, Total K (%) 0.66,
Total N (%) 3.61, N-NH3 (mg/
kg) 0.61, Cd (mg/kg) 3, Cu
(mg/kg) 469, Pb (mg/kg) 82,
Zn (mg/kg) 1288
Zinc 58.40 ± Eisenia fetida Sewage sludge treated soil: pH 28 days Survival NOEC = 1000 mg/ García-
oxide 30.13 7.0, EC (μS/cm) 1669, Organic kg Gómez et al.
matter (%) 28.29, Oxidizable (2014)
organic C (%) 20.32, Total P
(%) 1.02 Total K (%) 1.13,
Total N (%) 3.09, N-NH3 (mg/
kg) 0.57, Cd (mg/kg) 5, Cu
(mg/kg) 384 Pb (mg/kg) 108,
Zn (mg/kg) 868
10  Nanofertilizers for Sustainable Soil Management

Cerium 15 Caenorhabditis K-medium (0.032M KCl, 24 h Growth inhibition NOEC = 1 mg/L Roh et al.
oxide elegans Bristol 0.051M NaCl) Fertility inhibition EC28 = 1 mg/L (2009)
strain N2 Mortality LC20 = ± 141 mg/L
Cerium 45 Caenorhabditis K-medium (0.032 M KCl, 24 h Growth inhibition NOEC = 1 mg/L Roh et al.
oxide elegans Bristol 0.051 M NaCl) Fertility inhibition EC11 = 1 mg/L (2009)
strain N2 Mortality NOEC = 1 mg/L
Silver 81.8 ± 1.59 Eisenia fetida Sandy loam soils with a pH of 28 days Mortality LC2.5 ± 2.5 = 1000 Heckmann
5.8, total organic carbon mg/kg et al. (2011)
1.36%, clay 11.6%, silt 21.4%, Cocoon production EC100 = 1000 mg/
and sand 64.7%. The worms inhibition kg
were fed weekly with 5 g dried
cow-dung, pH of 8.5, from
non-medicated animals.
283

(continued)
Table 10.1 (continued)
284

Nano Diameter Test duration

a
particles (nm) Test organism Test media (h or days) Test endpoint Outcomes References
Silver 0.6–2 Flax (Linum Aqueous suspensions with 5 days Seed germination NOEC = 20 mg/L El-Temsah
usitatissimum 0.1% (v/v) of the surfactant Shoot length of LOEC = 10 mg/L and Joner
L.,cv. Electra) Tween 20 germinating seeds (2012)
Silver 0.6–2 Ryegrass Aqueous suspensions with 5 days Seed germination EC20 = 10 mg/L El-Temsah
(Lolium 0.1% (v/v) of the surfactant EC50 = 20 mg/L and Joner
perenne L., cv. Tween 20 Shoot length of LOEC = 10 mg/L (2012)
Tove) germinating seeds
Silver 0.6–2 Two-rowed Aqueous suspensions with 5 days Seed germination NOEC = 20 mg/L El-Temsah
barley 0.1% (v/v) of the surfactant Shoot length of LOEC = 20 mg/L and Joner
(Hordeum Tween 20 germinating seeds (2012)
vulgare L., cv.
Annabell)
Silver 20 ± 2.5 Flax (Linum Aqueous suspensions with 5 days Seed germination NOEC = 100 mg/L El-Temsah
usitatissimum 0.1% (v/v) of the surfactant Shoot length of LOEC = 20 mg/L and Joner
L., cv. Electra) Tween 20 germinating seeds (2012)
Silver 20 ± 2.5 Ryegrass Aqueous suspensions with 5 days Seed germination NOEC = 100 mg/L El-Temsah
(Lolium 0.1% (v/v) of the surfactant Shoot length of LOEC = 20 mg/L and Joner
perenne L., cv. Tween 20 germinating seeds (2012)
Tove)
Silver 20 ± 2.5 Two-rowed Aqueous suspensions with 5 days Seed germination EC10 = 10 mg/L El-Temsah
barley 0.1% (v/v) of the surfactant EC20 = 20 mg/L and Joner
(Hordeum Tween 20 EC20 = 100 mg/L (2012)
vulgare L., cv.
Shoot length of LOEC = 10 mg/L
Annabell)
germinating seeds
S.K. Sanivada et al.
Nano Diameter Test duration
a
particles (nm) Test organism Test media (h or days) Test endpoint Outcomes References
Silver 5 Flax (Linum Aqueous suspensions with 5 days Seed germination NOEC = 100 mg/L El-Temsah
usitatissimum 0.1% (v/v) of the surfactant Shoot length of LOEC = 10 mg/L and Joner
L., cv. Electra) Tween 20 germinating seeds (2012)
Silver 5 Ryegrass Aqueous suspensions with 5 days Seed germination NOEC = 100 mg/L El-Temsah
(Lolium 0.1% (v/v) of the surfactant Shoot length of LOEC = 10 mg/L and Joner
perenne L., cv. Tween 20 germinating seeds (2012)
Tove)
Silver 5 Two-rowed Aqueous suspensions with 5 days Seed germination EC10 = 10 mg/L El-Temsah
barley 0.1% (v/v) of the surfactant EC20 = 20 mg/L and Joner
(Hordeum Tween 20 EC20 = 100 mg/L (2012)
vulgare L., cv.
Shoot length of LOEC = 10 mg/L
Annabell)
germinating seeds
Silver < 100 Tomato Deionized water 3–5 days Germination % EC25 = 10 mg/L Ravindran
(Lycopersicum EC40 = 15 mg/L et al. (2012)
esculentum)
Silver 10 Eisenia fetida Artificial soil, 10% dried dairy 14 days Mortality NOEC = 500 mg/kg Hu et al.
10  Nanofertilizers for Sustainable Soil Management

80 manure, 20% kaolin clay, and (2012)

70% industrial sand, pH 6,
water content 35%
Silver 10 Pseudomonas 10 mL white silica sand 4 days Mortality (cfu/g on LOEC = 1 mg/L Calder et al.
chlororaphis autoclaved twice for 40 min, 3 LB plates without LC100 = 3 mg/L (2012)
O6 mL bacterial suspension, NaCl) NOEC = 3 mg/L
specific conductance 28 μS/cm,
4.0 mg/L Na, DOC <0.1%, pH
7.92
Silver 10 Pseudomonas 7 mL of white silica sand 4 days Mortality (cfu/g on LOEC = 1 mg/L Calder et al.
chlororaphis (UNIMIN Corp., ID, USA), LB plates without LC100 = 3 mg/L (2012)
O6 autoclaved twice for 40 min NaCl) LOEC = 1 mg/L
and 3 mL of kaolinite, 3 mL
LC100 = 3 mg/L
bacterial suspension
(continued)
285
Table 10.1 (continued)
286

Nano Diameter Test duration

a
particles (nm) Test organism Test media (h or days) Test endpoint Outcomes References
Silver 10 Pseudomonas 10 mL white silica sand 4 days Mortality (cfu/g on NOEC = 1 mg/L Calder et al.
chlororaphis (UNIMIN Corp., ID, USA), LB plates without LOEC = 3 mg/L (2012)
O6 autoclaved twice for 40 min, 3 NaCl) LOEC = 1 mg/L
mL bacterial suspension, 1 mL
undiluted pore water
Silver 15 (size Eisenia andrei 625 g RefeSol 01A,a loamy, 56 days Mortality NOEC = 200 mg/kg Schlich et al.
distribution medium-­acidic, and lightly Number of NOEC = 15 mg/kg (2013)
99%) humic sand (pH 5.67; Corg juveniles LOEC = 30 mg/kg
0.93%, sand 71%, silt 24%,
EC50 = 83.0–146.0
clay 5%), 55% WHC(max) 40
mg/kg
g cow dung (air dried, ground,
and moistened before
application)
Silver <100, Caenorhabditis k-media (0.032 M KCl, 24 h Mortality NOEC = 0.5 mg/L Roh et al.
mainly 20 elegans 0.051 M NaCl) Growth inhibition NOEC = 0.5 mg/L (2009)
72 h Reproduction EC20 = 0.05 mg/L
EC70 = 0.1 mg/L
Silver <100, Caenorhabditis k-media (0.032 M KCl, 24 h Mortality NOEC = 0.5 mg/L Roh et al.
mainly 20 elegans mtl-2 0.051 M NaCl) Growth inhibition NOEC = 0.5 mg/L (2009)
mutant 72 h Reproduction EC20 = 0.1 mg/L
EC60 = 0.5 mg/L
S.K. Sanivada et al.
Nano Diameter Test duration
a
particles (nm) Test organism Test media (h or days) Test endpoint Outcomes References
Silver <100, Caenorhabditis k-media (0.032 M KCl, 24 h Mortality NOEC = 0.5 mg/L Roh et al.
mainly 20 elegans sod-3 0.051 M NaCl) Growth inhibition NOEC = 0.5 mg/L (2009)
mutant 72 h Reproduction NOEC = 0.05 mg/L
EC10 = 0.1 mg/L
EC60 = 0.5 mg/L
Silver <100, Caenorhabditis k-media (0.032 M KCl, 24 h Mortality NOEC = 0.5 mg/L Roh et al.
mainly 20 elegans daf-12 0.051 M NaCl) Growth inhibition NOEC = 0.5 mg/L (2009)
mutant 72 h Reproduction EC45 = 0.05 mg/L
EC65 = 0.1 mg/L
EC75 = 0.5 mg/L
Silver 20.2 ± 2.5 Lumbricus 1 kg agricultural soil, 75% of 8 weeks Mortality NOEC = 100 mg/kg Lapied et al.
terrestris water holding capacity; 15 g of of dry feed (2010)
dried, ground horse manure 4 weeks Mortality NOEC = 100 mg/kg
moistened with 15 ml of the
nanoparticle suspensions
Silver 8.8; 45% Lumbricus 1 kg agricultural soil, 75% of 8 weeks Mortality NOEC = 20 mg/kg Lapied et al.
10  Nanofertilizers for Sustainable Soil Management

<2 terrestris water holding capacity; 15 g of of dry feed (2010)

dried, ground horse manure 4 weeks Mortality NOEC = 8 mg/kg
moistened with 15 ml of the
nanoparticle suspensions
Silver 20 Soil microbial Granitic, sandy and peaty soils, 176 days Microbial MCT25 2.46 on a Kumar et al.
community Al (11 g/kg), Ca (3.5 g/kg), Fe community scale of 3 at 0.066% (2011)
(21 g/kg), K (0.9 g/kg) and Mg toxicity (MCT25) (w/w; 660 mg/kg)
(5 g/kg), organic carbon (18.8
g/kg), inorganic (3 × 10–3 g/
kg), pH 5.6
(continued)
287
Table 10.1 (continued)
288

Nano Diameter Test duration

a
particles (nm) Test organism Test media (h or days) Test endpoint Outcomes References
Silver 15 Arthrobacter 0.6 g RefeSol 01-A field soil, a 3h Dehydrogenase EC50 = 34.16 Engelke et al.
globiformis dystric cambisol from arable activity (30.24–38.24) mg (2014)
land, loamy, medium acid, and Ag/kg
very light humic sand (pH 5.67,
organic carbon 0.93%, sand
71%, silt 24%, clay 5%); 600
μL deionized sterile water, 400
μL bacterial inoculum in 1:3
dilution of frowth medium
Silver 3–8 Folsomia Loamy sand soil with a pH 28 days Mortality NOEC = 673 mg Waalewijn-­
candida CaCl2 of 5.5, a total organic Ag/kg Kool et al.
carbon content of 2.09%, a Reproduction NOEC = 673 mg (2014)
cation exchange capacity of Ag/kg
10.0 meq/100 g and a
water-holding capacity of
46.5%
Titanium 32 Eisenia fetida Artificial soil (10% sphagnum 14 days Mortality NOEC = 10,000 Canas et al.
oxide peat, 20% kaolin clay, 69% fine mg/L (2011)
sand, 1% finely ground cow
manure) and 2% cow manure,
soil moisture 35% (w/w)
Titanium 21 Cyprinus Dechlorinated tap water, the 25 days Mortality NOEC = 10 mg/L Sun et al.
oxide carpio fish were fed with a (2014)
commercial food once a day
during the experiment.
Titanium 5 Eisenia fetida Artificial soil was composed of 28 days Survival NOEC = 10,000 McShane
oxide 70% silica sand (90% particles mg/kg et al. (2012)
having a diameter of less than Reproduction NOEC = 10,000
40 mm), 20% kaolin clay, and cocoon production mg/kg
S.K. Sanivada et al.

10% peat sieved to 2 mm, and Reproduction NOEC = 10,000

had a water content of 54% hatching rate mg/kg
Nano Diameter Test duration
a
particles (nm) Test organism Test media (h or days) Test endpoint Outcomes References
Titanium 21 Eisenia fetida Artificial soil was composed of 28 days Reproduction NOEC = 10,000 McShane
oxide 70% silica sand (90% particles cocoon production mg/kg et al. (2012)
having a diameter of less than Reproduction NOEC = 10,000
40 mm), 20% kaolin clay, and hatching rate mg/kg
10% peat sieved to 2 mm, and
had a water content of 54%
Titanium 5 Eisenia andrei Artificial soil was composed of 28 days Reproduction NOEC = 10,000 McShane
oxide 70% silica sand (90% particles cocoon production mg/kg et al. (2012)
having a diameter of less than Reproduction NOEC = 10,000
40 mm), 20% kaolin clay, and hatching rate mg/kg
10% peat sieved to 2 mm, and
had a water content of 54%
Titanium 21 Eisenia andrei Artificial soil was composed of 28 days Reproduction NOEC = 10,000 McShane
oxide 70% silica sand (90% particles cocoon production mg/kg et al. (2012)
having a diameter of less than Reproduction NOEC = 10,000
40 mm), 20% kaolin clay, and hatching rate mg/kg
10% peat sieved to 2 mm, and
had a water content of 54%
10  Nanofertilizers for Sustainable Soil Management

Titanium 5 Eisenia andrei Artificial soil was composed of 48 h Avoidance EC48 ± 23 = 10,000 McShane
oxide 70% silica sand (90% particles mg/L et al. (2012)
having a diameter of less than
40 mm), 20% kaolin clay, and
10% peat sieved to 2 mm, and
had a water content of 54%
(continued)
289
Table 10.1 (continued)
290

Nano Diameter Test duration

a
particles (nm) Test organism Test media (h or days) Test endpoint Outcomes References
Titanium 10 Eisenia andrei Artificial soil was composed of 48 h Avoidance EC24 ± 33 = 10,000 McShane
oxide 70% silica sand (90% particles mg/L et al. (2012)
having a diameter of less than
40 mm), 20% kaolin clay, and
10% peat sieved to 2 mm, and
had a water content of 54%
Titanium 21 Eisenia andrei Artificial soil was composed of 48 h Avoidance EC37 ± 15 = 10,000 McShane
oxide 70% silica sand (90% particles mg/L et al. (2012)
having a diameter of less than
40 mm), 20% kaolin clay, and
10% peat sieved to 2 mm, and
had a water content of 54%
Titanium – Soil bacteria 10 M sterile Bis-tris (2-(bis(2-­ 7 days Mortality EC50= > 100 mg/L Velzeboer
oxide hydroxyethyl)amino)-2- et al. (2008)
(hydroxymethyl)
propane-1,3-diol
Titanium 7 Caenorhabditis K-medium (0.032 M KCl, 24 h Growth inhibition EC9 = 1 mg/L Roh et al.
oxide elegans Bristol 0.051 M NaCl) Fertility inhibition EC21 = 1 mg/L (2009)
strain N2 Mortality LC30 ± 1.4 = 1
mg/L
Titanium 20 Caenorhabditis K-medium (0.032 M KCl, 24 h Growth inhibition NOEC = 1 mg/L Roh et al.
oxide elegans Bristol 0.051 M NaCl) Fertility inhibition NOEC = 1 mg/L (2009)
strain N2 Mortality LC10 = 1 mg/L
S.K. Sanivada et al.
Nano Diameter Test duration
a
particles (nm) Test organism Test media (h or days) Test endpoint Outcomes References
Titanium 30 ± 0.61 Eisenia fetida Sandy loam soil with a pH of 28 days Mortality LC2.5 ± 2.5 = 1000 Heckmann
oxide 5.8, total organic carbon mg/kg et al. (2011)
1.36%, clay 11.6%, silt 21.4%, Cocoon production EC19.3 ± 7.3 =
and sand 64.7%; The worms inhibition 1000 mg/kg
were fed weekly with 5 g dried Cocoon hatchability EC25.4 ± 5.7 = 1000
cow-dung, pH of 8.5, from
Juvenile production mg/kg
non-medicated animals.
EC49.3 ± 7.7 = 1000
mg/kg
Titanium <21 Lepidium Hydrated standard OECD soil 3 days Root growth EC23.9 = 100 mg/L Josko and
oxide sativum 70%fine quartz sand (50% inhibition Oleszczuk
particles, 0.05–0.2 mm), 20% (2014)
kaolin clay (kaolinite content
preferably above 30%) and
finely ground Sphagnum peat
Titanium <100 Vibrio fischeri Standard artificial OECD soil: 5 min Luminiescence EC20 = 28,110 Pereira et al.
oxide sand, kaolin clay and sphagnum inhibition mg/L (2011)
peat (4 mm sieved) in a 7:2:1
10  Nanofertilizers for Sustainable Soil Management

EC50 = 63,500 mg/L

mass proportion, pH to 6.0 ± EC50 = 66,820 mg/L
0.5, with calcium carbonate,
sample collected 2 h after
spiking
Titanium <100 Vibrio fischeri Standard artificial OECD soil: 15 min Luminiescence EC20 = 12,930 Pereira et al.
oxide sand, kaolin clay and sphagnum inhibition mg/L (2011)
peat (4 mm sieved) in a 7:2:1 EC20 = 17,580 mg/L
mass proportion, pH to 6.0 ± EC50 = 48,040 mg/L
0.5, with calcium carbonate,
EC20 = 9697 mg/L
sample collected 30 days after
spiking EC50 = 36,060 mg/L
(continued)
291
Table 10.1 (continued)
292

Nano Diameter Test duration

a
particles (nm) Test organism Test media (h or days) Test endpoint Outcomes References
Titanium <100 Vibrio fischeri Standard artificial OECD soil: 30 min Luminiescence EC20 = 37,150 Pereira et al.
oxide sand, kaolin clay and sphagnum inhibition mg/L (2011)
peat (4 mm sieved) in a 7:2:1 EC50 = 57,000 mg/L
mass proportion, pH to 6.0 ± EC20 = 11,110 mg/L
0.5, with calcium carbonate,
EC50 = 37,660 mg/L
sample collected 2 h after
spiking
Cupric 40–80 Soil bacteria Mineral pasture soil moisture 2h Growth inhibition EC50 = 35 mmol/g Rousk et al.
oxide content of 40% of water LOEC = 200 (2012)
holding capacity mmol/g
Organic pasutre soil, moisutre
content of 60% of water
holding capacity
a
Outcomes EC Effective Concentration, NOEC No Observed Effect Concentration,Outcomes: EC Effective Concentration, LC Lethal Concentration, NOEC No
Observed Effect Concentration, Outcomes: EC Effective Concentration, LOEC Lowest Observed Effect Concentration, NOEC No Observed Effect Concentration,
Outcomes: EC Effective Concentration, LC Lethal Concentration, LOEC Lowest Observed Effect Concentration, NOEC No Observed Effect Concentration,
Outcomes: EC Effective Concentration, NOEC No Observed Effect Concentration, Outcomes: NOEC No Observed Effect Concentration, Outcomes: EC Effective
Concentration, LC Lethal Concentration, Outcomes: EC Effective Concentration, LC Lethal Concentration, NOEC No Observed Effect Concentration, Outcomes:
EC Effective Concentration, LC Lethal Concentration, LOEC Lowest Observed Effect Concentration, NOEC No Observed Effect Concentration
S.K. Sanivada et al.
10  Nanofertilizers for Sustainable Soil Management 293

However, inorganic nanoparticles (metal, metal oxide engineered nanomaterials)

may have a more prominent hazardous potential than natural ones (fullerenes and
carbon nanotubes) to soil microorganisms. An exemption could be the iron oxide
magnetic nano particles, which show restricted negative consequences for microbial
groups notwithstanding when high concentrations were applied. Alarmingly, the
utilization of nano zero valent iron could have negative impacts on biodegradative
elements of microorganisms in a soil remediation frame work. Further research is
expected to focus the genuine effectiveness of nano zero valent iron action in soil
and their potential outcomes on soil working utilizing action and utilitarian quality
estimations. The soil properties appear to assume a key part for the bioavailability
of engineered nanomaterials, particularly the mud and natural matter content. We
unequivocally urge to mull over more the physicochemical qualities of the soil uti-
lized as a part of the tests and to analyze the ecotoxicity of engineered nanomateri-
als in a scope of diverse soils. The distinguishing proof of soil parameters controlling
the bioavailability of engineered nanomaterials is essential for a superior ecological
risk evaluation (Cornelis et al. 2014).
It ought to be noticed that the impacts of various engineered nanomaterials have
not been researched yet or just in a solitary study. Though lot of engineered nano-
materials are vulnerable to be discharged to soils (Keller et al. 2013). Some engi-
neered nanomaterials have been more considered than others (Ag, TiO2, ZnO) and
incomprehensibly, these are not so much the most manufactured and utilized engi-
neered nanomaterials. The general number of distributions on every class of engi-
neered nanomaterials stays still restricted to date and in this way, it is still hard to
sum up the outcomes. These tests surveyed the transient affectability of microbial
groups, yet to date, no information are accessible neither on the long haul impact
and the enduring toxicity of engineered nanomaterials nor on the capacity of micro-
organisms to be versatile to engineered nanomaterials unsettling influence after
some time. The determinations that the researchers make from their investigations
recommend that applying engineered nanomaterials deliberately or by chance to
soil organism groups is impossible with any meticulousness, regardless of the fact
that soil testing yields dependable and precise data about the soil microorganisms
that colonize soil categories. For an innovation appraisal about the utilization of
engineered nanomaterials in soil, a couple questions about the “great variability” of
each engineered nanomaterial measurement and every soil microorganism reaction
can be raise (Simonin and Richaume 2015).

10.9  Nanotechnology Regulation: A Non–linear Process

In spite of the technical reservations and the intense unpredictability of engineered

nanomaterial dose-effect in soils, globally efforts are in progress to move forward
engineered nanomaterials into the fields from laboratory. International Food Policy
Research Institute (IFPRI) survey, recommended that development of nanotechnol-
ogy should give high priority, as applications of nanotechnology are promising
294 S.K. Sanivada et al.

sustainable development of poor people in developing countries around the world

(IFPRI 2011). Nanotechnology can play an important role in meeting challenges
that hamper the progress of poor countries, especially in relation to health and
hygiene, food security, and the environment (Ravichandran 2010; Lavicoli et  al.
2014).
On the other hand, an official means for transfer of technology was needed that
reduce the sky-scraping costs and royalty expenses for these intensively patented
technologies to accomplish developing countries at a reasonable price. There is a
vital requirement for technology assessment prior to technology transfer, despite of
the political languish of technology transfer to developing countries. Technology
assessment which allow estimation of the social, legal, environmental, economic
and safety costs of funds in new technologies by U.N. Office was projected by the
Action Group on Erosion, Technology and Concentration (ETC) Group which is an
international non-profit civil society association among non-governmental organi-
zations researching nanotechnologies and new promising technologies (ETC 2012).
At this point, quite a few of questions recommended for a critical assessment of
technology have pointed to authorized establishment for the regulation of engi-
neered nanomaterials in soil additives (Box 10.2). But technology assessment will
not necessitate having as its function of regulation of nanotechnology goods, if the
outcome of assessments found an engineered nanomaterial or its product is too risky
or even technically tricky to control, mainly within the financial limits of an anti-­
regulatory political background. For instance, the use of biosolids as fertilizers in
the production of crops in accordance with existing guidelines and regulations in
US with greater or fewer limitations. If the biosolids are proved to be fastening with
carbon nanotubes and nanometal oxides, a technology assessment of engineered
nanomaterials in biosolids might show that the benefits of a less costly fertilizer for
farmers would be compensated by the loss of fertility, due to loss of advantageous
soil microbes and microfauna. (http://www.wef.org/Biosolids/page.aspx?id =
7542). In this case, for regulation to avoid embodiment of engineered nanomaterials
in biosolids may be made more efficaciously in the engineered nanomaterial manu-
facturing and waste control process, if the commercial value for biosolids subsided
as a result of the loss of soil fertility. Then again and furthermore, an innovation
evaluation can contrast nano-empowered soil added substances and natural soil
building strategies, both as far as hazards and advantages, and also costs. Up to this
point, the nanotechnology business has opposed compulsory regulation as well as
even the willful accommodation of information on engineered nanomaterial use in
their items.
Regulation starts with information of fabricated products and experimental
study. As of recently, organizations around the world have not commanded to engi-
neered nanomaterial fabricating organizations to record such realities of their
research examinations. On the other hand, the U.S. Food and Drug Administration
(FDA) have prompted industry that the organization would be unrealistic to con-
sider nano-scale nourishment fixings to be generally recognized as safe. Only in
light of the fact that the large scale partners of those fixings had been assigned gen-
erally recognized as safe. Attempts to inspire intentional collaboration through the
10  Nanofertilizers for Sustainable Soil Management 295

EPA’s Nanoscale Materials Stewardship Program, have met with little achievement
(Nanowerk 2012).
So for instance, as indicated by a U.S.  General Accountability Office (GAO)
report, “Environment protection agency evaluated that organizations gave data on
just around 10 percent of the nanomaterials that are liable to be financially accessi-
ble. Moreover, environment protection agency reported that its survey of informa-
tion submitted through the system uncovered occasions in which the points of
interest of the assembling, handling, and utilization of the nanomaterials, and also
information regarding exposure and toxicology, were not present.” However, some
researchers were apprehensive enough to perform laboratory tests regarding gradual
accumulation of already commercialized engineered nanomaterials in soil. The out-
come of those tests must elevate queries by civic body along with the policymakers
concerning in case of soil health and everything that bank on it can be continued
without regulation. Regulation entails not just political spirit but enough funds for
research into the effects of engineered nanomaterials on human health and the envi-
ronment. The research communities concerned with engineered nanomaterials in
agricultural soil and plants are just beginning this vital task to a certain extent.

10.10  Nanofertilizers Applications

Increasing fertilizer use efficiency is the end result of the interplay among agro
technological adjustment of the use of current fertilizers, ecological literacy, the
socio-economic realities of farmers and an improved scientific knowledge base. In
the latter case, the continuous, even if fragmented wealth of knowledge being gained
from (i) edaphic and soil ecological processes such as interactions among nutrients,
(ii) interaction between plants-microorganisms, and between nutrients -soil/water
that determine nutrient solubility and availability, (iii) alternative nutrient uptake
forms (nano) and (iv) alternative routes of plant nutrients uptake and delivery can
and should be leveraged to develop integrated fertilizer strategies that better address
a plant’s need (Bindraban et al. 2015).
While some new strategies may entail adjustments of farm practices, fertilizer
products could easily be integrated in current practices, while new approaches
might even reduce input costs and increase farm produce and income. Fertigation,
the delivery of nutrients through irrigation, is one such strategy that can be inte-
grated into fertilizer regimes, tuned to appropriate application rates and crop
demand, to potentially improving nutrient uptake efficiency (Yasuor et al. 2013).
Nano fertilizers could be used to reduce nitrogen loss due to leaching, emissions,
and long-term incorporation by soil microorganisms. They could allow selective
release linked to time or environmental condition. Slow controlled release fertilizers
may also improve soil by decreasing toxic effects associated with fertilizer over-
application (Suman et al. 2010).
The potential uses and benefits of nanotechnology are enormous. These include
agricultural productivity enhancement involving nanoporous zeolites for slow
296 S.K. Sanivada et al.

release and efficient dosage of water and fertilizer, nano capsules for herbicide
delivery and vector and pest management and nano sensors for pest detection
(Scrinis and Lyons 2007). New research also aims to make plants use water, pesti-
cides and fertilizers more efficiently, to reduce pollution and to make agriculture
more environmental friendly (Suman et al. 2010). The open door for utilization of
nanotechnology in horticulture is colossal. On the other hand, as customary cultivat-
ing practices turn out to be progressively insufficient, and needs have surpassed the
conveying limit of the physical biological system, we have little choice however to
investigate nanotechnology in all areas of farming. It is very much perceived that
reception of new innovation is essential in gathering of national prosperity.

10.11  Future of the Nanofertilizer Market Sector

It has been assessed that around 40–70% of nitrogen, 80–90% of phosphorus, and
50–90% of potassium substance of functional fertilizers are lost in the atmosphere
and couldn’t achieve the plant which causes feasible and financial losses (Ombodi
and Saigusa 2000). These issues have started rehashed utilization of fertilizer and
pesticide which antagonistically influences the natural nutrient equalization of the
soil. As per  an evaluation by International Fertilizer Industry Association, world
compost utilization sharply bounced back in 2009–2010 and 2010–2011 with devel-
opment rates of 5–6% in both crusades. World interest is anticipated to achieve
192.8 metric tons by 2016–2017 (Heffer and Prud’homme 2012). However, the
huge scale utilization of chemicals as fertilizers and pesticides has brought about
ecological contamination influencing typical vegetation.
Nanotechnology has provided the feasibility of exploring nanoscale or nano-
structured materials as fertilizer carrier or controlled-release vectors for building of
the so-called smart fertilizers as new facilities to enhance the nutrient use efficiency
and reduce the cost of environmental pollution (Chinnamuthu and Boopati 2009).
The popularity of the topic recently extended to major scientific meetings targeting
various scientific communities. The trend is expected to continue, as the topic has
recently been integrated as a research priority by various regulatory bodies and
research funding agencies (Kah 2015). Different types of existing fertilizers for dif-
ferent crop problems are:
Nitrogen Fertilizers  The element required in abundant, nitrogen (N), is essential
for plant growth and animal nutrition and is the nutrient taken up in largest amount
by all plants. There was an attempt to increase the uptake of nitrogen with the appli-
cation of 25  kg Mg Oha-1 which increased the positive uptake (El-bendary and
El-Helaly 2013).
Potash Fertilizers  Plants absorb potash in its ionic form K+. For the controlled
release of potash fertilizer, polyacrylamide supported covering of pellets were used.
Potash and clay was assorted mutually and desiccated for an hour, this was layered
10  Nanofertilizers for Sustainable Soil Management 297

with a tooth paste for suitable accessory of the polymer and this polymer was dipped
in polyacrylamide polymer. The research found the dissimilarity of dissolution with
and without the coating, after the potash used is fewer the release is also deliberate
down and the release can also be sustained with less water (Subbarao et al. 2013).
Nano Porous Zeolite  They typically aid in slow discharge of the fertilizer to the
plant, this way of doing makes the plant to capture entire quantity of nutrients com-
mencing the fertilizer abounding rather than the minimal uptake. While it has bigger
surface area many molecules can fit into it and get released each time the plant
requires (Naderi and Danesh-Shahraki 2013).
Zinc Nano Fertilizer  Micro nutrient, zinc has a severe scarcity crisis globally. The
quantity of zinc ingestion during daily foodstuff is very low consequently by using
zinc based fertilizer there are slightest probability of indirect supply to human
being. For the similar nano particles can be used to coat zinc in order to get diffused
and soluble zinc (Milani et al. 2015). Equal ratios among surface area and volume
of nano particles should be carefully designed If not, total solubility of the zinc will
be affected. This is shown taking ratio of nano ZnO and bulk ZnO available on
whole (Malik and Kumar 2014).
However the uptake, translocation, and fate of nanoparticles in plant system are
largely unknown resulting in the rise of various ethical and safety issues surround-
ing the use of nano-fertilizers in plant productivity. A systematic and thorough
quantitative analysis regarding the potential health impacts, environmental clear-
ance, and safe disposal of nanomaterials can lead to improvements in designing
further applications of nano-fertilizers. A research protocol to tune nutrient delivery
to plant need, therefore, ought to include the following five considerations: crop,
composition, packaging, application and ecosystem. More than ever before, a revisit
of fertilizer research is needed to move from a mainly ‘lifeless’ physico-chemical
process, to a ‘living’ biological process, where by biologists, in an interactive pro-
cess, work with chemists and chemical engineers in formulating and packaging the
nutrients to meet specific crop metabolic requirements. A coherent revisiting of fer-
tilizers and fertilisation strategies will set the stage for a new paradigm shift involv-
ing moving away from the current practice of largely using bulk generic fertilizers:
large volume-low value, to low volume-high value products. Clearly, transforming
from bulk to targeted fertilizers calls for a transition by the fertilizer and related
industry (Bindraban et al. 2015). Obviously, there is a chance for nanotechnology to
profoundly affect vitality, the economy and the earth, by enhancing fertilizer
­products. New prospects for incorporating nanotechnologies into fertilizers ought to
be investigated, discerning of any potential danger to the earth or to human wellbe-
ing. With focused endeavours by political and academics in growing such empow-
ered agri-products, we trust that nanotechnology will be transformative in this field.
298 S.K. Sanivada et al.

Box 10.2 A Set of Guiding Questions to Assess Technology of

Nano-­enabled Fertilizers or Engineered Nanomaterials as Fertilizer
(Suppan 2013)
1. If the fate of commercial cultivating is to incorporate the use of engi-
neered nanomaterials in soil, will the labs that right now test for soil
health be likewise prepared to do testing for engineered nanomaterials
exposure and even to endorse dosing the soil with nanoscaled chemical
fertilizers and soil added substances?
2. Will the prescribed engineered nanomaterials dosing be characterized
and managed by the individuals who own the innovation?
3. If fertilizers, for example, Mosaic’s “small scale essentials” incorporate
micron-sized (1000 nm) P, K or N, if they be hazard evaluated for their
conceivable harmfulness as ultra-fine particles under the U.S. Clean Air
Act, despite the fact that large scale estimated P, K and N are as of now
controlled under the Clean Water Act?
4. Should micron-sized P, K or N in fertilizers or nano-sized soil supple-
ments go through a pre-market safety appraisal for commercialization
regard or refusal on the premise of lab risk evaluation just or ought to
field trials, including related safety testing, likewise be needed?
5. In the event that research centre investigations with nano-fertilizer seg-
ment chemicals demonstrate critical potential for harm to ecological
health and security, what innovation evaluation procedure can be utilized
to judge whether research centre demonstrated harm exceeds that brought
on by current fertilizer utilization practice?
6. What arrangement or innovation choices arrive to nanotechnology for the
manageable utilization of fertilizers and micronutrient supplements in
soil?
7. If their bio-accumulation represents a peril to human and/or ecological
health, should governments boycott engineered nanomaterials in biosol-
ids or if they attempt to focus Maximum Residue Levels (MRLs) of engi-
neered nanomaterials in biosolids that would in any case ensure consumer
health? On the other hand, consumers attempt to ensure their relying so
as to well on company assurances that their supply chains are free of
products developed with biosolids?
8. As indicated by the action group on erosion, technology and concentra-
tion (ETC), solid nano-toxicity tests are decade’s way for a few engi-
neered nanomaterials. On the off chance that MRLs can’t be dependably
assessed for those engineered nanomaterials, should governments permit
the commercialization of agricultural products that are empowered with
those engineered nanomaterials, for example, yields developed with
engineered nanomaterials imbued biosolids?

(continued)
10  Nanofertilizers for Sustainable Soil Management 299

Box 10.2  (continued)

9. If a government organization discovers that there is a “safe” measure of
particle dispersion of engineered nanomaterials that can be present in soil
in which crops are developed, and another office discovers that unsuitable
measures of green house gasses are discharged from engineered nanoma-
terials treated soil, how should these varying determinations be mediated
or accommodated?
10. In the event that researchers had the capacity distinguish dose-response
level for particular engineered nanomaterials that would slaughter par-
ticular pathogenic organisms while leaving advantageous microorgan-
isms unharmed, would such a measurement reaction rate additionally
leave unharmed soil large scale and microfauna?
11. If a fertilizer could be fabricated that contained a accurately figured mea-
surements rate for one or more engineered nanomaterial segments, would
farmers need to apply such a fertilizer with a like level of accuracy for
every soil sort in their fields all together for the measurement not to be
toxic to the microbial groups in their fields?
12. If economically accessible fertilizers that claim to fuse nano particles
were tested by researchers with the imperative hardware and preparing to
do as such in a field trial, and found to be destructive to microbial groups,
is there any current law that would approve government to boycott such
fertilizers or soil added substances?
13. Since silver nanoparticles in the dosage tried don’t have an antimicrobial
impact, to a limited extent in light of the water in the pores of the wheat
roots, does the lethal impact of silver nanoparticles rise amid times of
drought?

10.12  Conclusion

Researchers will look to reproduce and augment the way revolutionary examina-
tions inspected up this review. Given the predominance of biosolids used to fertilize
rural fields, if there are no gross mistakes in exploratory configuration or informa-
tion translation of these and subsequent trials, administrative powers will be con-
fronted with a troublesome choice. Possibly they will keep on allowing treatment
with biosolids, a economical source of nutrients, and trust that nanomaterials don’t
gather adequately to damage soil health and the health of the individuals who trans-
form and apply biosolids. On the other hand, they will close on the premise of
associate surveyed science, that there is adequate confirmation to warrant a ban on
preparing with biosolids delivered in sewage treatment plants close nanomaterial
assembling and nano-fabrication plants. A ban will permit time to figure out if there
are approaches to make nanomaterials safe in soil, and to investigate how to
300 S.K. Sanivada et al.

fabricate soil health without reliance on biosolids. A ban would likewise take into
consideration the incorporation of the consequences of national innovation
appraisals.
Innovation appraisal is a piece of a more extensive due constancy that adminis-
trations ought to do preceding putting open stores in private-public organizations
for nanotechnology product improvement. As of now, in the administration, there is
no open innovation appraisal that analyzes one mechanical application to another
for accomplishing an open strategy or innovative target. Nationals can’t sit tight for
governments that have put so vigorously in nanotechnologies to drive the
“Subsequent Industrial Revolution” to assess impartially whether there are less
unsafe and extravagant routes than nano-empowered soil added substances to
upgrade soil health and enhance crop yields. We ought not leave the natural and
synthetic architects who delivered the sort of in fact conscientious examination sur-
veyed above to talk just to different authorities or to their administration or private
industry funders. The sooner we can hold hearty innovation evaluations about nano-­
empowered soil added substances with the interest of organic specialists, soil
researchers, agriculturists and concerned nationals, the sooner we will comprehend
what nanotechnology can do well and securely and what it can’t do well and securely
for our soil.
Such innovation appraisals likely will cover with other environmental and civic
health issues, e.g., the pre-nano powerless regulation of biosolids spread on farming
fields, yet such a cover, however theoretically untidy as far as characterizing nano-­
particular risks and advantages, will reflect better this present reality connection of
agri-nanotechnology aspiration. There is a dire open arrangement need to secure the
information important to focus the ecological destiny of agri-nanotechnology
­applications from the field to the fork. Justifiably, maybe, there is more noteworthy
familiarity with about the risks of eating engineered nanomaterials in sustenance’s
than there speaks the truth any risks to soil health. Be that as it may, on the off
chance that we are what we eat, unquestionably what we eat is just as sound and
manageable as the soil it originates from. Overtime, the report clarifies that nanoma-
terials in these rural inputs can amass and damage soil health. More research is
earnestly expected to enough comprehend conceivable long haul effects of
nanotechnology.

Acknowledgments  The authors would like to thank Head, Department of Microbiology and
Food Science & Technology, GIS, Department of Biochemistry, GIS, Department of Biotechnology,
GIT and Management of GITAM University for providing facilities to carry out the work.

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Chapter 11
Impact of Nanomaterials on the Aquatic Food
Chain

Govind Sharan Gupta, Rishi Shanker, Alok Dhawan, and Ashutosh Kumar

Abstract  The unique properties of nanoscale materials have made nanotechnology

the major technology of the twenty-first century. Nanotechnology is now predicted
to reach a market value of $3 trillion by 2020. Today, more than 1800 nano-enabled
products are available in the consumer market. Nano-products and technologies are
used in health and fitness, biomedicine, textiles, agriculture and waste-water treat-
ment. As a consequence this has induced inadvertent release of engineered nanoma-
terials in the environment, particularly in waters. Engineered nanomaterials can
interact with organisms of the food chain at lower and upper trophic levels. In recent
years, progress has been made on the assessment of bioaccumulation, and on the
trophic transfer of engineered nanomaterials.
Here we review the release and impact of nanomaterials, with focus on aquatic
organisms, trophic transfer, biomagnification and policies. The major points are:
engineered nanomaterials can move up to three trophic levels of the food chain.
Biomagnification of quantum dots, gold nanoparticles and cerium oxide nanoparti-
cles up to two trophic levels show a biomagnification factor greater than 1.
Nonetheless, no studies have shown biomagnification at the third trophic level. It
has been also observed that accumulation of engineered nanomaterials induces
physiological processes of plants, protozoans, crustaceans and fish.

Keywords Engineered nanomaterials • Bioconcentration • Bioaccumulation •

Biomagnification • Trophic transfer

G.S. Gupta • R. Shanker • A. Kumar (*)

Division of Biological and Life Sciences, School of Arts and Sciences, Ahmedabad
University, University Road, Navrangpura, Ahmedabad, Gujarat 380009, India
e-mail: govind.gupta@ils.ahduni.edu.in; rishishanker@gmail.com;
ashutosh.kumar@ahduni.edu.in
A. Dhawan
Nanotherapeutics & Nanomaterial Toxicology Group, CSIR-Indian Institute of Toxicology
Research (CSIR-IITR),
PO. Box – 80, Vishvigyan Bhawan, 31- M.G. Marg, Lucknow, Uttar Pradesh 226001, India
e-mail: alokdhawan@iitr.res.in

© Springer International Publishing AG 2017 309

S. Ranjan et al. (eds.), Nanoscience in Food and Agriculture 5, Sustainable
Agriculture Reviews 26, DOI 10.1007/978-3-319-58496-6_11
310 G.S. Gupta et al.

11.1  Introduction

The idea of “nanotechnology” was initiated by Richard P.  Feynman, in a lecture

entitled “There’s plenty of room at the bottom” that further revolutionize this area of
research (Feynman 1960; Maynard et  al. 2006). Nanomaterial is defined as the
ultrafine particles having a size range between 1 nm and100 nm within at least one
dimension (Ghosh and Pal 2007; Bai et al. 2014). Nanomaterials have extraordinary
properties and bioactivities due to their small size and large surface area to volume
ratio, which makes it to be used for variety of applications (Dasgupta et al. 2017;
Shukla et al. 2017; Walia et al. 2017; Balaji et al. 2017; Maddinedi et al. 2017; Sai
et  al. 2017; Ranjan and Chidambaram 2016; Janardan et  al. 2016; Ranjan et  al.
2016; Jain et al. 2016; Dasgupta et al. 2016). It is predicted that the nanotechnology
will achieve a market value of $3 trillion till 2020 (Roco et al. 2011). In a very short
span of time, the nanomaterials have been incorporated in to more than 1800 con-
sumer and industrial products, which has been registered into nanodatabase (Vance
et al. 2015). The number of registered nano-products in consumer product inventory
of PEN in third quarter of 2016 with most extensively used nanoparticles are: Ag
(442) > TiO2 (92) > SiO2 (42) > ZnO (38) (PEN 2016). These nanoparticles are
being used in diverse areas such as drug delivery, diagnostics, medicine, medical
devices, electronics, textiles, personal care products, waste water treatment, sensor
development and agrochemicals (Chen et al. 2014; Gogos et al. 2012; Kahru and
Dubourguier 2010; Scott and Chen 2003; Joseph and Morrison 2006; Robinson and
Morrison 2009). These extensive developments have also increases their release and
toxicological concerns in the environment.
The great progress has been made in the last few years on understanding the
bioavailability, toxicity and food chain impact of engineered nanomaterials. Most of
the studies in trophic transfer assessment have shown movement of engineered
nanomaterial up to two trophic levels with a few studies up to three trophic level
(Dalai, et al. 2014; Kumar et al. 2011; Ghafari et al. 2008, Werlin et al. 2011; Zhu
et  al. 2010a; Pakrashi et  al. 2014; Mielke et  al. 2013; Judy et  al. 2011, 2012;
Holbrook et al. 2008; Zhao et al. 2013; Majumdar et al. 2015; Mortimer et al. 2016;
Kim et al. 2016; Chae and An 2016). The bioaccumulation and biomagnification of
these engineered nanomaterials can also alter the reproductive potential, bacteriv-
ory, swimming behaviour and growth rate in some of the aquatic animals such as
Tetrahymena, Daphnia and Zebrafish (Werlin et  al. 2011; Mielke et  al. 2013;
Bouldin et al. 2008; Zhu et al. 2010b).
The spread of engineered nanomaterials in the ecosystem hierarchy from indi-
vidual organism to population and community will pose a risk to ecosystem services
such as carrying capacity, biogeochemical cycling, nutrient recycling, and energy
transformation (Holden et al. 2013).
11  Impact of Nanomaterials on the Aquatic Food Chain 311

11.2  R
 elease of Engineered Nanomaterials in Environmental
Matrices

The release of engineered nanomaterials in the environment is increasing exponen-

tially due to discovery of new applications in different areas from electronics to
biotechnology (Fig. 11.1). The extent of the release of nanomaterial in environment
has also been increased in proportion to the development of nano-enabled products.
In this context, Keller and Lazareva (2014) have reported that the engineered nano-
materials applications in cosmetics, paints, pigments and coatings are the major
sources of their direct release in the environment. While, the waste water treatment
plants and aquatic environment are the sink of engineered nanomaterials disposal
after completion of the life cycle of nano-based products. It has been estimated that
the 189,200 and 69,200 metric tons of nanoparticles are releasing per year globally
into landfills and water, respectively (Keller and Lazareva 2014).
Engineered nanomaterials enters in the environment at various stages of their life
cycle, viz. during production, transport, research and development, fabrication, con-
sumers use, waste treatment plants, and disposal (Walser et  al. 2012; Keller and
Lazareva 2014; Gottschalk et al. 2009; Lee et al. 2010; Holden et al. 2013; Bernhardt
et al. 2010). As the engineered nanomaterials enters into the environment they pass
through various routes and interacts with the biological, chemical and physical envi-
ronmental entities, that may prevent their behavior and transport in the environmen-
tal matrices (Fig. 11.2).

Fig. 11.1  The present and future areas for innovation of nano-enabled products in the world
market
312 G.S. Gupta et al.

Fig. 11.2  The entry and possible routes of distribution of engineered nanomaterials (ENMs) in the
terrestrial and aquatic environment. ENMs reach in the environment through various stages during
production, transportation, research & development, and recycling. ENMs in the aquatic environ-
ment can enter directly by disposal of industrial and recycled waste, washing of nano-enabled
clothes, pigments and face cream. In the environment, the ENMs can interact with various biologi-
cal and chemical entities such as, phosphates (PO42−), sulphates/sulphides (H2S/SH), nitrates/
nitrites (NO22(3)−) natural and dissolved organic matters (NOM & DOM), macromolecules and clay
particles. Engineered nanomaterials can also interact with organisms present in the food chain at
different trophic levels

Table 11.1  The environmental concentrations of Nanoparticles predicted by risk assessment

studies
Predicted concentration in water (ng/L)
Gottschalk Sun et al. Gottschalk Tiede et al. Mueller and
Nanomaterial et al. (2015) (2014) et al. (2009) (2009) Nowack (2008)
nTiO2 0.6–100 530EU, 670SW 15EU, 2US, 21SW 24,500a 700RE, 1600HE
nZnO 0.09–13 90EU, 120SW 10EU, 1US, 13SW 76,000a NA
nAg 0–0.044 0.66 ,
EU
0.76EU, 0.11US, 10a 30RE, 80HE
0.45SW 0.71SW
Predicted concentrations of engineered nanomaterials arising from use in consumer products
a

EU Europe, US United States, SW Switzerland, RE Realistic senario, HE High emmision scenario

At present, the predicted concentrations of engineered nanomaterials in the natu-

ral water bodies are very low, even the three most used nanoparticles (nTiO2, nZnO
and nAg) are present at a level of ng/L (Table 11.1). It has been established in previ-
ous studies that the toxicity of the engineered nanomaterials essentially depends on
their dose (Bernhardt et al. 2010). However, the available concentration range of
engineered nanomaterials in the environment is several folds lower than their
detected toxic or lethal concentrations in the model organisms.
11  Impact of Nanomaterials on the Aquatic Food Chain 313

However, the increase in number and extent of applications is expected to raise

concentrations very rapidly in not too distant future due to improper disposal and/or
lack of management practices. Hence, it cannot be denied that assessment of ENMs
safety to the environment and human health is an urgent requirement for the sustain-
able development of nanotechnology sector.

11.3  Environmental Impact of Engineered Nanomaterials

The studies on environmental toxicity of engineered nanomaterials have been con-

ducted using different aquatic model organisms such as, bacteria (E. coli and
Pseudomonas aeruginosa), ciliated protozoan (Tetrahymena spp.), crustacean
(Daphnia spp.) and fish (Danio rerio). Bondarenko et al. (2016) have categorized
the hazard ranking of the seven most characterized engineered nanomaterials by
conducting eco-toxicity assays in model organisms. The ranking of hazard was in
the order of: Ag > ZnO > CuO > TiO2 > MWCNTs > SiO2 > Au. Hansen et  al.
(2016) have presented the risk of engineered nanomaterials to the human and envi-
ronmental health on the basis the category of nano-products and their abundance in
the market. They discussed that the nanomaterials based products, which are being
used under the category of health and fitness pose high risk to the human health and
environment. So far, most the studies which carried out under the risk assessment of
engineered nanomaterials have determined their acute effects on the model organ-
isms after direct exposure through aqueous medium. The impact of engineered
nanomaterials at the organisms, population, community and ecosystem level is
majorly depends on their exposure routes and fate in the environment.

11.3.1  Fate of Engineered Nanomaterials in Environment

Engineered nanomaterials, upon entry into the aquatic environment interact with
biotic and abiotic components (Fig. 11.3). The biological entities (bacteria, protozo-
ans, algae, plants and their exudates and bio-macromolecules) interact with engi-
neered nanomaterials and alter their fate by transformation of their original
properties. In previous studies, it has been shown that bacterial cells are ubiquitously
present and have a high ratio of surface area to their volume; thus, the cells interact
with and absorb high levels of engineered nanomaterials (Holden et  al. 2014).
Further, the presence of exopolymeric substances (EPS) on the outer membrane of
bacterial cells promotes the adsorption of engineered nanomaterials from the aquatic
environment (Zhang et  al. 2011; Chojnacka 2010). Jucker et  al. (1998) and Host
et al. (2010), suggested that numerous bacterial exopolymers, such as lipopolysac-
charides (LPS) and siderophores (in Pseudomonas aeruginosa), participate in the
adsorption of nTiO2 and other metals on the bacterial surface. Li and Logan (2004)
have observed that long chain LPS in E. coli cells adheres more strongly to nTiO2
than short chain LPS. Ciliated protozoans such as Tetrahymena secrete mucus from
mucous membranes under stress conditions, and this surface coating affects the fate
314 G.S. Gupta et al.

Fig. 11.3  Possible fate of engineered nanomaterials (ENM) after interaction with environmental
factors.The pristine ENM interacts with the biotic (living organisms and their components) and
abiotic factors (clay particles) after entering into the aquatic systems that may change their fate by
physical changes (aggregation/agglomeration and sedimentation), chemical changes (dissolution
or speciation) and biological changes: surface interactions and biouptake in the living organisms

of engineered nanomaterials in the medium (Ghafari et al. 2008). Ma et al. (2015)

have shown the hetero-agglomeration and co-sedimentation of metal oxide
NANOPARTICLE with algal cells. Similarly, the interactions of engineered nano-
materials with of abiotic factors such as clay particles can influence the hetero-
agglomeration and sedimentation of engineered nanomaterials in the aquatic
environmental matrices (Zhou et  al. 2012; Labile et  al. 2015). It has also been
observed that the biomacromolecules (carbohydrates and proteins), inorganic acids,
(humic acid, fulvic acid, hematite and lignite) and other inorganic substances, (sul-
phates, sulphides, phosphates and nitrates) can also alter the fate of engineered nano-
materials by adsorption or absorption, agglomeration or aggregation, sedimentation,
speciation, ionization, capping and biouptake (Glenn and Klaine 2013; Hernandez-
Viezcas et al. 2013; Sun et al. 2009; Lowry et al. 2010). The change in the fate of
engineered nanomaterials may cause positive or negative effects on engineered
nanomaterials stability. The humic and fulvic acids are known to increase the disper-
sion of engineered nanomaterials in the environment, while the clay particles, algae
and exo-polysaccharides destabilize the engineered nanomaterials in natural envi-
ronment (Lowry et al. 2010; Zhou et al. 2012; Domingos et al. 2009; Ma et al. 2015).
Such transformations on engineered nanomaterials behavior in the environment
can also modify the bioavailability and toxicity potential of engineered nanomateri-
als to the producers, consumers and decomposers. The previous studies have shown
that interactions of Ag nanoparticles with clay particles at different pH conditions
11  Impact of Nanomaterials on the Aquatic Food Chain 315

Fig. 11.4  Routes of

engineered nanomaterials
(ENM) exposure in aquatic
organisms. Direct and
indirect exposure of ENM
to the predator species
from aqueous suspension
and diet (prey),
respectively

can influence the toxicity of Ag nanoparticles to the zebrafish eleutheroembryos

(Gupta et al. 2016). The lipophilic coating of the engineered nanomaterials in envi-
ronment can influence their bioaccumulation and biomagnification potential in food
chain (Hoet et al. 2004; Holbrook et al. 2008).

11.3.2  R
 outes of Engineered Nanomaterials Exposure
in the Aquatic Organisms

Engineered nanomaterials are the special kind of the pollutants. their uptake rate
and adverse effects are particularly depends on the routes of exposure and internal-
ization in the cell and organisms. on the basis of the exposure route their uptake can
be classified into three different types (Fig. 11.4).
In the aquatic environment, when the exposure of engineered nanomaterials to
the organisms occurs particularly through the aqueous medium then it is defined as
bioconcentration (Hou et al. 2013). The passive uptake mechanism may lie in the
process (van der Oost et al. 2003; Thomann et al. 1992). While, the exposure of
engineered nanomaterials through the all possible routes, including contaminated
food defined as bioaccumulation (Dalai et al. 2014). The increase in the concentra-
tion of pollutant over the time, will also be considered as major factor in the process
of bioaccumulation. The transfer of engineered nanomaterials from prey to predator
with more than one time higher magnitude is defined as biomagnification. The eco-­
toxicological studies on the established pollutants have suggested biomagnification
of any pollutant as the most dangerous to the human health and environment.
316 G.S. Gupta et al.

11.4  T
 rophic Transfer and Biomagnification Potential
of Engineered Nanomaterial

The unique properties of engineered nanomaterials, such as small size, high-­

reactivity, long term persistence, poor water solubility and slow degradability can
lead to their bioaccumulation and biomagnification in the environmental food chain
(Hoet et al. 2004; Holbrook et al. 2008). It has been well-established from the ear-
lier studies on potential environmental pollutants such as dichlorodiphenyltrichloro-
ethane (DDT), lead, asbestos, and mercury, that if the substance is highly
accumulative then it can pose more threats to the human health and environment
(Werlin et al. 2011; Holbrook et al. 2008). The studies have shown the transfer of
engineered nanomaterials from first to second trophic level with increasing concen-
tration, however reaching at third trophic level the concentration of nanomaterials
decreased to several fold (Fig. 11.4).
In two trophic food chain, Werlin et  al. (2011) showed the trophic transfer of
CdSe QDs from Pseudomonas aeruginosa to Tetrahymena thermophile with five
times higher concentration (BMF ~5). Chen et al. (2015) showed the biomagnifica-
tion TiO2 Nanoparticles from Scenedesmus obliquus to Daphnia magna with a bio-
magnification factor of 7.8–2.2. Judy et  al. (2011) and Unrine et  al. (2012) have
observed an increase in the concentration of Au Nanoparticles up in the food chain
from Lycopersicon esculentum to Manduca sexta with a factor of 6.2–11.6. Holbrook
et al. (2008) have shown the trophic transfer quantum dots from protozoans to roti-
fer, with a biomagnification factor of 0.62–0.29. Zhu et  al. (2010a) have investi-
gated the trophic transfer of TiO2 nanoparticles from Daphnia magna to Danio rerio
with a biomagnification factor of 0.1. Mortimer et al. (2016) have shown the trophic
transfer of carbon nanotubes without biomagnification in a microbial food chain
that comprised of Pseudomonas aeruginosa as prey and Tetrahymena thermophile
as predator organisms.
In three trophic level food chain, Majumdar et al. (2015) have demonstrated the
trophic transfer of CeO2 nanoparticles with five times higher concentration from
Phaseolus vulgaris to Epilachna varivestis and then to Podisus maculiventris. Lee
and An (2015) have provided evidence on the trophic transfer of QDs up to three
trophic levels among from Astasia longa to Moina macrocopa to Danio rerio with
a biomagnification factor of 0.1 (Fig. 11.5).
Earlier studies regarding the biomagnification have been performed under the
controlled laboratory conditions without the influence of any environmental factors.
Hence, the observations made from these studies raise several questions such as (1)
extrapolation of the lab data into the realistic environment (2) similar obsrvations in
the other existing organisms of same genera. Most of the available data on biomag-
nification has been performed in aquatic organisms. Therefore, it is needed to per-
form more work in the terrestrial organisms.
11  Impact of Nanomaterials on the Aquatic Food Chain 317

Fig. 11.5  Trophic transfer of nanoparticles in a multi trophic level aquatic food web. The food
web can be consists of bacteria, phytoplanktons, algae or plants at lower trophic level, protozoans,
crustaceans and snail at second trophic level and fish and rotifers at the top. When the Nanoparticles
concentration increases from one trophic to another with a factor of more than one, it indicates the
biomagnification. Biomgnification factor (BMF), a ratio of Nanoparticles concentration in preda-
tor to prey. (ppm) parts per million

11.4.1  Relationship Between Bioaccumulation

and Biomagnification Behaviour of Engineered
Nanomaterials

The pollutants showing the BCF and BAF higher than 5000 are known to be bioac-
cumulative. However, if the pollutant shows the value of TMF > 1, it is known as
effective biomagnifying substance. The earlier studies on engineered nanomaterials
on laboratory scale aquatic food chains ensure that if the TMF > 1, it indicates to
biomagnification. However, if the TMF > 3. It is known to be critical biomagnifica-
tion. A comparison of TTF with BAF and BCF is given in Fig. 11.6.
318 G.S. Gupta et al.

BCF or BAF ≥ 5,000 and TMF >1

Bioaccumulation (+), Biomagnification (+)

-+ ++
Bioaccumulation (-), Biomagnification (+)
BCF or BAF < 5,000 and TMF >1 BCF or BAF > 5,000 and TMF <1

Bioaccumulation (+), Biomagnification (-)

-- +-
Bioaccumulation (-), Biomagnification (-)

BCF or BAF < 5,000 and TMF <1

Fig. 11.6  Criteria for determination of food chain impacts of engineered nanomaterials (ENMs).
The ENMs can be considered as bioaccumulative and biomagnifying, if their factors of accumula-
tion are more than 5000 and 1, respectively in the organisms. BAF bioaccumulation factor, TMF
Trophic magnification factor; BCF Bioconcentration factor

11.5  I mpact of Engineered Nanomaterials on the Producers

of the Ecosystem

The available literature on the effects of engineered nanomaterials in the plants

shows that engineered nanomaterials may accumulate in the agriculture crops and/
or increase concentrations of the constituted metal of nanomaterials in the fruits or
grains of particular plant (Gardea-Torresdey et al. 2014). The accumulation of engi-
neered nanomaterials can cause harmful effects on the yield and productivity of
plants, alter the nutritional value of food crops, and also transfer them across the
trophic levels. Algal cells are also the primary producers of the aquatic environment.
Accumulation of engineered nanomaterials in the algal cells can be transfered across
the trophic levels of a food chain (Zhang et al. 2012). Literatures on the bioaccumu-
lation and trophic transfer studies on the producers to primary consumers have been
given in the Table 11.2. The studies on the phytotoxicity of most used engineered
nanomaterials (Ag, ZnO, TiO2, Cu/CuO, and carbon based) has been summarised in
Table 11.3. It was observed that engineered nanomaterials can pose multiple adverse
effects on plants such as alteration of physiological processes (Yan et  al. 2013;
El-Temsah and Joner 2010; Stampoulis et al. 2009; Kumari et al. 2009; Lee et al.
2008; Darlington et al. 2009; Lin and Xing 2008), gene expression (Ghosh et al.
2011, 2015; Khodakovskaya et  al. 2011, 2012) DNA damage (Katti et  al. 2015;
Castiglione et al. 2011) and increased formation of ROS (Begum and Fugetsu 2012;
Liu et al. 2013; Hernandez-Viezcas et al. 2011). These phytotoxicological studies
were focused on the certain parameters such as rate of seed germination, root and
shoot development, yield measurement, biomass growth, DNA damage, cell wall
damage, transpiration potential, cell cycle, leaf growth, flowering delay and germi-
nation index. Studies need to be conducted to understand the toxicity mechanism of
engineered nanomaterials in plants. Additionally, no relevant standard toxicity
Table 11.2  Accumulation of engineered nanomaterials in the producers and consumers of the environmental food chain
BAF/BCF/BMF or
Test TTF or TMF/BSAF/ Type of
Nanoparticle Test organism Mode of exposure Concentration duration Percent food chain References
Producers: Plants-primary consumers
Tannate coated au Tobacco Tomato leaf tissue 100 mg/L au 7 day BAF = 0.16 Terrestrial Judy et al.
nanoparticles hornworm (2012)
(Manduca
sexta)
caterpillars
CeO2 & ZnO Cucumber Soil 400, & 800 40 day 1.27 mg of Ce and Terrestrial Zhao et al.
nanoparticles plants mg/kg 110 mg Zn per kg (2013)
dry weight
Al2O3 nanoparticles Ceriodaphnia Algae (chlorella 120 μg/mL 72 h BMF = 0.19 Aquatic Pakrashi et al.
dubia ellipsoids) (2014)
AuNanoparticles (5, 10, & Manduca sexta Nicotiana tabacum L. 100 mg au/L 41 h BMF = 6.2, 11.6 & Terrestrial Judy et al.
15 nm) (tobacco cv Xanthi 9.6 for 5, 10, & (2011)
hornworm) 15 nm
11  Impact of Nanomaterials on the Aquatic Food Chain

Au Nanorods (CTAB Estuarine Water 7.08 × 108 12 day BCF (L kg−1 DW) Esturine Ferry et al.
coated) mesocosm (sea particles/ mL Biofilm = 15,300, (2009)
water, sea grass = 8.21,
sediment, sea Shrimp = 115, Fish
grass, = 474, Snail = 167,
microbes, Clam = 22,800
bioflms, snails,
clams,shrimp
and fish)
ZnO nanoparticles Soybean Root 500 mg/L 49 days BCF Leaf =0.69, Terrestrial Hernandez-­
(Glycine max) stem =0.25, root Viezcas et al.
=0.24, nodule =0.07 (2013)
(continued)
319
Table 11.2 (continued)
320

BAF/BCF/BMF or
Test TTF or TMF/BSAF/ Type of
Nanoparticle Test organism Mode of exposure Concentration duration Percent food chain References
ZnO nanoparticles Peanut (Arachis Leaves 133 mg/L 110 day Zn bioaccumulation Terrestrial Prasad et al.
hypogaea L.) in leaf =42% (2012)
TiO2 nanoparticles Tomato Root 50, 100, 6-week % accumulation Terrestrial Song et al.
1000, 2500, old plant Stem =11.0–11.4%, (2013)
5000 mg/L to Leaves =6.1–8.4%
maturity
CeO2 nanoparticles Soybean Root 1000 mg/L 49 day BCF Terrestrial Song et al.
Root =0.21, nodule (2013)
=0.011, Stem
=0.0001, leaf =3 ×
10−7
ZnO nanoparticles Isopods Diet (nanoparticles 6.2 and 2.5 g 28 day BAF (kg dry leaf Terrestrial Pipan-Tkalec
(Porcellio contaminated leaves) ZnO per kg per kg dry biomass) et al. (2010)
scaber) dry leaf = 0.1 and 0.2
Consumers: Primary consumers (invertebrates)-top consumers (vertebrates)
TiO2 nanoparticles Ceriodaphnia Diet, (Scenedesmus 1, 2, 4,8, 21 day BAF = 214.38 (L/ Aquatic Dalai et al.
Dubia obliquus) and water 16,32 & 64 kg) BMF = 0.218 (2014)
μg/mL
TiO2 nanoparticle Daphnia Water and diet 1 mg/L 72 h BCF = 118062.84 Aquatic Zhu et al.
aggregates magna (Pseudokirchneriella L/kg BAF = (2010b)
subcapitata) 1232.28 L/kg
Nanocrystalline fullerenes Daphnia Water 0.2 mg/L 24 h BCF (L/kg DW) = Aquatic Tao et al.
as C60 Magna 15,000 and 437,500 (2009)
for mother and baby
daphnia
G.S. Gupta et al.
 BAF/BCF/BMF or
Test TTF or TMF/BSAF/ Type of
Nanoparticle Test organism Mode of exposure Concentration duration Percent food chain References
AgNANOPARTICLE-­ Polychaete Sediment 0.75, 7.5 and 28 day Ag accumulation = Estuarine Wang et al.
citrate, (Nereis virens) 75 mg/kg dry 32–44%, relative to sediment (2013)
AgNANOPARTICLE-­ sediment the sediments
PVP weight
CdSe core - ZnS shell Rotifer Ciliated protozoan Cd2+/g QDs 48 h BMF (dry weight) = Aquatic Holbrook
Carboxylated and (Brachionus (Tetrahymena Carboxylated Carboxylated et al. (2008)
Biotinylated QDs calyciflorus) pyriformis) =985.4 ng QDs-0.62
Biotinylated Biotinylated
=624.3 ng QDs-0.29
TiO2 nanoparticle Tetrahymena Bacteria (Pseudomonas 0.10 mg/mL 16 h BMF = 0.16 Aquatic Mielke et al.
Thermophila Aeruginosa) (2013)
TiO2 nanoparticle Zebrafish Daphnia Magna 1 mg/L 21 day BMF = 0.009 Aquatic Zhu et al.
(Danio rerio) (2010a)
AgNANOPARTICLE Daphnia Water 0.02–0.5 48 h BCF = 46,000 104 Aquatic Zhao and
(coated with carbonate) Magna mg/L (L kg−1 dry Weight) Wang (2011)
C60 Daphnia Water and diet 30 mg/L 48 h BCF (L kg−1 DW) Aquatic Oberdorster,
Magna (30 mg/L) = 38,000 et al. (2006)
C60 Daphnia Water 0.5–2 mg/L 24 h BCF (L/kg DW) Aquatic Tervonen et al.
11  Impact of Nanomaterials on the Aquatic Food Chain

Magna uptake & (0.5 mg/L) = 95,000 (2010)

2 day (2 mg/L) = 25,000
depuration
(continued)
321
Table 11.2 (continued)
322

BAF/BCF/BMF or
Test TTF or TMF/BSAF/ Type of
Nanoparticle Test organism Mode of exposure Concentration duration Percent food chain References
MWCNT Daphnia Water 0.04–0.4 48 h BCF (L/kg dry Aquatic Petersen et al.
Magna mg/L uptake & biomass) = (2009)
2 day 350,000–440,000
depuration
CdSe QDs (citrate coated) Ciliated QDs loaded bacteria 75 mg/L 24 h BMF (DW) ¼ 5.4 Aquatic Werlin et al.
protozoa Aeruginosa) (2011)
(Tetrahymena
Thermophila)
SWCNT and MWCNT Oligochaetes River sediment 0.03 and 28 day BSAF (kg OC kg−1 Sediment Petersen et al.
(Lumbriculus 0.37 mg exposure lipid) (2008)
variegates) CNT/kg SWCNT =0.28
dry-sediment MWCNT = 0.40
MWCNT Oligochaetes River sediment 0.37 mg 28 day BSAF (kg dry Sediment Petersen et al.
(Lumbriculus CNT/g dry exposure sediment per kg dry (2010)
variegates) sediment biomass) = 0.67
TiO2 nanoparticles Polychaets Marine sediment 1–3 g TiO2 10 day BSAF (kg OC per Sediment Galloway
(Arenicola Per kg kg Lipid) = et al. (2010)
marina) sediment 0.156–0.196
TiO2 nanoparticles Carp (Cyprinus Water 10 mg/L 25 day BCF (L kg−1 whole Aquatic Sun et al.
carpio) DW) = 495 vertebrate (2007)
TiO2 nanoparticles Carp (Cyprinus Water 10 mg/L 20 day BCF (L kg−1 whole Aquatic Zhang et al.
Carpio) body DW) = 325 vertebrate (2007)
G.S. Gupta et al.
 BAF/BCF/BMF or
Test TTF or TMF/BSAF/ Type of
Nanoparticle Test organism Mode of exposure Concentration duration Percent food chain References
TiO2 nanoparticles Carp (Cyprinus Water 10 mg/L 20 day BCF (L kg−1 whole Aquatic Sun et al.
Carpio) body DW) = 617 vertebrate (2009)
TiO2 nanoparticles Zebrafish Water 0.1–1 mg/L 14 day BCF (L kg−1 DW) = Aquatic Zhu et al.
(Danio Rerio) 25 & 181 vertebrate (2010a)
CdSe-ZnS QD (coated Zebrafish QD loaded Daphnids Adult fish 21 day BMF = 0.04 and Aquatic Lewinski et al.
with poly(acrylic (Danio Rerio) =10 QD/ 0.004 for adult and (2011)
acid)-octylamine) daphnia juvenile zebrafsh
Juvenile fish
=1 mL of
QD/ 3000
Artemia
TiO2 nanoparticles Earthworm Artificial soil 0.1–5 g/kg 7 day BSAF(kg dry soil Terrestrial Hu et al.
(Eisenia fetida) dry soil per Kg wet biomass) (2010)
= 0.01–0.02
ZnO nanoparticles Earthworm Artificial soil 0.1–5 g/kg 7 day BSAF(kg dry soil Terrestrial Hu et al.
(Eisenia fetida) dry soil per Kg wet biomass) (2010)
= 0.01–0.37
XAS X-ray absorption spectroscopy, ICP-MS inductively coupled plasma mass spectrometry, HR-ICP-MS High resolution inductively coupled plasma mass
11  Impact of Nanomaterials on the Aquatic Food Chain

spectrometry, ICP-AES inductively coupled plasma atomic emission spectroscopy, ICP–OES inductively coupled plasma–optical emission spectrometry, AAS
Atomic Absorption Spectrophotometer, LSC Liquid scintillation counting
323
324 G.S. Gupta et al.

Table 11.3  The direct toxicological impact of Ag, ZnO, TiO2, Cu/CuO and Carbon based
engineered nanomaterials in plants
Nanoparticle
type Concentration Plant species Toxicity References
Ag 10 mg/L Barley, flax Decreases seed El-Temsah et al.
germination and (2010)
reduces shoot
length
Ag 100, 500, 1000 Zucchini Reduced Stampoulis et al.
mg/L transpiration, (2009)
biomass and root
growth
Ag 25–100 mg/L Allium cepa Effect mitosis Kumari et al. (2009)
cell cycle with
altered
metaphase.
The fragmentation
and disruptions in
the cell wall
Chromosomal
aberrations
Cu 200–800 mg/L Mungbean and Effect the normal Lee et al. (2008)
wheat growth of
seedling and
shoot
Cu 1000 mg/L Zucchini Reduce the Darlington et al.
biomass (2009)
production, root
growth
ZnO 1000 mg/L Ryegrass Reduced biomass Lin and Xing (2008)
production,
contracted root
tips, damage in
the epidermis and
root cap,
vacuolated and
collapsed cortical
cells
ZnO 2000 mg/L Corn, reddish, Reduced seed Lin and Xing (2007)
rape, ryegrass, germination and
lettuce, root growth
cucumber
ZnO 1000 mg/L Zucchini Reduced biomass Stampoulis et al.
production (2009)
ZnO 2000–4000 Soybean Decreased root Lopez-Moreno et al.
mg/L growth 2010
SWCNT 400 mg/L Rice Flowering delay, Lin et al. 2009
decreased in the
yield
(continued)
11  Impact of Nanomaterials on the Aquatic Food Chain 325

Table 11.3 (continued)
Nanoparticle
type Concentration Plant species Toxicity References
SWCNT 104, 315, 1750 Tomato Reduction in the Canas et al. (2008)
mg/L root growth
MWCNT 1000 mg/L Zucchini Reduced biomass Stampoulis et al.
production (2009)
MWCNT 2000 mg/L Lettuce Reduced root Lin and Xing (2007)
length
MWCNT 20, 40, 80 Rice Cell shrinkage, Tan et al. (2009)
mg/L plasma
membrane
detachment from
cell wall,
apoptosis
MWCNT 50–200 mg/L Lycopersicon Increased the Khodakovskaya et al.
esculentum expression of (2011)
stress related
gene
MWCNT 0.1 mg/L Nicotiana Increased the Khodakovskaya et al.
tabacum expression of (2012)
genes related to,
cell-wall
assembly, cell
growth,
regulation of cell
cycle progression
and synthesis of
aquaporins.
TiO2 300, 1000 Maize Repressed Asli and Neumann
mg/L transpiration, (2009)
hydraulic
conductivity and
leaf growth
TiO2 2–10 mM Allium cepa, DNA damage Castiglione et al.
mg/L Nicotiana was observed (2011)
tabacum, Zea using comet
mays, Vicia assay,
narbonensis, chromosomal
Arabidopsis aberrations,
thaliana micronuclei test
was positive,
altered mitotic
activity
ZnO 500–4000 Proposis julif Increases in the Hernandez-Viezcas
mg/L lora-velutina catalase activity et al. (2011)
in whole plant,
Decrease in
ascorbate
peroxidase
activity in roots,
while increases in
leaves and stem.
326 G.S. Gupta et al.

assays has been developed to study the effect of photoperiod on the toxicity of
photo-catalytic nanoparticles. The selection of experimental duration needs to be
considered, while conducting phytotoxicity assays of engineered nanomaterials.

11.6  R
 egulations and Policies on the Human Health
and Environmental Safety of Engineered Nanomaterials

Considering the challenges of sustainable development of nanotechnology, the

safety of nano-products has become important to define. The various international
agencies are already working independently and together on bringing the safety
regulation of nanomaterials to the human health and environment. In 2006,
Organization for Economic Co-operation and Development (OECD) has formed a
committee named as “Working Party on Manufactured Nanomaterials (WPMN),
which is currently working on the development of new guidelines for the safer use
of nanomaterials for the human health and environment (OECD 2012). In 2009,
OECD reported the guideline manuals for the testing of manufactured nanomateri-
als (Park and Yeo 2016). In 2013–2014, the OECD WPMNs steering group 9 (SG9)
publishes the test guideline on ecotoxicity and environmental fate of manufactured
nanomaterials (Park and Yeo 2016). The International Organization for
Standardization (ISO) has given guidelines for the safety of engineered nanomateri-
als to the human health and environment in a Working Group 3 (WG3). The guide-
lines on WG3 document suggest that nanomaterials toxicity should be recognized
on the basis of measurements on their characteristics such as size, surface charge,
composition, and aggregation/agglomeration state as defined in WG2 (Murashov
and Howard 2011). The REACH (Registration, Evaluation, Authorization and
Restriction of Chemicals) is a regulation committee of the EU that involved in the
registration of substances including nanomaterials and other bioaccumulative as
well as toxic substances that are manufactured or imported at a rate higher than one
ton per year. In accordance with Classification, Labelling, and Packaging (CLP), the
European Chemicals Agency (ECHA) must categorize nanomaterials with regards
to their hazardous potential. Additionally, inventory that contains nanomaterials
must be labelled to notify consumers (Europian commission, Nanomaterials). In
2015, the United States (US)-Environmental Protection Agency (EPA) declared a
conditional registration of silver nanoparticles constituted pesticide products
(Nanotech). The evaluation of this conditional registration was based on the effects
of silver nanoparticles to the human health and environmental.

11.7  Conclusion

The chapter has discussed about the current status on release of engineered nanoma-
terial in the aquatic environment and their accumulation in the different trophic level
organisms of food chain. At present scenarios, the concentration of engineered
11  Impact of Nanomaterials on the Aquatic Food Chain 327

nanomaterial are very low in natural environment, but the unique physicochemical
properties of the engineered nanomaterial have the potential to enhance bioavailabil-
ity that can enable their biomagnification and consequent toxicity in aquatic organ-
isms. The available data have shown that the engineered nanomaterials can transfer
from one trophic level to another in the terrestrial, aquatic and estuarine food chain.
But, the potential of trophic transfer depends on the type of nanoparticle. Quantum
dots, gold and cerium oxide nanoparticles transferred to another trophic level with
increasing concentration (biomagnification factor > 1) in contrast to zinc oxide, and
titanium dioxide nanoparticles (biomagnification factor < 1). The biomagnification
of the contaminants can be very harmful to the ecosystems as we learnt form the past
in case of mercury and DDT. Therefore, it is an urgent demand to test the biomagni-
fication of engineered nanomaterials to organisms that are still not been investigated
for such effects and are the most relevant to the ecosystem services.

Acknowledgements The authors acknowledge the funding received from Department of

Biotechnology under the project NanoToF (grant number BT/PR10414/PFN/20/961/2014), CSIR
Network Projects NWP35 and BSC0112 (NanoSHE), India, and the EU-FP7/2007-2013/Grant
Agreement 263147 (NanoValid-Development of reference methods for hazard identification, risk
assessment and LCA of engineered nanomaterials), Europe. Financial assistance by The Gujarat
Institute for Chemical Technology (GICT) for the Establishment of a Facility for environmental
risk assessment of chemicals and nanomaterials and Centre for nanotechnology research and appli-
cations (CENTRA) is also acknowledged.

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Chapter 12
Nanoremediation for Sustainable Crop
Production

Hassan El-Ramady, Tarek Alshaal, Mohamed Abowaly, Neama Abdalla,

Hussein S. Taha, Abdullah H. Al-Saeedi, Tarek Shalaby, Megahed Amer,
Miklós Fári, Éva Domokos-Szabolcsy, Attila Sztrik, József Prokisch,
Dirk Selmar, Elizabeth A.H. Pilon Smits, and Marinus Pilon

Abstract Nanoremediation is a promising strategy to controlling pollution.

Nanoremediation involves the use of nanomaterials and plants, named phyto-­
nanoremediation, animals, named zoo-nanoremediation and microbes, named
microbial nanoremediation. Here we review environmental pollution, crop protec-
tion and nanoremediation.

Keywords Nanoremediation • Sustainable crop production • Polluted lands •

Pollution

H. El-Ramady (*) • T. Alshaal • M. Abowaly

Soil and Water Department, Faculty of Agriculture, Kafrelsheikh Uni, Kafr El-Sheikh, Egypt
e-mail: ramady2000@gmail.com; alshaaltarek@gmail.com; mabowaly@yahoo.com
N. Abdalla • H.S. Taha
Plant Biotechnology Department, Genetic Engineering Division, National Research Center,
Dokki, Giza, Egypt
e-mail: neama_ncr@yahoo.com; hussein.taha2@yahoo.com
A.H. Al-Saeedi
College of Agricultural and Food Sciences, King Faisal University,
Al-Hassa, 31982, Saudi Arabia
e-mail: 2012ahs@gmail.com
T. Shalaby
College of Agricultural and Food Sciences, King Faisal University,
Al-Hassa, 31982, Saudi Arabia
Horticulture Department, Faculty of Agriculture, Kafrelsheikh Uni, Kafr El-Sheikh, Egypt
e-mail: tashalaby@yahoo.com
M. Amer
Soils, Water and Environment Research Institute (SWERI), Agricultural Research Center,
Giza, Egypt
e-mail: dr_megahed120@yahoo.com

© Springer International Publishing AG 2017 335

S. Ranjan et al. (eds.), Nanoscience in Food and Agriculture 5, Sustainable
Agriculture Reviews 26, DOI 10.1007/978-3-319-58496-6_12
336 H. El-Ramady et al.

12.1  Introduction

There are several global problems threatening the life on the Planet including envi-
ronmental pollution, climate changes, food security, soil security, energy etc. The
polluted environments (e.g. water, soil, air, etc) also can be considered an emerging
issue (McCrink-Goode 2014; Lodeiro et al. 2016; Ibrahim et al. 2016; Belal and
El-Ramady 2016). These pollutants can be resulted from different sources including
industrial activities (Zheng and Shi 2017; Wang et  al. 2017), traffic (Hjortebjerg
et al. 2016; Laña et al. 2016; Pan et al. 2016; Patton et al. 2016; França et al. 2017),
mining activities (Diego and Cebada 2016; Caraballo et al. 2016; Campos-Herrera
et al. 2016) and agricultural activities (Jacobsen and Hansen 2016; Ouyang et al.
2016a; Parelho et al. 2016; Rocco et al. 2016; Toro et al. 2016; Slabe-Erker et al.
2017). The polluted lands suffer from the high concentration of toxic pollutants
destroying the agroecosystem (Brambilla et al. 2016; Stiborova et al. 2017). This
toxic level of pollutants prevents the sustainable management and pollution control
of these lands (Tripathi et al. 2015; Stiborova et al. 2017). So, an international col-
laboration between different countries should be established concerning the global
pollution (Günther and Hellmann 2017).
The global crop production was and still not enough to feed all people all over
the world (Fraser et al. 2017; Sala et al. 2016). There is a serious gab between the
global food production and the global consumption (Sundbo 2016; Dandage et al.
2017; Sandström et al. 2017). Therefore, all countries should seek to design an inte-
grated production system in frame of the food energy water nexus (Kucukvar and
Samadi 2015; Hang et  al. 2016; Smajgl et  al. 2016; Peterson 2017). So, some
emerging solutions should be addressed to resolve the global food crisis including
biotechnology - as several nanomaterials have been developed with a target to use
as nutraceuticals, and drug active compounds (Fraser et al. 2017; Dunbar 2016) and
nanotechnology (Dasgupta et al. 2015; Ghorbanzade et al. 2017; Magalhães et al.
2017; Syedmoradi et al. 2017; Dasgupta et al. 2017; Shukla et al. 2017; Walia et al.

M. Fári • É. Domokos-Szabolcsy
Plant Biotechnology Department, Debrecen Uni,
Böszörményi Útca. 138, 4032 Debrecen, Hungary
e-mail: fari@agr.unideb.hu; domokosszabolcsy@gmail.com
A. Sztrik • J. Prokisch
Institute of Bio- and Environmental Enegetics, Debrecen Uni,
Böszörményi Útca. 138, 4032 Debrecen, Hungary
e-mail: atyesz@gmail.com; jprokisch@agr.unideb.hu
D. Selmar
Applied Plant Science Department, Institute for Plant Biology,
TU Braunschweig, Braunschweig, Germany
e-mail: d.selmar@tu-bs.de
E.A.H. Pilon Smits • M. Pilon
Department of Biology, Colorado State University,
Fort Collins, CO 80523 187880523 1878, USA
e-mail: epsmits@lamar.colostate.edu; pilon@lamar.colostate.edu
12  Nanoremediation for Sustainable Crop Production 337

2017; Balaji et  al. 2017; Maddinedi et  al. 2017; Sai et  al. 2017; Ranjan and
Chidambaram 2016; Janardan et  al. 2016; Ranjan et  al. 2016; Jain et  al. 2016;
Dasgupta et al. 2016). Furthermore, production safe and enough food was and still
a great challenge faces all countries particularly the developing countries (Bordeleau
et  al. 2016; Haukijärvi and Lundén 2017). Not only the production of safe and
enough food but also the handling of these foods is an emerging issue in the global
food crisis (Choi et  al. 2016; Gong et  al. 2016; Haukijärvi and Lundén 2017;
Mudiyanselage et al. 2017).
Therefore, the remove of pollutants from soils and waters could be linked with
both the sustainable remediation and the sustainable energy production (Kovacs and
Szemmelveisz 2017; Zheng and Shi 2017). Many strategies for the sustainable and
integrated management of polluted lands should be addressed depending on several
factors e.g., type of pollutants and their level, the purpose of land use after processes
of remediation, soil characterization and its topography, climate and cropping pat-
tern, and the availability of resources and their economics (Saha et al. 2014; Pandey
et al. 2016a). Furthermore, a great debate concerning using of lands in crop food
production (for growing global population) or energy crop production was and still
for ages (Paschalidou et al. 2016; Jezierska-Thöle et al. 2016). Therefore, a global
and holistic strategy in facing the main three threats including hunger, lack of energy
and pollution of environment should be established (Abhilash et  al. 2016;
Paschalidou et al. 2016).
On the other hand, nanoparticles are the most important strategy for remediation
these contaminated environments. This remediation for different environments
using nanoparticles/nanomaterials is called nanoremediation (Jain et  al. 2016;
Gillies et al. 2016; Gil-Díaz et al. 2016a; Gomes et al. 2016; Kuppusamy et al. 2016;
Wang et  al. 2017). This nanoremediation could be performed in the presence of
nanoparticles/nanomaterials using plants or phyto-nanoremediation (Rajan et  al.
2015; Chung et al. 2016; Shalaby et al. 2016; Singh et al. 2016; Wang et al. 2016),
microbes or microbial nanoremediation (Gil-Díaz et al. 2016a; Kuppusamy et al.
2016; Patil et  al. 2016) or animal or zoonanoremediation (Belal and El-Ramady
2016). Therefore, there is an urgent need for the environmental pollution control
under a sustainable management (Abhilash et al. 2016; Cai et al. 2016; Pandey et al.
2016a). Several applications of nanomaterials/nanoparticles have been used in
many sectors including sustainable crop production, reduction nutrient losses, sup-
pression disease and enhancement crop yield (Ditta et al. 2015; Tripathi et al. 2016;
Pandey et al. 2016b; Panpatte et al. 2016; Shalaby et al. 2016). The nanoremediation
for sustainable crop production in polluted lands should be managed in a proper
way before the expansion in such polluted lands for the agricultural production
(Kuppusamy et  al. 2016; Panpatte et  al. 2016; Patil et  al. 2016). This currently
resulted from the difficulty in measuring the sustainability of crop production in
such polluted lands as well as lack in evaluating techniques for the performance of
phytoremediation in frame of bioeconomy (Shalaby et  al. 2016; Tripathi et  al.
2016). Therefore, the aim of this review was to evaluate the nanoremediation and its
strategy in polluted lands seeking about the sustainable crop production.
Nanotechnology and its using in pollution control, as well as the environmental pol-
lution and its sustainable management also will be highlighted.
338 H. El-Ramady et al.

12.2  Environmental Pollution: A Global Issue

Environmental pollution is a major global issues (McCrink-Goode 2014). This pol-

lution occurs in soil, water, air, and ecosystems (Fig.  12.1). Pollution is defined
according to US EPA as “the presence of a substance in the environment whose
chemical composition or quantity prevents the functioning of natural processes and
produces undesirable environmental and health effects” (Mehndiratta et  al. 2013)
(United States Environmental Protection Agency 2008). Concerning the air pollu-
tion, it is the major threat to health as reported by World Health Organization (WHO;
Venkatesan 2016). Regarding soil and water pollution, they are also a real threat for
health (Lu et al. 2015; Chen et al. 2016a). Environmental pollution includes different
forms such as organic and inorganic pollutants but the most important and new types
are electronic wastes (Awasthi et al. 2016) and nanoparticle or nanomaterial pollut-
ants (Ibrahim et al. 2016; Li et al. 2016a). The common pollutants include the heavy
metals (Li et  al. 2016b; Chen et  al. 2016c; Yin et  al. 2016), persistent organic

Fig. 12.1  Some photos for many sources of pollution including river water in Munch (Germany;
Photo 1), soil in Rome (Italy; Photo 2), soil and water in Baltim, Tanta, Baltim and El-Hamoul
(Egypt; photos from 3 to 6, resp.) (All photos by El-Ramady)
12  Nanoremediation for Sustainable Crop Production 339

pollutants (Brambilla et al. 2016; Liu et al. 2016; Wilson et al. 2016), environmental
persistent pharmaceutical pollutants (Zhou et al. 2015; Huber et al. 2016), polycyclic
aromatic hydrocarbons (Kenessov et al. 2016), volatile organic compounds (Oiamo
et al. 2015; Pantoja et al. 2016), and environmental xenobiotics (Witczak et al. 2016).
Developing and developed countries suffer from environmental pollution and its
problems. So, new methodologies should be developed to detect and monitor not
only well known pollutants but also different new contaminants (Lodeiro et al. 2016).
Different pollutants should be removed from different environments including soil,
water, air and ecosystem within different technologies of remediation.
Year by year and day by day, enormous pollutants or xenobiotic compounds have
been increased in ecosystems considerably. Environmental pollution nowadays is
considered a major human and environmental problem (Adki et al. 2014; Pandey
et al. 2016b; Noguera-Oviedo and Aga 2016). This environmental pollution can be
defined as any discharge of material or energy into natural resources (i.e., water,
land, air, forest, etc) causing or may cause acute (through short-term) or chronic
(through long-term) damage to the universe (Adki et al. 2014). Several sources of
pollution or many synthetic substances represent these sources including (1) the
natural activities (geological erosion and saline seeps), (2) the human activities
(e.g., construction and mining), (3) industrial activities, (4) agricultural activities
(e.g. fertilizers, pesticides) (5), acidic deposition, (6) radioactive fallout, and (7)
pharmaceuticals (Adki et al. 2014).
Concerning soil pollution, it is very important to monitor and remediate different
toxic pollutants in soils because of the global food safety (Kenessov et al. 2016).
Due to the complexity and dynamics of soils, it is represented as the sink and/or the
source of contaminants, which can be found in exchanging with air, water and the
biosphere (Kenessov et al. 2016). Hence, the soil properties can be used as a good
indicator for soil pollution such as soil basal respiration (Romero-Freire et al. 2016),
soil data (Chen et al. 2016b), soil microbial communities (Azarbad et al. 2016), etc.
In order to quantify soil pollutants, four requirements are necessary i.e. estimation
the spatial and temporal trends of pollutant concentrations, development of the effi-
ciency of the technology of soil remediation, determination the pollution source and
the soil map for polluted areas and verification that soil quality fulfills the standards
of safety (Kenessov et al. 2016).
Regarding water pollution, it has attracted the attention of several researchers.
Different sources of water pollution have been reported including the industrial sources
(petrochemical, pharmaceutical, textile, leather, plastics, paper, food, dye industries,
etc.), agricultural practices and activities (e.g., pesticides and fertilizers), municipal
wastewater and other environmental (Zhou et al. 2015). Therefore, different kinds of
water bodies may be suffered from pollution risks including ground waters (Zeng et al.
2016a, b), river water (Lyubimova et al. 2016; Effendi 2016; Kar et al. 2016), sea water
(Zeng et al. 2016a, b; Al-Rousan et al. 2016), waste water (Singh et al. 2016; Ouyang
and Guo 2016; Sharma and Malaviya 2016), etc. Several water pollutants can cause
very dangerous healthy problems including mutagenicity, embryotoxicity and carci-
nogenicity (due to its side effects), as well as reproductive system, dysfunction of
kidney, liver, brain and central nervous system (Zhou et al. 2015).
340 H. El-Ramady et al.

Due to the industrial pollution, air pollution is common in these industrial areas,
where the air contains numerous pollutants. Concerning the most important pollut-
ants in air, it includes heavy metals (e.g., As, Cr, Pb, Cd, Hg and Zn), carbon mon-
oxide, chlorofluorocarbons, hydrocarbons, nitrogen oxides, organic chemicals (i.e.
volatile organic compounds), sulfur dioxide and particulate materials (Ingle et al.
2014). It is well documented that, the effects of air pollution on human health is
considered a serious issue. Different strategies have been used in recognizing this
relationship between human health and air pollution including the time-series stud-
ies, the fixed-effects or panel studies, the cross-sectional and cohort-based studies
and finally the natural experimental studies (He et al. 2016). Some researchers con-
firmed that air pollution in developing countries has a high and significant level
comparing with those in developed countries (Greenstone and Hanna 2014;
Ebenstein et al. 2015; He et al. 2016). It is found that, the level of ambient air pol-
lution is high in different Asian countries, where the annual average of fine particu-
late matter (PM2.5; particle diameter is 2.5 μm) in China (Beijing) was 85.9 μg m−3
comparing with the annual reference level of WHO is 10 μg m−3 (Selmi et al. 2016)
or 25 μg m−3 for 24 h (Kim et al. 2016) and the European Union (EU) daily limit
values is 50 μg m−3 (Wu et al. 2016).
Due to the importance of air pollution monitoring, several workers from many
countries published their evaluation of air pollution levels such as China (Chen et al.
2016d; He et al. 2016; Lu et al. 2016; Tambo et al. 2016; Wu et al. 2016; Zeng et al.
2016a, b), the United Kingdom (Elliot et al. 2016; Zhong et al. 2016), Japan (Ng
et  al. 2016), France (Selmi et  al. 2016), Belgium (Simons et  al. 2016), the USA
(Laurent et al. 2016; Tu et al. 2016), Sweden (Taj et al. 2016), Italy (Carugno et al.
2016), Spain (Estarlich et  al. 2016), Canada (Pinault et  al. 2016), South Africa
(Klausbruckner et al. 2016), and Egypt (El Ghorab and Shalaby (2016). Therefore, it
could be concluded that, environmental pollution is a global problem and all coun-
tries should collaborate together in monitoring and remediating this issue. This envi-
ronmental pollution includes soil, water and air pollution, which differ from place to
place and from country to other. New approaches and different strategies should be
followed in handling these pollution problems towards the sustainable management.

12.3  E
 nvironmental Pollution and Its Sustainable
Management

The management of natural resources should be performed under the umberella of

sustainable utilization. Because these natural resources are the main source for our
life and support this life with essential food, feed, fibre, and fuel (Akhtar et al. 2016;
Shalaby et al. 2016). The best solution for sustainable pollution management is to
prevent this pollution first or reducing or managing it (Ullwer et al. 2016). Due to
the significance of sustainable pollution management, about 50,000 titles have been
published by SpringerLink or ScienceDirect (by June 1, 2016). This reflects the
high interest of researchers in this serious issue.
12  Nanoremediation for Sustainable Crop Production 341

Soil pollution in the European Union is estimated by more than 2.5 million pol-
luted sites represnting about 60% of them heavy metals and/or hydrocarbons
(Domínguez et al. 2016). Many anthropologic activities cause soil pollution includ-
ing mining and smelting, agricultural production, industrial activity wastes, etc. (Liao
et al. 2016a, b). Concerning the soil pollution management, it is the great challenge
and target several years ago for all countries. Many practices have been performed in
dealing with this management depending on the type and level of pollution.
Recently, many best management practices in dealing with soil pollution have
been published including these issues, the outdoor shooting ranges (Fayiga and
Saha 2016; Rodríguez-Seijo et al. 2016), pesticides (Ouyang et al. 2016b), cement
plant wastes (Cutillas-Barreiro et  al. 2016), mining and smelting (Kapusta and
Sobczyk 2015; Lei et al. 2016), heavy metals (Sołek-Podwika et al. 2016; Cutillas-­
Barreiro et al. 2016; Liao et al. 2016a, b), and agricultural pollution (Babin et al.
2016; Domínguez et  al. 2016). Therefore, it could be sustained soil in general
through recycling of nutrients, the cleaning of air and water, as well as climatic
cycles, where these previous issues represent the fundamental factors in the man-
agement of the natural resources as well (Akhtar et al. 2016).
Due to the urbanization and rapid population growth, there is an increasing
demand of water for all peoples. Due to population explosion and economic expan-
sion, the demand of water by these previous using is continuously increasing across
the world, so a huge amount of waste water resulted. Therefore, an environmental
concern should be taken into account for management water pollution or treatment
in sustainable way (Ahmad et al. 2016; Cai et al. 2016). On the other hand, there is
a serious challenging within a water allocation system in order to effectively utilize
water resources for satisfaction multiple purposes without causing too much envi-
ronmental stress for natural water bodies (Zhang et al. 2014; Cai et al. 2016). Hence,
several potential conflicts will be appeared in many cities across the world due to
this increasing demand and limited water resources (Zhang et al. 2014), particularly
under high reliance on freshwater, which has resulted in severe water tension in
urban water allocation systems (Cai et al. 2016).
Concerning the sustainable water pollution management, it is very important
issue due to the scaricity of water all over the world. Springer International
Publishing already started to publish an international Journal entitled “Sustainable
Water Resources Management” from 2015. It is also published by Springer a new
book entitled “Sustainable Water Management in Urban Environments”, which
edited by Younos and Parece (2016), “Water Pollution and Water Quality Control of
Selected Chinese Reservoir Basins” edited by Huang (2016) as well as this book
“Sustainable Water Management: New Perspectives, Design, and Practices” edited
by Nakagami et al. (2016). This reflects the importance of this issue and how the
handling of water pollution should be holistic. Therefore, many countries estab-
lished several strategies in remediating with this problem such as China (Zhang
et al. 2016; Zhou et al. 2016), Turkey (Alkaya and Demirer 2015; Yuksel 2015),
India (Ahmad et al. 2016), Pakistan (Akhtar et al. 2016; Nazeer et al. 2016), United
Kingdom (Vrain and Lovett 2016) and Egypt (Donia and Bahgat 2016; Khalil and
El-Gharabawy 2016).
342 H. El-Ramady et al.

It could be monitored the pollution of air through collection all information

about nature of air pollutants and its effects as well as different emissions in air and
their concentrations. Due to problems caused by air pollution, the human physical
health and visibility of ecosystems should be addressed (Knox et  al. 2013). So,
several studies have been linked air pollution exposure to some negative outcomes
such as irregular heartbeat, aggravated asthma, decreased lung function, nonfatal
heart attacks and increased respiratory symptoms (Giovanis 2015). Concerning the
sustainable air pollution management, recently a wonderful book entitled
“Sustainable Air Pollution Management: Theory and Practice” edited by
Chandrappa and Kulshrestha (2016) published by Springer. This book includes very
important titles or chapters such as (1) the perspectives and needs for sustainable air
pollution management, (2) different treatments and process design for air pollution
control and (3) safety issues in sustainable air pollution management.
Many strategies have been adopted across the world towards the sustainable air
pollution management differ from place to place depending on the type of air pollu-
tion and its level. These strategies include (1) vegetation in urban areas or using
trees e.g., in France (Selmi et al. 2016), in Greece (Sawidis et al. 2012), in China
(Zeng et al. 2014), etc. (2) prioritizing air pollution in policies, (3) monitoring air
pollution (Gioda et al. 2016; Elliot et al. 2016; Kouddane et al. 2016), (4) identifica-
tion sources of air pollution and pollutants, (5) building smaller self sustaining cities
and new polices as well as legislation should be adopted (Chandrappa and
Kulshrestha 2016). In different an overview, Adams and Kanaroglou (2016) listed
different strategies for reducing air pollution exposure to be include (1) limiting or
capping air pollution emitters, (2) improving technology in order to reduce or elimi-
nate emissions, and (3) providing awareness concerning health risks for citizens.
Therefore, the universe is facing a strong challenge of managing air pollution sus-
tainably because of the complexity of air pollution sources, insufficient resources or
funds for monitoring and enforcement, and political as well as social challenges
issues in defining policy to limit emissions. Global sustainable management issues
for air pollution cannot be remediated and several steps or strategies have to be
considered in minimizing air pollution impacts (Adams and Kanaroglou 2016).

12.4  Environmental Pollution and Crop Production

Crop production should be sufficient to feed all people all over the world. These
sufficient productions are in completion between human feeding (food crops) and
producing non-food crops, e.g. floriculture, horticulture, biomass, and biofuels.
From this point of view, a new approach concerning the use of polluted lands in crop
production is needed. Furthermore, due to one-third of arable lands are already pol-
luted, so using of these polluted lands will be a proper solution in modern agricul-
ture. That means, using of such polluted lands will be resulted more and additional
challenges for the environmental point of view. So, more suitable interventions in
the agri-technological sector are necessary for ensuring the sustainability and safety
12  Nanoremediation for Sustainable Crop Production 343

of these relevant production systems (Abbas et al. 2015; Abhilash et al. 2016). It
could be concluded that, any sustainable crop production system should be consid-
ered that using of arable lands depends on the actual situation for water, energy,
climate changes, and soil.
Recently, some articles have been published regarding the crop production under
pollution such as Sierra et al. (2016), Abhilash et al. (2016), Bu et al. (2016), Tripathi
et al. (2016), and Pandey et al. (2016b). For sustainable crop production in polluted
lands (Table  12.1), some important questions are needed according to Abhilash
et al. (2016). These inquiries include (1) the low income of polluted lands, (2) the
dominant factors controlling the sustainable crop production under multiple con-
taminants, (3) the safety and issues associated with the certification of crop produc-
tion (phytoproducts) from these polluted lands, (4) the biological behavior of crop
under polluted lands and climate changes.
Although polluted or contaminated lands are considered a potential threat for
human health and the safety of foods, these lands should be exploited for both agri-
and environmental sustainability because of the increase demand for arable lands
(Abhilash et al. 2016). Therefore, there is a need to use these polluted lands, beside
the agricultural production, in cultivating of biofuel and biomass crops and in bio-
fortifying crops. Concerning the global debate about fuel or food production, pol-
luted and marginal lands should be considered a promising approach to overcome
the competition between these previous productions (Edrisi and Abhilash 2016).
One profit more for using polluted lands for biofuel crops is to reduce pollution and
the emission of carbon dioxide. Regarding plant species that could be cultivated for
biofuel production, there are several candidates can grow in polluted, degraded and

Table 12.1  Different field experiments conducted for crop production from cadmium polluted
soils and the level of accumulation in edible parts
Cd level
Plant species (Scientific name) (mg kg−1) Plant parts References
Maize (Zea mays L.) 0.07 Grains Meers et al. (2010)
0.89 Whole Ruttens et al. (2011)
plant
Rapeseed (Brassica napus L.) 0.20 Whole Yu et al. (2014)
plant
Spinach (Spinacia oleracea L.) 0.05 Shoots Ismail et al. (2014)
Chrysanthemum indicum L. 7.40 Shoots Lal et al. (2008)
Gladiolus (Gladiolus grandiflorus 8.00 Shoots Lal et al. (2008)
Andrews)
Marigold (Tagetes erecta L.) 7.00 Shoots Lal et al. (2008)
Castor (Ricinus communis L.) 0.43 Stem Irshad et al. (2014)
Common reed (Phragmites < 0.2 Shoots Bonanno et al. (2013)
australis)
Mesquite (Prosopis juliflora DC.) 0.17 Whole Solı’sDomı’nguez et al. (2011)
plant
Yellow lupin (Lupinus luteus L.) 1.60 Shoots Dary et al. (2010)
344 H. El-Ramady et al.

marginal lands including physic nut (Jatropha curcas L.), castor bean (Ricinus cum-
munis L.), Indian beech (Pongamia pinnata L.  Panigrahi), poplar (Populus sp.),
giant reed (Arundo donax L.), switchgrass (Panicum virgatum L.) and Miscanthus
giganteus (Edrisi et al. 2015; Abhilash et al. 2013a, b; Edrisi and Abhilash 2016).
Due to the importance of biomass and biofuel production from polluted lands,
several studies have been conducted for crop production in polluted lands such as
Abhilash et al. (2013b), Bourgeois et al. (2015), Cheng et al. (2015), Edrisi et al.
(2015), Evangelou et al. (2015), Barbosa et al. (2015), Prasad (2015), Edrisi and
Abhilash (2016), Paschalidou et al. (2016), Bauddh et al. (2016), Bian et al. (2016),
Ruiz-Felix et al. (2016), Nishiwaki et al. (2016), Kubátová et al. (2016), and Pandey
et al. (2016a). Therefore, it could be concluded that, crop and its production, like all
biological systems, influences by the environmental pollution and its level. So, it is
very important to reduce or prevent this pollution by a sustainable management.
Moreover, this pollution is not only threatens the crop production and its quality but
also the global food safety. On the other hand, the polluted lands can be considered
an important source for energy crop production as a great approach and a good solu-
tion concerning the global debate about the competition between fuel or food
production.

12.5  Nanotechnology and Pollution Control

Nanotechnology, which emerged in 1980s, is the science of understanding and con-

trolling of matter at dimensions between 1 nm and 100 nm (National Nanotechnology
Initiative 2009). This science has been played an important role in addressing differ-
ent effective and innovative solutions to many different environmental challenges
(Patil et al. 2016). Therefore, a new branch is already emerged calling environmen-
tal nanotechnology, which deals in general with different remediation methods
using the application of nanoparticles. This reflects the recent increasing efforts in
using this branch of nanotechnology in different environmental sectors (Patil et al.
2016). Due to the intensive urbanization and human activities, pollution has become
one of the most important environmental challenges. So, the environment will not
suffer from new pollutants resulting from different advanced technologies but also
the environmental ability for self remediation will be decreased (Mehndiratta et al.
2013). Therefore, an urgent need is needed to find the suitable solutions in order to
reduce these pollutant levels. Hence, nanotechnology is not only considered an
emerging solution for cleaning environment but also for combating pollution
through preventing pollutants formation or reducing the release of these pollutants
(Mehndiratta et al. 2013).
On the other hand, remediation can be defined as the science of reduction or
removal pollutants in soil, sediments, air and water environments using physical,
chemical and biological methods. This remediation can be achieved using nanopar-
ticles or nanomaterials. These nanoparticles have a several benefits owing to their
12  Nanoremediation for Sustainable Crop Production 345

high surface area and small size. These nanoparticles/nanomaterials have a great
diversity in their types that can be used for the remediation purpose including car-
bon nanotubes, dendrimers, nanoscale zeolites, bimetallic particles, enzymes and
metal oxides (Mehndiratta et  al. 2013). Therefore, nanotechnology offers a new
generation of nanomaterials for environmental remediation. This remediation has
cost effective solutions in challenging the problems of the environmental cleanup
from pollutants (El-Temsah et al. 2016). For example, some nanoparticles can be
used in remediation of soil or waste water or groundwater pollution because these
nanomaterials have the following characterizations (1) the very small size of these
nanoparticles can make the injection of them into very small spaces easy and remain
active for a long time, (2) the large surface area can help to a high enzymatic activ-
ity, (3) the movement of these nanoparticles can be transported with the flow of
water and is controlled by gravitational sedimentation, (4) and these nanoparticles
can be adsorbed on the solid matrix (Zhang 2003; Mehndiratta et al. 2013; Bora and
Dutta 2014; Kumar et al. 2014; Tosco et al. 2014; Araújo et al. 2015; Guan et al.
2015; Liu et al. 2015; Louie et al. 2016; Zhao et al. 2016).
Remediation methods can be classified into physical, chemical and biological
methods. Concerning the physico-chemical and engineering methods, they are very
expensive requesting the digging up of polluted and disposal of the wastes to a land-
fill in soils, leading to pollution elsewhere as well as the handling and transport of
hazardous materials within the environment (Adki et al. 2014). Regarding bioreme-
diation processes, it is involved the removal of hazardous pollutants using microbes
(microbial remediation), plants (phytoremediation) and animals (zooremediation).
Regarding zooremediation, it has been accounted as a tool for removal of pollutants
from aquatic ecosystems. Due to the ethical or human health concerns, animals are
rarely considered for bioremediation initiatives (Gifford et al. 2006). Many studies
have been published regarding the suitable solutions of nanotechnology in control-
ling the pollution such as Shan et al. (2009), Wiek et al. (2012, 2014), Baruah and
Dutta (2009), Wang et  al. (2016), Patil et  al. (2016), Devi and Ahmaruzzaman
(2016), Ibrahim et al. (2016), and Subramanian et al. (2016).
The using of plants and their associated microbes in cleaning up different pollut-
ants from soils and water is a promising technology calling phytoremediation (Ma
et al. 2016). Several researchers have been studied phytoremediation process and its
strategies including phytoextraction, phytostabilization, phytofiltration, phytovola-
tilization, etc. (El-Ramady et al. 2015a,b; Agnello et al. 2016; Ji et al. 2016; Liao
et al. 2016a, b; Luo et al. 2016; Ma et al. 2016; Mitton et al. 2016; Shah et al. 2016;
Wan et al. 2016). It is also reported that, phytoremediation of contaminated environ-
ments using nanoparticles (e.g., nano-Au, Ag, CuO, ZnO and C60) have been per-
formed, where these nanoparticles can be absorbed and translocated by plants either
as nano- or in their ionic form (Capaldi Arruda et al. 2015; Andreotti et al. 2015;
Tripathi et al. 2015, 2016; Mustafa and Komatsu 2016; Singh and Lee 2016; Patil
et al. 2016). Concerning the microbial remediation, it is recently reported that, a
developed strategy was established using genetically modified microbes in detoxi-
fying and degradation of environmental pollutants (Chandra 2015). Therefore,
doubtless, the global deterioration of natural resources i.e. soil, water and air by
346 H. El-Ramady et al.

releasing of toxic substances from the continuous anthropogenic activities is nowa-

days a serious problem across the world. This poses numerous issues relevant to the
global ecosystem and human health. The great challenge now is how all countries
can maintain the sustainability of the environment. The control of pollution can be
achieved using the emerging applications of nanotechnology, but more control is
needed with many regulations depends on the nature and size of used
nanoparticles.

12.6  N
 anoremediation and Crop Production from Polluted
Lands

Nanoremediation is the application of nanoparticles or nanomaterials for clean up

or remediation of the environement including soil, groundwater, sediment, air and
wastewater (Hamza et al. 2016; Patil et al. 2016). For example, nanoremediation has
some techniques in treating wastewater including nanomembrane filtration tech-
niques, photocatalysis and adsorption (Qu et al. 2013; Hamza et al. 2016).
Many studies have been published on the benefits of nanoremediation or nano-
technology for environmental clean-up including heavy metals removing from soils
(Ingle et al. 2014; Araújo et al. 2015; Jain et al. 2015; Fajardo et al. 2015; Jain et al.
2016; Gillies et al. 2016; Gil-Díaz et al. 2016a), using plants in clean up (Ghormade
et al. 2011; Capaldi Arruda et al. 2015; Gil-Díaz et al. 2016b), remediation of waste
water (Hamza et al. 2016; Peeters et al. 2016) degradation of pesticides in soil and
water (El-Temsah and Joner 2013; Gomes et al. 2014; El-Temsah et al. 2016). Some
applications of nanoparticles can be used in remediating soil and air are presented
in Table 12.2 (Ibrahim et al. 2016).
Nanoremediation using nanomaterials is one of the most strategies for enhancing
the sustainability of crop production from polluted lands. These strageties including
(1) the application of agro-biotechnology, (2) root biology or rhizospheric engineer-
ing, (3) molecular biology and (4) nano-biotechnology can be used for sustainable
crop production from such lands (Germaine et al. 2009; Hur et al. 2011; Houben
et al. 2013; Meister et al. 2014; Abhilash and Dubey 2015; Abhilash et al. 2016).
The great challenge and most important concern is involved the cultivating edible
plants in polluted lands and its relationship to food chain. Hence, it should be pre-
vented any potential risks for human health resulted from the biomagnification the
pollutants by plants in the food chain (Abhilash et al. 2016). This is the difficult
equation: how can we produce edible plants from polluted lands and at the same
time these harvested plants will be safe without any threat for human health. This
may request some approaches including (1) breeding via selection low accumulator
cultivars for these pollutants, (2) reducing the bioavailability of these pollutants in
soils and (3) restricting the pollutants uptake and their translocation to these edible
parts (YeTao et al. 2012; Abhilash et al. 2016). It is worth to mention that, the ben-
efits of the revitalization of polluted lands include safe phytoproducts, soil carbon
12  Nanoremediation for Sustainable Crop Production 347

Table 12.2  Application of some nanoparticles in air and soil remediation

Nano-particles Target pollutants Observations or effects References
Nanoparticles for air remediation
Silica Atmospheric lead (Pb) The increased capture of Pb by Yang et al.
nanoparticle SiNPs was explained by the (2013)
(SiNPs) large surface and the
negative-charged groups in the
SiNPs
Zn12O12 Carbon disulfide (CS2) At the increasing number of Ghenaatian
nanocage the CS2 molecules, the et al. (2013)
adsorption energy of CS2 per
molecule decreased which
may be due to the steric
repulsion between the CS2
molecules
Aligned carbon Aerosols The filtration performance of Yildiz and
nanotube the novel filters showed that Bradford
when the number of carbon (2013)
nanotubes layers increased, the
filtration efficiency increased
dramatically, while the
pressure drop also increased
Nanoparticle for soil remediation
Ni/Fe Decabromodiphenyl ether Ni/Fe bimetallic nanoparticles Xie et al.
bimetallic (BDE209) were able to degrade (2014)
BDE209 in soil at ambient
temperature, and the removal
efficiency can reach 72%
Nano Organo-chlorine 1 g nZVI kg−1 was efficient for El-Temsah and
zerovalent iron insecticides (DDT) dichloro-diphenyl Joner (2013)
(nZVI) trichloroethane (DDT)
degradation in spiked soil,
while a higher concentration
was applied for the treatment
of aged contaminants in soil
Nano-­ Cadmium and lead (nHA) significantly formed
crystalline Pb/Cd phosphate (e.g.,
Hydroxyl-­ hydroxypyromorphite-like
apatite (nHA) mineral) that was able to
reduce water-soluble,
bioaccessible, and
phytoavailable Pb/Cd

sequestration, biofortification (improvement the nutrient content of agricultural

products) and phytoremediation (removal pollutants from the environment).
Nanoremediation of soils, as a promising strategy in minimizing the entry of pol-
lutants in plant parts, can be performed using nanoparticles such as zero-valent iron
nanoparticles (nZVI), ZnO, TiO2, carbon nanotubes, fullerenes and bimetallic nano-­
metals. These nanoparticles have four missions in soil nanoremediation including
348 H. El-Ramady et al.

(1) reducing the soil heavy metal concentration in leachates to acceptable level, (2)
immobilization of soil heavy metals (e.g. Cr VI, Pb II, As III and Cd) in polluted
soils (Mallampati et al. 2013), (3) remediation the redox potential enhancing the
convert of some soil heavy metals (like Cr VI) to less toxic forms and (4) degrada-
tion of organic contaminants (e.g. DDT, chlorinated organic solvents, carbamates,
etc) (Abhilash et al. 2016). A summary of some important review articles on differ-
ent environmental issues including pollution, nanotechnology and pollution control,
nanoremediation and crop production in polluted lands can be listed in Table 12.3.

Table 12.3  Different published environmental issues including pollution during 2016
Focus area of the study References
(1) Environmental pollution
The electronic wastes and its recycling in India as a source of the Awasthi et al. (2016)
environmental pollution
Different environmental applications of nanotechnology in air, soil Ibrahim et al. (2016)
and water for remediation these natural resources
The environmental significance of selenium and its pollution as well Tan et al. (2016)
as the biological treatment technologies
Environmental pollution resulted from engineered nanomaterial and Caballero-Guzman and
its release in the environment Nowack (2016)
Using polluted lands in sustainable crop production: Biomass and Abhilash et al. (2016)
biofuel as well as edible plants
(2) Soil and water pollution
Arsenic pollution in groundwater in Southwest China: As Zhang et al. (2016)
geochemical characteristics and its significance
Application of iron sulfide particles for groundwater and soil Gong et al. (2016)
remediation
Soil pollution resulted from the outdoor shooting ranges: Its health Fayiga and Saha (2016)
effects, bioavailability and best management practices
Occurrence, impacts and removal of emerging substances of concern Hamza et al. (2016)
from wastewater
(3) Air pollution
The environmental pollution of air: Coupling dynamics and Zhong et al. (2016)
chemistry in modeling of street canyons
Pollution of particulate matter and its implications for environmental Rai (2016)
biomonitoring
The cognitive functioning resulting from exposure to air pollution Clifford et al. (2016)
The relationship between ambient air pollution and suicide in Tokyo Ng et al. (2016)
city during 11 years
(4) Environmental nanotechnology
Different applications of nanotechnology in improving the Hussein (2016)
performance of solar collectors and its recent advances
Nanotechnology and the new opportunities in plant sciences Wang et al. (2016)
(continued)
12  Nanoremediation for Sustainable Crop Production 349

Table 12.3 (continued)
Focus area of the study References
The race between China and the United States in the nanotechnology Dong et al. (2016)
sector and its environmental issue
Nanotechnology in agriculture sector: New approached in Servin and white (2016)
understanding engineered nanoparticle exposure and its risk
(5) Nanoremediation
Environmental nanotechnology for cleaning up the environment Patil et al. (2016)
including the potential risks and emerging solutions
The nanoremediation strategy for the recovery of polluted soil with Gil-Díaz et al. (2016a)
arsenic
Nanoremediation approach using zeolite particles Gillies et al. (2016)
Using barley plants as a stability of the nanoremediation Gil-Díaz et al. (2016b)
Nanoremediation using green nano-scale zerovalent iron Rede et al. (2016)
nanoparticles through the ecotoxicological impact on lettuce plants
and soil remediation
Nanoremediation coupled to electro-kinetics for removal Gomes et al. (2016)
polychlorinated biphenyls from soil

Therefore, it could be concluded that, promising results have been obtained from
the application of nanotechnology for the remediation of contaminants. Furthermore,
nanoremediation also can provide us with a way in purifying soil, air and water
resources by using nanoparticles/nanomaterials as a catalyst and/or sensing sys-
tems. Groundwater remediation for drinking and reuse is a promising field, which
can be achieved by using nanomaterials such as zero-valent iron and carbon nano-
tubes. However, there are still some open questions remaining concerning the
potential risks and human health associated with this use of nanomaterials in the
environment. Concerning the sustainable crop production from polluted lands using
nanoremediation, there are many economic, social and ecotoxicological consider-
ations and some strategies regarding minimizing the potential risks for human
health should be kept in mind. Furthermore, restoration soil functionality and
growth of plants monitoring in polluted lands are necessary before any field recom-
mendations for application of nanoremediation.

12.7  Conclusion

As mentioned above, nanoremediation can be considered an interesting approach in

dealing with both environmental health and safety terms whereas, there is not fully
understanding concerning the behavior of nanoparticles/nanomaterials on the large
scale. Therefore, the use of nanoparticles/nanomaterials for remediation should be
followed after further safety and appropriate researches. Furthermore, the polluted
350 H. El-Ramady et al.

lands represent a real threat for the environment espeacilly in case of the dangerous
contaminants but on the other hand these polluted soils may offer a real opportunity
for the multiple cropping in both the production of foods and the biorefineries for
the bioeconomy. Further studies are needed in dealing with nanremediation includ-
ing (1) the biotoxicity of nanomaterials/nanoparticles (e.g., the mobility and bio-
geochimstry of these nanoparticles in particular under the field conditions), (2) the
investigation of local environmental conditions and their effects on the fate, trans-
port and transformation of nanoparticles/nanomaterials, and (3) study the antago-
nistic or synergistic effects of nanoparticles and microbial activities in soils.

Acknowledgements Authors thank the outstanding contribution of STDF research teams

(Science and Technology Development Fund, Egypt) and MBMF/DLR (the Federal Ministry of
Education and Research of the Federal Republic of Germany), (Project ID 5310) for their help.
Great support from this German-Egyptian Research Fund (GERF) is gratefully acknowledged.

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Index

A Cytotoxicity, 124, 126, 129–131, 149,

Accumulation, 10, 16, 27, 28, 32, 34, 46, 54, 222, 223, 225, 227, 244–247,
69, 130, 169, 171–175, 183, 186–188, 250–253, 255
190, 221, 247, 293, 316–319, 324, 341
Agricultural nanotechnology, 21–37
Agriculture, 1–17, 21–37, 41–71, 151, 167, D
203–229, 265, 316, 340 Detoxification pathways, 178, 179, 184
Agro-food, 24, 205–210, 213, 214, 221
Anticancer, 124, 128, 130, 131, 226
E
Ecofriendly, 14, 294
B Electrochemical nanobiosensors, 44–45, 66
Bioaccumulation, 100, 111, 222, 243, 308, Emulsions, 80, 84–94, 96–109, 111, 130, 139,
313–316, 318 141–144, 149, 219, 220
Bioactive compounds, 79–84, 91, 92, 98, Emulsomes, 107
100–107, 109, 112, 139, 151, 162 Encapsulation, 10, 11, 80–85, 87, 91–98, 100,
Bioavailability, 23, 26, 81, 83–85, 92–94, 101, 103–105, 108, 111, 112, 130, 139,
97, 106, 109–112, 123, 125–129, 132, 142–144, 150, 152–154, 156–158, 162,
141, 146, 151, 158–161, 175, 206, 219, 218–220, 274
220, 251, 252, 272, 291, 308, 312, 325, Engineered nanomaterials, 22, 23, 159, 221,
344, 346 255, 266, 268–270, 272, 275–293,
Bioconcentration, 313, 316 296–298, 308–324, 346
Biodiversity, 268–270 Environment, 7, 9–11, 14, 22, 23, 26–28, 35,
Biological, 9, 24, 43–46, 52, 54, 71, 110–112, 42, 51, 64, 145, 148, 168, 170, 172,
129, 145, 146, 155, 158, 204, 205, 208, 174, 185, 203–229, 242–244, 251,
214, 216, 218, 220, 227, 229, 242, 244, 254–257, 268–271, 276, 292, 293,
247, 249, 251, 254, 257, 266–271, 273, 308–314, 316, 324, 325, 335, 336,
294, 295, 309–312, 341–343, 346 342–348
Biomagnification, 243, 308, 313–316,
325, 344
Biotransformation, 180–181 F
Fertilizers, 1, 2, 5, 6, 9, 11, 12, 14, 16, 23, 24,
42, 43, 51, 61, 71, 205, 207, 208, 214,
C 218, 255, 266–276, 292–297, 337
Caseins, 138, 139, 141–150, 152, 162 Food, 2, 21–37, 41–71, 79–112, 137–162, 183,
Critical theory, 32–34 203–229, 242, 269, 307–325, 334

© Springer International Publishing AG 2017 365

S. Ranjan et al. (eds.), Nanoscience in Food and Agriculture 5, Sustainable
Agriculture Reviews 26, DOI 10.1007/978-3-319-58496-6
366 Index

Food nanotechnology, 15 P
Food quality, 2, 30, 43, 52, 68, 204, 225 Patents, 1–17, 25, 27, 28, 30, 31. 43,
68–71, 132, 159–161, 211, 220, 271,
273, 275, 292
G Phenomics, 193
Genotoxicity, 183, 243–245, 250, 251, Politics, 21–37
253, 257 Polluted lands, 334, 335, 340–342, 344–347
Green house gas emissions, 274–275 Pollution, 42, 294, 334–344, 346
Power, 7, 22, 27–29, 32–34, 37, 45, 51, 242
Precision agriculture, 43, 51, 205
I
Intellectual property rights (IPRs), 12–15, 30,
31, 43, 69–70, 160–161 R
Regulation, 22, 26–30, 34, 36, 42, 110,
111, 179, 184, 203–229, 248,
M 255–257, 271, 291–293, 298,
Metabolomics, 178, 193 323, 324, 344
Resveratrol, 105, 121–133, 143, 153
Risk assessment, 26, 36, 109–110, 183, 228,
N 229, 254, 310, 311
Nanobiosensors, 42–45, 52–68, 70, 71, 272
Nanobiotechnology, 2, 70, 343
Nanoemulsion clusters, 105–106 S
Nanoformulation, 9, 16, 23, 29, 133, 145–150 Soil health, 268–271, 276, 293,
Nanomaterials, 6, 22, 43, 80, 158, 167–193, 296–298
203–229, 241–257, 266, 307–325, 334 Soil management, 265–298
Nanoparticles, 9, 23, 43, 99, 123, 138, 168, Structured nanoemulsions, 98–106
206, 241, 266, 308, 335 Sustainable crop production, 333–348
Nanoremediation, 9, 12, 333–348
Nanosciences, 2–6, 12–15, 205–208, 229
Nanosensors, 5, 7, 9, 15, 23, 29, 41–71, T
159, 216 Targeting, 48, 123, 127, 129, 141, 150, 158,
Nanostructures, 43–45, 47, 54, 56, 61, 64, 66, 245, 273, 294
70, 71, 79, 145, 146, 150, 159, 170, Technological change, 31–34, 36, 37
219, 253, 267, 294 Toxicity, 25, 27, 65, 109–111, 125, 132, 138,
Nanotechnology, 2, 21, 42, 111, 157, 167, 204, 148, 167–193, 203–229, 241–257, 268,
241, 266, 308, 334 270, 273, 275–277, 279, 285, 291, 308,
Nanotoxicity, 168, 179–186, 205, 206, 221, 310–313, 316, 322–325
227, 276, 296 Translocation, 172–175, 186–188, 192,
Nanotoxicology, 206, 215, 242, 245–250 206, 224, 225, 274, 277,
Natural barriers, 169 295, 344
Trophic transfer, 308, 314–316, 325

O
Oxidative stress, 53, 92, 176–179, 185, 187, W
189, 191–193, 205, 224, 243, 247, 250, Whey proteins, 89–91, 103–105, 109, 138,
251, 257, 268 139, 141–144, 151–154