materials

Review
Naturally Derived Cements Learned from the Wisdom of
Ancestors: A Literature Review Based on the Experiences of
Ancient China, India and Rome
Zhan Su 1 , Zhen Yan 1, *, Kazunori Nakashima 2 , Chikara Takano 2 and Satoru Kawasaki 2

1 Division of Sustainable Resources Engineering, Graduate School of Engineering, Hokkaido University,

Sapporo 060-8628, Japan
2 Division of Sustainable Resources Engineering, Faculty of Engineering, Hokkaido University,
Sapporo 060-8628, Japan
* Correspondence: zhenyan-geotech@elms.hokudai.ac.jp

Abstract: For over a thousand years, many ancient cements have remained durable despite long-term
exposure to atmospheric or humid agents. This review paper summarizes technologies of world-
wide ancient architectures which have shown remarkable durability that has preserved them over
thousands of years of constant erosion. We aim to identify the influence of organic and inorganic ad-
ditions in altering cement properties and take these lost and forgotten technologies to the production
frontline. The types of additions were usually decided based on the local environment and purpose
of the structure. The ancient Romans built magnificent structures by making hydraulic cement using
volcanic ash. The ancient Chinese introduced sticky rice and other local materials to improve the
properties of pure lime cement. A variety of organic and inorganic additions used in traditional lime
cement not only changes its properties but also improves its durability for centuries. The benefits they
bring to cement may also be useful in enzyme-induced carbonate precipitation (EICP) and microbially
induced carbonate precipitation (MICP) fields. For instance, sticky rice has been confirmed to play
Citation: Su, Z.; Yan, Z.; Nakashima, a crucial role in regulating calcite crystal growth and providing interior hydrophobic conditions,
K.; Takano, C.; Kawasaki, S. which contribute to improving the strength and durability of EICP- and MICP-treated samples in a
Naturally Derived Cements Learned sustainable way.
from the Wisdom of Ancestors: A
Literature Review Based on the
Keywords: naturally derived cement; Portland cement; enzyme-induced carbonate precipitation
Experiences of Ancient China, India
(EICP); microbially induced carbonate precipitation (MICP)
and Rome. Materials 2023, 16, 603.
https://doi.org/10.3390/
ma16020603

Academic Editors: Chadi Maalouf, 1. Introduction

Guillaume Polidori and
With the acceleration of urbanization, modern Portland cement is gradually becoming
Christophe Bliard
the most commonly used construction material due to its excellent properties [1,2]; however,
Received: 29 November 2022 modern Portland cement still has some noteworthy drawbacks. For example, the use of
Revised: 4 January 2023 modern Portland cement in geotechnical reinforcement foundations increases the pH of
Accepted: 5 January 2023 the soil and surrounding groundwater. In addition, modern Portland cement is considered
Published: 8 January 2023 to have a fairly high carbon footprint. As the production of 1 ton of cement emits about
1 ton of CO2 , the cement industry accounts for 5–8% of global CO2 emissions [3–5]. In
2021, cement consumption was expected to reach 4.4 billion tons, and its production was
expected to generate 450 kg/m3 of CO2 emissions, representing 25% of total annual global
Copyright: © 2023 by the authors.
manufacturing emissions [6–8] and 8% of anthropogenic CO2 emissions [9]. It is estimated
Licensee MDPI, Basel, Switzerland.
that by 2050, global CO2 emissions from cement production will reach 2.34 billion tons [10].
This article is an open access article
In order to be more sustainable and reduce the environmental burden, a great deal of
distributed under the terms and
conditions of the Creative Commons
research has been conducted to develop new technologies to reduce the consumption of
Attribution (CC BY) license (https://
modern Portland cement in ground improvement practices.
creativecommons.org/licenses/by/
With archaeological discoveries, there have been different types of calcareous and
4.0/). gypsum cements found that were widely used in buildings around the world as early as

Materials 2023, 16, 603. https://doi.org/10.3390/ma16020603 https://www.mdpi.com/journal/materials

Materials 2023, 16, 603 2 of 15

thousands of years ago [11]. Using specific natural additives, our early ancestors improved
the performance of ancient cements to meet various needs. For example, the strength and
durability of cement was more important when used to maintain living infrastructure
construction or buildings that played an important role, such as city walls and harbors, and
corresponding additives would be added [12]. Some of which gave these ancient cements
extraordinary strength and durability, allowing ancient buildings to survive, even through
thousands of years of environmental erosion.
Recently, similar to our ancestors’ practice of adding various additives to ancient ce-
ments, attempts have been made to use biopolymers in geotechnical engineering. Biopoly-
mers are polymers produced from natural resources, including polysaccharides (e.g., cellu-
lose), proteins (e.g., gelatin, casein and silk), and marine prokaryotes; biopolymers can also
be produced by chemical synthesis of biologically derived monomers (e.g., polylactic acid)
or microbial activities (e.g., xanthan gum or gellan gum) [3,13–17]. Biopolymers are envi-
ronmentally friendly and have been widely used in food and medical applications [18,19].
Recent studies have shown how biopolymers can be used for soil consolidation [20–25],
soil permeability control [26–28], erosion reduction [29–34], dust control [35–38] and even
water treatment [39–42]. However, the durability of biopolymers is often questioned given
the current limited yield of biopolymers and specifically regarding biopolymer-based
soil treatments.
Meanwhile, the study of biocements has attracted many researchers [43–46]. This
promising technology in specific geotechnical engineering could replace conventional
methods for various situations, e.g., pre-construction soil improvement; slope and dam
stabilization; stabilization of sandy soils; protection against wind and water erosion; water-
proofing of ponds, canals, landfills and reservoirs; and chemical, radiological and biological
soil immobilization. It could have a wide range of practical applications in the future [47].
There are two main types of biocement technology: MICP and EICP [48]. The mechanism of
MICP is the use of the urea decomposition capacity of microorganisms to metabolize urea,
producing ammonium and carbonate. The carbonate can then be combined with calcium
ions to produce calcium carbonate precipitates (Equations (1)–(5)). Calcium carbonate pre-
cipitates can bind loose particles, strengthening and improving the strength and stiffness of
the soil [49–52]. Similar to MICP, EICP also improves soil properties by inducing calcium
carbonate precipitation. The difference is that EICP uses urease isolated from bacteria or
plant solutions to carry out the reaction, and urease is a nickel-dependent metalloenzyme
rather than a microorganism. However, biocement has some problems to overcome, such
as the high cost of using EICP and MICP. In addition, one of the byproducts of the reac-
tion, ammonium, is toxic to the natural environment and to humans. The combination of
biopolymers and biocements may be a promising method to overcome the drawbacks from
using biopolymers or biocements alone.

CO(NH2 )2 + H2 O → NH3 + NH2 COOH (1)

NH2 COOH + H2 O → NH3 + H2 CO3 (2)

2NH3 + 2H2 O → 2NH4 + + 2OH− (3)
2OH− + H2 CO3 → CO3 2− + 2H2 O (4)
2+ 2−
Ca + CO3 → CaCO3 (5)
In this paper, we summarize and compare some ancient cement and modern prin-
ciples of using biopolymer-reinforced foundations from different regions and try to link
the high durability of ancient cements with the advantages of biopolymer-reinforced
foundations and apply them to biocements. Thus, we try to solve the shortcomings of
current biocements.
Materials 2023, 16, 603 3 of 15

2. Types and Characteristics of Ancient Cements

2.1. The Wisdom of Ancient Rome
In the republican period of Rome, dated from the late 2nd century to mid-1st century
B.C., the ancient Romans discovered how to create hydraulic cement, a kind of building
material with exceptional performance [53,54]. Hydraulic cement was used as a durable
building material. As an example, concrete structures in ports along the central Italian coast
and in Mediterranean regions have maintained cohesion and integrity for 2000 years while
partially or fully submerged in seawater. Consisting of lime and sandy volcanic ash, it is
rich in chemically reactive aluminosilicates [55]. Pozzolanic reactions of volcanic ash with
hydrated lime is thought to dominate the cementing fabric and durability of 2000-year-old
Roman harbor concrete.
Ca2+ + 2OH− + SiO2 → C-S-H (6)
Ca2+ + 2OH− + Al2 O3 → C-A-H (7)
Modern Portland cement is a crystalline-structured amorphous material made from
clinker that is ground at 1450 ◦ C, mixed with water and non-reactive aggregates (such as
sand or gravel) and pumped into a mold in a fluid state. The concrete sets within a few
hours and hardens within a few weeks as the Portland cement hydrates to form various
compounds, mainly poorly crystalline calcium silicate hydrates (C-S-H), which bind to the
sand and coarse aggregate (Equations (6) and (7)). Improper construction or maintenance
results in uneven drying shrinkage of the hardened cement paste and concrete aggregates
and microcracks in the concrete matrix, leading to a decrease in Young’s modulus and
compressive strength. If the temperature is above 65 ◦ C, uncontrolled hydration leads
to the development of C-S-H, which absorbs sulfate and is subsequently expelled during
cooling and aging to form deleterious ettringite, which causes the cement paste to swell
and decouple from the aggregate, creating characteristic voids around these particles [56].
When extreme high temperature conditions are reached, Portland cement will begin to
decompose [57]. This can significantly reduce the service life of Portland cement.
Compared with ordinary Portland cement, the amount of lime used in ancient Roman
cement was only about 1/3 of that used in modern concrete; therefore, the amount of carbon
dioxide emissions produced during the manufacturing of ancient Roman concrete was only
about 1/3 of that of modern concrete. Meanwhile, the lifespan of Roman buildings is one to
two orders of magnitude higher than that of modern buildings. Recent analytical techniques
have shown that the remarkable durability of Roman hydraulic cements comes from the
crystalline calcium aluminum silicate hydrate (C-A-S-H binder) in the cementitious matrix,
which is produced by a reaction of seawater, lime, and volcanic ash [58–61]. One of the
main components of Roman hydraulic cements, volcanic ash is a siliceous, aluminous
material that has no cementing ability on its own, but can chemically react with water and
calcium hydroxide to form compounds with cementing properties. When mixed with lime
and rubble, they not only provide strength for other constructions, but when used for piers
built in the sea, they solidify in the water and neither the waves nor the force of the water
can dissolve them. Roman engineers soon realized the remarkable potential of this new
material, as it was particularly suitable for building hydraulic installations, bridge footings
and harbor structures. Roman engineers could build harbors wherever political, economic
or military considerations existed, not limited to areas with favorable geographical features.
The resulting changes in Roman architecture could only be described as “revolutionary”.
Al-tobermorite—a rare, layered calcium silicate hydrate mineral in ancient Roman
cement—is composed of aluminosilicate chains bounded by interlayer regions and calcium
oxide sheets [59]. Aluminum tobermorites are crystals with a plate-like shape, and these
crystals are interlaced to strengthen the cementitious matrix, thus improving the resistance
of concrete to brittle fracture. Researchers believe that as tobermorite grows throughout the
concrete, it provides strength because of its long plate-like crystals that allow the concrete
to flex without breaking when subjected to forces. Moreover, when the tobermorite (Al-
Materials 2023, 16, 603 4 of 15

tobermorite) forms between the aggregate and cement, it prevents further extension of
microcracks, thus greatly enhancing durability [60].
Despite Roman cement having many disadvantages compared with modern Portland
cement, such as its slower hardening time and the considerable time it takes for the seawater
to strengthen the cement, as well as the final material being compressively weaker than
Portland cement, its use has clear environmental advantages. The use of volcanic ash
in Roman cement results in a reduced need for lime and correspondingly lower energy
consumption and CO2 emissions than the Portland cement materials typically used today.
Moreover, the longevity of Roman constructions is one to two orders of magnitude higher
than that of modern constructions. Reinforced concrete (rebar) is used to construct massive
structures in current construction, but its life expectancy is only several decades. Part
of the reason for this is that when the surrounding concrete cures, oxidation takes place
and the reinforcing bars rust over decades, causing sufficient expansion that causes cracks
to form in the concrete. If the structure comes in contact with seawater, rebars could
be corroded in less than 50 years, and reactions with calcium hydroxide would cause
expansion within the concrete structure. Ancient Roman structures did not have steel
reinforcement, but rather reinforced concrete on a structural scale. Roman cement was
“self-healing” when it encountered seawater, meaning that when cracks appeared in the
cement, the infiltrated seawater reacted with the phillipsite in the volcanic ash to form
aluminium tobermorite crystals that filled the cracks and strengthened the whole [62–64].
Recently, some researchers have tried to apply the mechanism of Roman cement to improve
modern cement. For instance, fly ash, a material which is produced by the combustion
of coal, has been used for cement production. Fly ash has similar (pozzolanic) properties
to the volcanic ash that Romans used to make their concrete, due to its broadly similar
chemical composition; thus, it has greatly improved the strength and durability of concrete
and has become a critical factor in the preservation of buildings [65].

2.2. The Wisdom of Ancient China

Archaeological evidence suggests that lime-based cementitious materials were widely
used to reinforce columns, make ground improvements and build roofs from the mid-
to late Western Zhou Dynasty (1046–771 B.C.) [66]. By the time of the Northern and
Southern Dynasties (386–589 A.D.) [67], glutinous lime cement was already a mature
technology. Glutinous rice, also known as waxy rice, is a type of rice grown mainly in East
and Southeast Asia. It is characterized by its white appearance, high straight-chain starch
content, and sticky texture [68]. In addition to being a staple food in China, glutinous rice
has been widely used in various other applications, including building construction. For
example, many historical Chinese documents report the use of lime–sticky rice mortar
for the construction of river dams, barns, food gates and tombs. The architectural work,
Tian Gong Kai Wu, records in detail its composition, production methods and properties:
“Cement was made by adding glutinous rice soup and actinomycetous sugar cane juice
to a mixture of 1/3 lime and 2/3 loess and river sand, and mixing thoroughly. The
buildings constructed with it are strong and durable, and this material is called Tabia.”
This “Tabia” is the glutinous rice–lime cement mentioned above. The addition of natural
organic compounds, such as glutinous rice soup, greatly improved the performance of
cement building material. Due to its excellent properties and performance, such as high
bond strength, good toughness, high water erosion resistance, and durability, sticky rice
cement became the most established and widely used technology in ancient Chinese
construction [69].
Modern evaluations show that the bonding properties of sticky rice cement are good
enough to match modern cement. In addition to its high strength, sticky rice cement was
characterized by its amazing durability [69]. It was used to build important architecture,
such as city walls, palaces, stone bridges, dams, etc. After hundreds and even thousands of
years, such architecture is still well-preserved. Further research have found that sticky rice
pulp plays the role of a biological template, regulating and coordinating the carbonation
Materials 2023, 16, 603 5 of 15

of cement to generate nano-sized calcium carbonate crystals with a fine structure, and
improves its toughness, impermeability, and compressive strength [70]. The reason why
sticky rice can endure in cement for a long time is due to the anticorrosion effect of lime. The
organic and inorganic compositions wrap and pad each other, similarly to the formation
process of biomineralization products, such as bones, teeth, and shells. The partially
reactive calcium hydroxide, wrapped in sticky rice pulp, inhibits the growth of bacteria
and thus protects the glutinous rice from decay for a long time [71–73].
In addition to sticky rice soup, blood cement was also common in ancient China, and
was mainly used for building painted floors [74]. According to relevant records, pig blood
was used on the floor of the Xianyang Palace site during the Qin Dynasty (221–206 B.C.) [75],
mixing lime and ginger stone into a dark red, smooth surface with a moisture-proof effect.
It was found that animal blood played an important role in cement as it added air, reduced
water, prevented freezing and thawing, resisted cracking and increased bond strength. The
underlying mechanism is as follows: Firstly, the protein in the blood is expected to have a
foaming ability. Thus, the tiny bubbles can improve the cement’s workability. Secondly,
anions and hydrophilic groups in blood protein can generate electrostatic repulsion between
cement particles and improve their dispersion. Thirdly, blood protein is decomposed in an
alkaline environment, connects with calcium ions in cement, and enhances bond strength.
Fourthly, the amino and carboxyl groups in blood protein provide waterproof ability.
Tung oil is another material that was widely used as a cement additive. This building
material was mainly composed of boiled tung oil and lime mortar [76] because it had good
water tightness, anti-codling effects and high bond strength. Thus, in ancient China, it
was widely used in water well hooks, greasy seams in wooden boats, hole filling, housing
grounds, and buildings with special requirements for waterproof ability and durability.
According to recent research, the high performance of tung oil–lime cement was likely
caused by the compact structure of this material. In this cement, calcium hydroxide reacts
with tung oil and carbon dioxide, and produces calcium carboxylate and calcium carbonate,
respectively. Thus, a lot of particles in mortar are bonded together through the coordination
of calcium ions and crosslinking of tung oil, and a compact structure is formed [77]. This
reaction between calcium hydroxide and tung oil was the most important factor causing
tung oil–lime cement curing at an early stage. At this stage, the probability of calcium
hydroxide being converted into calcium carbonate was very still very low, which is totally
different from common pure lime cement; the early strength of tung oil–lime cement was
given by the compact microstructure established by carboxylate. Even 10-year-old tung
oil–lime mortar could not reach the relative degree of carbonization found in common
lime mortar that had remained for 90 days [77]. The compact microstructure established
by cement curing blocked carbon dioxide and water from entering the interior of cement.
In addition, the hydrophobicity of tung oil also kept calcium hydroxide from water. As a
result, tung oil–lime cement could keep alkalinity for a long time, further ensuring that the
tung oil did not decompose and had long-lasting durability.

2.3. The Wisdom of Ancient India

The ancient Indians mainly used various plant and animal extracts to improve the
strength and durability of ancient cements. For example, it was found from previous
research literature that Indians added rennet, herbs, cactus extracts, lentils, castor oil, and
many other natural animal or plant extracts to lime cement to build their temples, palaces
and other important structures [78].
Several researchers have analyzed the effects of organic extracts and inorganic min-
eral additions used in lime cements in ancient India on mechanical properties [79]. The
results showed that, in pure lime cement, for ease of construction, there are more water
molecules between successive lime particles, which reduces bond strength and leads to
early damage [80]. In addition, this may generate cracks in the lime cement and allow for
their random propagation. Thus, under compressive conditions, pure lime fails earlier than
cement with additives.
Materials 2023, 16, 603 6 of 15

The addition of organic additives can change the properties of lime cements. For
example, they increase the bond strength between particles in lime cements by enhancing
adhesion, or by reducing the pore size. For example, the presence of proteins in the organic
matter interacts with carbon dioxide to increase the hydrophobicity of the cement [81].
This interaction leads to the formation of calcium complexes, which increase compressive
properties. In addition, fermented organic matter has air-entraining properties in the
lime matrix. An organic matter additive can introduce millions of tiny air bubbles into
the lime cement, improving the workability of the mix and thus reducing the necessary
water/binder ratio, increasing its strength. In addition, when organics are added to lime
cement, the entrained air promotes the carbonation process and this increased rate of
carbonation increases the precipitation of carbonate crystals, leading to an increase in
weight and mass, which ultimately increases the strength of the cement.
The addition of organic matter to the lime matrix could also affect the crystal core of
calcium carbonate, changing the form of calcium carbonate or promoting the generation
of other substances, thus changing the properties of the cement [80]. For example, when
adding traditional herbal additives such as jaggery, the addition of organics in the lime
matrix enhances the carbonation rate of lime and converts portlandite to form a new
type of mineral, weddellite (calcium oxalate monohydrate). Formation of weddellite
in the lime matrix can fill the gap between two lime particles and enhance the binding
strength of mortar. Additionally, the calcium complexes formed during the interaction of
proteins with the divalent calcium ions contribute to reduced water absorption, similar to
synthetic polymers [81]. The proteinaceous material present in the lime mortar samples
converts calcium oxide into calcium oxalate. These proteins can chemically react with clay
particles by exchanging the inorganic cations of the clay with organic cations, resulting in
a mechanism that uses the ability of amino acids (amides) to encourage clay flocculation.
Therefore, organic material protects cement structures from environmental deterioration.
Overall, the carbohydrate, protein and fat compositions in different organic materials
and their interaction with lime are important factors that affect compressive strength and
increase bonding properties [82].

3. Future Prospects for New Ground Consolidation Technologies Learned from

Ancient Cements
In general, additives used in cements throughout antiquity fall into two broad cat-
egories: organic and inorganic additives. In most cases, additives could contribute to
strength improvements in strength and durability of the material by adjusting the crystal
form, increasing viscosity, and reducing porosity.
In addition, it is worth noting that due to ancient productivity limitations, most
additives were obtained directly from natural materials or from low-cost products and
fertilizers from human life. This feature was a prerequisite to make an additive or cement
widely available. Even royalty or religious leaders could not afford to use an additive for
large-scale construction if the production costs were too high or the manufacturing process
too complex to produce enough material.
Recently, similar to the ancestral practice of adding various additives to ancient
cements, attempts have been made to start directly adding biopolymers for geotechni-
cal engineering. Biopolymers are polymers produced from natural resources, including
polysaccharides, proteins, chemically synthesized bio-derived monomers and microbial
activity. Biopolymers are environmentally friendly and widely used in food and medical
applications [26]. Table 1 summarizes common biopolymers used in geotechnical research
and practice [83].
As one of the most prevalent natural biopolymers, starch is found in large quantities in
the seeds, grains and roots of many different types of plants, including maize, rice, wheat,
corn, potato and cassava. Depending on the source, this natural biopolymer has different
characteristics and appearances [84]. Starch is used as thickeners and stabilizers [85],
fortifying agents [86] and binders [87] in a variety of industries, including those in the food,
Materials 2023, 16, 603 7 of 15

textile, cosmetic, plastic, paper and pharmaceutical sectors. Starch has been utilized as
a drilling fluid binder in the fields of geotechnical engineering and construction [88–90].
By cross-linking, it can increase the soil’s resistance to shear stress, and thus enhance the
mechanical properties of the soil.
Xanthan gum is made up of two glucose, two mannose and one glucuronide that are
mostly arranged in a helical pattern [91]. The viscosity of xanthan gum solutions increases
linearly with increasing xanthan gum content and is highly stable over wide temperature,
pH and electrolyte concentration ranges [23]. Due to its temperature stability, compatibility
with food ingredients and pseudoplastic rheological properties, xanthan gum is widely
used in the food industry [92]. Furthermore, xanthan gum is used in the petroleum industry
as a gelling and suspending agent (flocculant) for viscosity control, as well as a thickening
agent for drilling mud [93]. Recently, xanthan gum was found to be effective in increasing
the shear strength and modulus of elasticity of soils, making them more suitable for use
in foundation excavations and retaining walls. In these studies, the addition of small
amounts of xanthan gum to soils was found to significantly increase their shear strength
and modulus of elasticity. This makes xanthan gum a useful tool for improving the stability
and bearing capacity of soils in geotechnical applications [94–96].
Guar gum is a neutral polysaccharide with random branching points of α-D-galactose
units and a 1,4-linked β-D-mannopyranose backbone [97]. Foods frequently contain guar
gum as a thickener, emulsifier or stabilizer. The ability of guar gum to hydrate quickly
in cold water systems, producing highly viscous solutions even at low concentrations, is
its most significant characteristic [18]. Guar gum solutions exhibit higher viscosity than
xanthan gum solutions at the same biopolymer–water ratio [98]. Guar gum has been
used to stabilize mine tailings in civil and geotechnical engineering by increasing their
undrained shear strength by a factor of about 11 (2 to 22 kPa at 30% moisture content). It
can also be used to prevent shallow cracking by stabilizing swollen soils on slopes and
desert sands [99,100]. Additionally, it has been noted that guar gum slurry is utilized
when building vertical barrier walls [101,102]. However, guar gum slurry can naturally
decompose because of microorganisms or enzymes; as a result, durability becomes a crucial
concern when using guar gum biopolymers in geotechnical engineering practice.
Eighty percent of the protein in cow’s milk is a phosphoprotein biopolymer called
casein. Due to its hydrophobicity, casein biopolymers, which is a waste product of dairy and
milk, have been used in a wide range of applications, including food, industrial coatings,
adhesives, plastics and medical practices [103,104]. Casein has a higher wet strength when
used in geotechnical and construction engineering practices because of its hydrophobicity.
Dextrose is a flexible biopolymer that can form coils with a high density and low level
of permeability in aqueous media [105,106]. It is a homoglycan made up of glucose in linear
chains connected by α-1,6-linkages. One of the first extracellular microbial polymers to be
used in industry was dextran, which is frequently employed as a plasma extender [107].
Dextran was also utilized in tissue engineering [108–110]. The industrial isolation of plasma
proteins, particularly albumin, immunoglobulins, proinsulin and other blood factors, is
another significant application [111–113]. Dextran is also employed as an emulsifier in the
food industry [114]. Dextran has been used as an additive in oil drilling mud [115,116] and
as a soil stabilizer; it is an effective soil aggregate in civil and construction engineering.
According to some reports, dextran increases the proportion of aggregates (>75 m) and
changes the size distribution of microaggregates [117].
Chitin, found in insect, squid and crustacean shells, is converted into the linear
polysaccharide chitosan by deacetylation. Human cells can tolerate chitosan, which has no
adverse effects on the immune system. In order to thicken, stabilize and manufacture food
and biological materials, chitosan is widely used. In earthen construction, chitosan has
been introduced as a workable and sustainable additive [42]. Chitosan’s cationic charge
interacts electrostatically with the negative charges of clay particles to produce condensates
in clay suspensions [15,118,119] and faceted packing of clay deposits [120]. Chitosan wraps
Materials 2023, 16, 603 8 of 15

around sand particle surfaces to improve waste removal through pore plugging, which
significantly lowers the hydraulic conductivity of the soil for soil remediation [26,121].
Agar gum is frequently used as a gel thickener and food stabilizer because it is
made of linearly linked galactose molecules [106]. Agar gums can also be used for drug
therapy [122,123] and as culture media for genetic and microbiological research [124,125].
Agar gum is generally derived from various species of Rhodophyta (red algae), and it
has recently been used as a low environmental load additive to increase soil strength. By
gelating, agar gum can produce significant quantities of soil–biopolymer aggregates. Agar
gum also has a longer molecular structure, which enables it to coat and coagulate soil
particles, thereby enhancing soil strength.

Table 1. Common biopolymers used in geotechnical engineering.

Biopolymers Composition Cost [$/kg] Source Reference

Seeds, grains and roots
Starch C27 H48 O20 1–5 [84,86–90]
of plants
Xanthomonas
Xanthan Gum C35 H49 O29 2–5 [23,91–96]
campestris
Cyamopsis
Guar Gum C10 H14 N5 Na2 O12 P3 1–30 [18,92,93,97–102]
tetragonoloba
Casein C81 H125 N22 O39 P 5–50 Milk [103,104]
Dextran C18 H32 O16 15–60 Lactic acid bacteria [105–117]
Insects, squid bones,
Chitosan C18 H35 N3 O13 10–100 [15,39,42,118–121]
and crustacean shells
Agar Gum C14 H24 O9 10–100 Rhodophyta [22,106,122–125]

In recent years, the rise in sustainable development has promoted the development
of biocements in the geotechnical field. Biocement technology is at the intersection of
the natural environment and architectural disciplines, which have a significant impact
on the economy, society and environment and broad prospects. As mentioned above,
there are two types of biocement technologies: EICP and MICP. The mechanisms of these
two technologies is to induce calcium carbonate precipitation in the soil matrix using
microorganisms (Figure 1) or urease (Figure 2), respectively. The connection of calcium
carbonate particles and matrix particles can improve soil properties.

Figure 1. A representation of calcite precipitation due to the MICP method [48].

Materials 2023, 16, 603 9 of 15

Figure 2. A representation of calcite precipitation due to the EICP method [48].

From ancient cements and modern biopolymers comes the possibility of using some
low-cost materials from our natural resources and productive life as additives to im-
prove the properties of biocements. Compared with traditional technologies, biocement
has many advantages, such as less carbon dioxide emissions and low-pressure injection
work [126,127]. It is considered a promising technology and has been actively studied over
the past two decades. However, both EICP and MICP technologies have some problems.
For example, the costs are relatively high, and it is difficult to accurately control the intensity
and uniformity [128].
Therefore, some researchers have tried to use some low-cost production and domestic
wastes as a calcium source, ammonium source, or additives for reactions in experiments,
hoping to control costs and strengthen performance of improved soil. For example, solid
leather waste has been used to promote the carbonate precipitation process [129]. Lime
solution was used as a substitute for a calcium source, and the leather hydrolysate powder
obtained from thermal hydrolysis of leather waste residues was used to produce urease
for the EICP reaction. As a result, production costs were reduced by about 51.4%. In
addition, the use of meat waste reduced the total amount of solid waste produced during
leather processing by approximately 21.77%. The consumption of suspended matter in
lime solution can also reduce the pollution load by 31.95%.Thus, the utilization of low-cost
leather industry waste for EICP could reduce costs and protect the environment.
Additionally, conducting MICP experiments with low-grade products instead of the
high-grade chemicals that are often used in the laboratory is another method to control
costs [130]. Compared with using pure, lab-grade chemicals as raw materials, a group
using low-grade materials showed higher UCS strength. According to the SEM images, the
combination of soil particles and calcium carbonate precipitations were widely observed
in these samples. The unusual formation of a dense matrix is due to the presence of other
polymer substances (PS) in low-grade chemicals. When calcite precipitation occurs, the pre-
cipitate encapsulates the PS and fills the void spaces, effectively providing necessary matrix
support. By replacing pure chemicals with low-grade chemicals, a significant improvement
in the UCS of soil was obtained, together with a 96% reduction in treatment costs.
Materials 2023, 16, 603 10 of 15

Some researchers used jute fiber as an additive and found that jute fiber had significant
effects on microbial performance, calcium carbonate precipitation patterns and sand solidi-
fication [131]. Fluorescence microscopy showed that the addition of jute fiber obviously
improved the viability of microorganisms. The amount and length of jute fiber effectively
improved the bacterial properties and mechanical properties (UCS and ductility) of sand,
resulting in an increase in UCS with an increase in fiber content. However, when the
amount of added fiber exceeded a certain point (3% and 15 mm), entanglement between
fibers easily occurred, which hindered the entry of bacteria and reduced their living space,
thus decreasing the formation of calcium carbonate and eventually reducing UCS. SEM
analysis showed that the added jute fibers coupled well with calcium carbonate crystals
and formed a reliable bridge within the soil matrix, limiting the development of failure
surfaces inside the specimen and improving the mechanical properties of the specimen.
Overall, the use of low-cost materials from natural resources and productive life as
additives for improving biocement performance should be further studied and discussed.
Additives used in ancient cements, such as glutinous sticky rice and volcanic ash, were
shown to improve some properties of calcium carbonate crystallization at the micro level
and thus improve the performance of lime cement. In addition, these additives have many
advantages, such as low cost, being easy to obtain from the natural environment, being
harmless to the environment and so on, which meet the requirements for sustainable de-
velopment. Therefore, this paper summarizes some additives used in ancient civilizations
and makes the following conclusions: As mentioned above, there have been many experi-
mental studies on additives in microbial cement using low-cost natural materials or wastes,
but most of them are derived from modern chemical materials or products. Research on
whether low-cost additives in ancient lime cement can be applied to the field of biocement
is rare. Moreover, given that most buildings built by ancient lime cement have survived
hundreds or thousands of years under natural erosion, the use of the same kind of additive
may contribute to remarkable anti-corrosion properties, such as water erosion resistance.
We recommend conducting a hybrid study that combines ancient cement technology with
current biocement technology to overcome the high costs, low strength and durability
problems of biocement usage.

4. Conclusions
The current consensus in geotechnical engineering is to adopt low-cost, environmen-
tally friendly technologies for sustainable development. This paper summarizes the types
and specific additives of ancient cement and draws several conclusions.
Lime cement has a long history. Additives can significantly alter the properties of lime
cement and have allowed ancient architectures to be preserved for hundreds of thousands
of years. The ancient Romans improved the strength and watertightness of lime cement by
adding volcanic ash. It has been shown that volcanic ash can form a new crystal structure of
tobermorite in cement, which presents a plate-like structure and can increase the toughness
of concrete and improve the structure’s mechanical properties. The ancient Chinese made
their cement mainly by adding glutinous sticky rice and some other animal and plant
products, of which glutinous rice cement was the most brilliant. On a microscopic level,
glutinous rice can regulate calcium carbonate crystals to form tiny, dense structures and
wrap around them to fill the gaps between them, thereby reducing porosity and increasing
strength. In addition, the alkaline environment in cement can effectively help the starch
from breaking down over a long period of time, thus improving the life of the entire
structure. The ancient Indians used plant and animal products to make additives. Plant
juice promotes calcium oxalate production, whereas animal products contain ingredients
such as protein and animal glue to fill gaps and improve performance.
Overall, the additives used in ancient cements improved the performance of lime
cement. Most of these additives are low-cost, environmentally friendly, easy to obtain and
so on, meeting the needs of the geotechnical engineering field, today and for the future.
In addition, as one of the fields of geotechnical engineering, biocement technology has
Materials 2023, 16, 603 11 of 15

many advantages, and its future development is promising. From a sustainable engineering
perspective, this soil stabilization technology is not only a practical resource/waste manage-
ment approach, but also contributes to the creation of countless jobs. Therefore, this paper
summarizes some additives used in ancient civilizations, making valuable suggestions for
future biocement technology in the selection and research of additives.

Author Contributions: Z.S. and Z.Y. performed the literature survey and wrote the manuscript.
K.N., C.T. and S.K. contributed in the design, analysis, methodical guidance and technical assistance
regarding the subject area. All the authors reviewed the manuscript. All authors have read and
agreed to the published version of the manuscript.
Funding: This research received no external funding.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: No new data were created or analyzed in this study. Data sharing is
not applicable to this article.
Conflicts of Interest: The authors declare no conflict of interest.

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