P15
FTIR COUPLED WITH PLS-DA AGAINST FRAUDS: THE CASE OF
HEAVY-SALTED DESALTED AND LIGHT-SALTED COD FILLETS
M. De Rubeis, D. Pizzoni, D. Compagnone, M. Chiarini, A. Serio, A. Paparella
Facoltà di Bioscienze e Tecnologie Agro-Alimentari e Ambientali, Università di
Teramo, Via C.R. Lerici, 1 – 64023 Mosciano S.A (TE).
Cod (Gadus morhua L.) is a widespread white fish. In the Mediterranean
countries, it is commercialized mainly as salted cod with different moisture
content depending on the extension of the drying step [1].
Different salting process can lead to very different attributes of the final product,
however no analytical method has been proposed to discriminate samples salted
with or without the use of brine.
Vibrational spectroscopy methods, such as NIR and FT-IR, are fast and easy
techniques, that can be used with minimal sample preparation and have been
reported to be effective, coupled with chemometric data processing, particularly
for food authentication issues [2].
In this work, the use of Fourier transform infra-red (FTIR) spectroscopy has been
proposed in order to discriminate heavy-salted desalted (HS) cod samples from
light-salted (LS). The method take advantage of Horizontal Attenuated Total
Reflectance (HATR) FTIR to record cod loin samples spectra in the range 4000-
650 cm-1. Cod loin samples are homogenised before analysis. Spectral data were
then processed with partial least square discriminant analysis (PLS-DA) in order
to discriminate the two analysed classes (HS and LS).
Different sources of variability of the sample were considered (such as packaging,
storage time, producers, region of origin and freezing processes). A total of 258
samples were analysed. Both cross validation (CV) and external validation were
performed in order to evaluate the discriminant ability of the method. 100% of the
samples were correctly assigned in CV in any case, while for external validation
data set, the final proposed model showed from 91 to 98 % of correct assignation.
Robustness of the method has also been evaluated. The proposed method is a fast,
cheap and “green” way to discriminate against frauds for cod production.
Authors wish to thank the Norvegian Seafood Research Fund SALDICOD project
for financial support.
[1] A. Andrés, S. Rodríguez-Barona, J. M. Barat, P. Fito, J. Food Eng. 69
(2005) 467–471.
[2] M. Bevilacqua, R. Bucci, A. D. Magrì, A. L. Magrì, F. Marini, Anal.
Chim. Acta 717 (2012) 39–51.
201
P16
DETECTION OF COFF E POWDER ORIGIN BY ELECTRONIC NOSE
AND GC-MS ANALYSIS
D. Compagnone1, D. Mutarutwa1, D. Pizzoni1, P. Pittia1, L.Bucci1, L. Navarini2.
1
Facoltà di Bioscienze e Tecnologie Agro-Alimentari e Ambientali, Università di
Teramo, Via C.R. Lerici, 1 – 64023 Mosciano S.A (TE).
2
Illycaffè spa, Via Flavia 110 – 34137 Trieste.
In the last years, the use of oligopeptide modified piezoelectric sensors has been
demonstrated to be a very useful tool for many different applications. Gold
electrodes on quartz crystal microbalances (QCMs) resulted particularly useful to
immobilise peptides via self-assembled monolayer, using cysteine as terminal
amino acid or, alternatively, a thiolated spacer.
More recently, the use of gold nanoparticles (AuNPs) modified with oligo-
peptides as QCMs surface modifying agent has been proposed (e.g. [1]).
Encouraging results have been obtained due to the ease of derivatisation, high
number of possible configuration and possibility to design via molecular
modelling the ligands.
In this work, an application of a AuNP-peptide based sensors array on coffee
powder samples is presented. Illy SpA (Trieste, Italy) kindly supplied Coffee
powder samples. Five different kinds of samples were analysed (they were all
commercial product from Illy SpA). Three coffe powders were from a single
geographical origin (Costa Rica, Colombia and India – commercial name: Illy
Monoarabica). One kind was a blend of coffees from nine different countries
(commercial name: Illy Espresso) and the fifth was the same as the ”Illy
Espresso” but after decaffeination (obtained by industrial process with supercritic
CO2 – commercial name: Illy Deca). All samples were analysed on a TEN 2011
(Tor Vergata Sensors Group – Rome, Italy) e-nose apparatus equipped with 20
MHz QCMs. The sensors surfaces modified with seven GNP-peptides
(Thioglycolic acid, Glutathione, Cys-Ile-His-Asn-Pro, Cys-Ile-Gln-Pro-Val, Cys-
Gly, Cys-Arg-Gln-Val-Phe, Cys). The peptides were selected according to their
chemical and physical properties. E-nose data were compared by GC-MS
analytical data. Sensors arrays data showed the ability of multivariate statistical
analysis on electronic nose and GC data to separate samples according to the
geographical origin. GC-FID/FPD data for geographical discrimination was also
tested with good results. With both techniques Colombia and Costa Rica samples
showed a partial overlapping while India was well separated. It is worth noting
that the not completely separate geographic area were the closest.
[1] D. Compagnone, G. Fusella, M. Del Carlo, P. Pittia, E. Martinelli, L. Tortora,
R. Paolesse, C. Di Natale, Biosensors and Bioelectronics 42 (2013) 618–625.
202
P17
INORGANIC COMPOSITION AND RAMAN SPECTROSCOPY AS NEW
METHODS FOR THE IDENTIFICATION OF ANIMAL MEALS
RESIDUED IN FEED.
A. Giacomino1, L.M. Mercurio2, M. Malandrino2, O. Abollino2, L. Mandrile3,
A.M. Rossi3, D. Marchis4.
1
Dipartimento di Scienza e Tecnologia del Farmaco, Università di Torino, Via
Giuria 9, 10125 Torino
2
Dipartimento di Chimica, Università di Torino, Via Giuria 7, 10125 Torino
3
Divisione di Termodinamica, Istituto Nazionale di Ricerca Metrologica, Strada
delle Cacce 91, 10135 Torino
4
Istituto Zooprofilattico sperimentale del Piemonte, Liguria e della Valle d’Aosta,
Via Bologna 148, 10154 Torino
Our study is aimed at evaluating the possibility of using inorganic composition
and Raman spectroscopy as possible alternative methods of analysis for the
individuation and characterization of Processed Animal Proteins (PAPs) in animal
feeds.
The official analysis method approved by European Commission is based on
optical microscopy [1], and on Real Time PCR. However, both methods present
some drawbacks, (e.g. high staff specialization). Particularly, microscopy does not
permit the identification of animal species present in feed. PCR methods are
specific and sensitive in nature [2], but they are not able to distinguish between
allowed and not allowed ingredients (e.g. Milk versus PAP). Many other
techniques, as infrared microscopy, immunoassay methods, chromatographic and
mass-spectrometry, were just evaluated as possible alternative methods. All these
methods show advantages and limitations [3].
Four types of pure PAPs, namely bovine, swine, poultry and fish-based PAPs,
have been analyzed using an inductively coupled plasma optical emission
spectrometer (ICP-OES) and a FT-RAMAN spectrometer. All the procedure steps
(samples pretreatment and analysis) and all the parameters and conditions were
considered and optimized.
The application of multivariate chemometric techniques to the experimental
results allowed us to determine the identification capability of the two techniques,
to identify correlations among the variables and to reveal similarities and
differences among the different species.
[1] European Official Gazette, N.51/2013, January 16th, 2013.
[2] A. Dalmasso, E. Fontanella, P. Piatti, T. Civera, S. Rosati, M.T. Bottero,
Molecular and Cellular Probes 18 (2004) 81-87.
[3] G. Gizzi, C. von Holst, V. Baeten, G. Berben, L. van Raamsdonk, Journal of
AOCD International 87 (2004) 1334-1341.
203
P18
DETERMINATION OF OLIVE OIL ACIDITY: A NOVEL
ELECTROANALYTICAL APPROACH
M.A. Baldo1, P. Oliveri2, R. Simonetti2, S. Daniele1
1
Dipartimento di Scienze Molecolari e Nanosistemi, Università Ca’ Foscari
Venezia, Dorsoduro 2137, Calle Larga Santa Marta – 30123 Venezia
2
Dipartimento di Farmacia, Università di Genova, Via Brigata Salerno, 13 –
16147 Genova
Free fatty acids (FFAs) content in olive oil is a key parameter routinely
determined to classify and/or assess the quality, the freshness, and the economic
value of the final product available on the market. The official method, suggested
by ECC Regulation, for the quantification of the olive oil acidity - expressed as
mass percentage of free oleic acid -, is a classical acid/base volumetric titration,
performed in non-aqueous solvents [1]. The procedure is simple, but very slow,
laborious and organic solvent consuming. Considering the large number of routine
measurements necessary for marketing purposes, the development of fast, simple,
low-cost, solvent-free and reliable instrumental analytical methodologies for
quantifying the olive oil acidity is a task of great interest.
To this purpose, in the present study an electroanalytical strategy for a direct
evaluation of the acidity in olive oils is presented. The experimental conditions for
exploiting the reduction process of the acidic species present in this food matrix
were defined and optimised, under both deoxygenated and oxygenated conditions,
taking as acid probe the oleic acid (OA), which is the prevailing long-chain FFA
component of olive oil. Oil samples were prepared by adding, as supporting
electrolyte, the room temperature ionic liquid (RTIL) tri-
hexyl(tetradecyl)phosphonium bis(trifluoromethylsulfonyl) imide
([P14,6,6,6]+[NTf2]-), that is soluble in vegetable oil and enhance the matrix
conductivity [2,3]. The measurements were performed in a 2 mL glass vial as
electrochemical cell, using a 12.5 µm radius Pt microdisk as working electrode.
By applying a properly optimised chronoamperometric setup, reliable acidity data
in some extravirgin, virgin, and lamp olive oil samples were found. The results
obtained indicates that the electrochemical procedure developped can be
advantageously exploited as a fast, low-cost and solvent-saving analytical tool for
the determination of olive oil acidity.
Financial support from PRIN 2010-11 prot. 2010AXENJ8, is acknowledged.
[1] ECC Regulation n° 2568/91.
[2] P. Oliveri, M.A. Baldo, S. Daniele, M. Forina, Anal.Bioanal.Chem. 395
(2009) 1135-1143.
[3] M.A. Baldo, P. Oliveri,R. Simonetti, S. Daniele, J.Electroanal.Chem. 731
(2014) 43-48.
204
P19
A NOVEL ANALYTICAL STRATEGY FOR THE ASSESSMENT OF
TRACE HEAVY METAL CONTAMINATION IN OLIVE OILS
M.A. Baldo1, M. Ongaro1, A.M. Stortini1, G. Cozzi2, M. Roman2, L.M. Moretto1,
S. Daniele1, P. Ugo1
1
DSMN, Università Ca’ Foscari Venezia;
2
IDPA-CNR, Venezia S. Marta 2137 – 30123 Venezia
Trace heavy metals dangerous to human health, as Pb, Cd or Cu, can be present in
olive oil because of contamination from soil and fertilizers, production or storage
procedures, or exposition of the olive plants to vehicular and industrial emissions
[1]. This problem has lead to increasing interest in the development of sensitive
and accurate analytical methods to monitor trace levels of these elements directly
in edible oils, characterized by a high viscous organic matrix where traditional
analytical techniques can hardly be applied without strong and time-consuming
sample pretreatments.
To this aim, in this work a novel analytical approach combining electrochemical
and inductively coupled plasma mass spectrometric (ICP-MS) measurements is
proposed.
The experimental conditions for the voltammetric analysis in such low-conductive
food matrix were defined taking lead as target analyte. Tri-
hexyl(tetradecyl)phosphonium bis(trifluoromethylsulfonyl) imide
+ -
([P14,6,6,6] [NTf2] ), a room temperature ionic liquid (RTIL) soluble in vegetable
oil, was used as supporting electrolyte [2]. The measurements were performed in a
2 mL glass vial, using a 10 µm radius Pt microdisk or a glassy carbon (r=1.5 mm)
as working electrodes.
For the development and validation of the analytical procedure, standard reference
solutions of lead were produced by galvanostatic dissolution of a bar of high-
purity Pb directly in the pure RTIL. Varying the dissolution time, a set of
Pb2+/[P14,6,6,6]+[NTf2]- standards at concentration between 10 and 200 mg L-1,
calculated by the Faraday law, was prepared. ICP-MS analysis of Pb2+ standards,
after mineralization in a microwave unit by a digestion procedure properly set up,
validated the method.
The strategy proposed here for the determination of Pb content in olive oils
consists in the following steps: 1) metal preconcentration onto a thin Pt coil
directly from the oil sample mixed with RTIL; 2) potentiostatic re-oxidation of the
metal at +1.5V in 10% HNO3 solution; 3) quantification by ICP-MS or
voltammetric measurements in the acid solution obtained by step 2). The
experimental results are presented and discussed.
Financial support from PRIN 2010-11 prot. 2010AXENJ8, is acknowledged.
[1] L. La Pera et al, J.Agricolt. Food Chem, 50 (2002) 3090.
[2] M.A. Baldo, P. Oliveri, R. Simonetti, S. Daniele, J. Electroanal.Chem. 731
(2014) 43-48.
205
P20
SPME-GC-qMS AND SPME-GCxGC-TFM-TOFMS
CHARACTERIZATION OF VOLATILE COMPOUNDS OF
AUTOCTONOUS WHITE WINES FROM THE COLLIO AREA
A. Tolloi1, S.C. Briguglio1, E. Muzic1, L. Calamai2, F. Villanelli3, E. Sebastiani3,
G. Adami1, P. Barbieri1,4
1
Dipartimento di Scienze Chimiche e Farmaceutiche, Università degli Studi di
Trieste, Via Licio Giorgieri, 1 – 34127 Trieste
2
Dipartimento di Scienze Produzioni Agroalimentari e dell'Ambiente, Università
degli Studi di Firenze, Piazzale delle Cascine, 28 - 50144 Firenze
3
SRA Instruments S.p.A., Via alla Castellana, 3 20063 Cernusco sul Naviglio
(MI)
4
ARCo SolutionS srl, spin off del Dipartimento di Scienze Chimiche e
Farmaceutiche, Università di Trieste, Piazzale Europa, 1 – 34127 Trieste
The Collio is a vineyard area near Gorizia in Italy and close to the Slovenian
border, renowned for excellent white wines. In this research we charachterize
three wines – namely Friulano, Ribolla Gialla and Malvasia Istriana – for their
volatilome/VOCs qualitative and semi-quantitative profiles in order to identify
aroma features of the different species. After optimization of instrumental
parameters and derivatization of wine samples with PFBHA, HSSPME–GC-qMS
was performed allowing the identification of 40 compounds, with abundance of
aldehydes, esters and ketones. A pool of compounds was common and very
similar in level to all the wine varieties, while Friulano presented relatively high
concentration of some ketones and one ester while Ribolla Gialla had low values
of some heavy esters. All these and other features can be highlighted by a
Principal Component Analysis of the data set. The compounds with highest
loadings on the first components are known to provide specific fruity aroma.
More, focusing on Friulano wine, the composition of VOCs from Collio was
compared with those of other areas from Friuli Venezia Giulia region, allowing a
first identification of typical features of different regional wine production zones.
An abundance of longer chain esters and aldehydes characterizes the Collio
Friulano’s versus those of other areas, richer in pentanal. An improvement in
selectivity and sensitivity is allowed by SPME Total Flow Modulation GCxGC-
TOFMS, highlighting the presence of compounds at low concentration but with
significant odor threshold.
206
P21
SIMULTANEOUS DETERMINATION OF VITAMINS AND CAROTENES
BY ON-LINE COLUMN FOCUSING FOLLOWED BY LIQUID
CHROMATOGRAPHY AND UV DETECTION
D. Nardiello1, C. Palermo1, M. Muscarella2, M. Quinto1, D. Li3, D. Centonze1
1
Dipartimento di Scienze Agrarie, degli Alimenti e dell’Ambiente and CSRA-
Centro Servizi di Ricerca Applicata, Università degli Studi di Foggia, Via Napoli,
25 - 71100 Foggia
2
Istituto Zooprofilattico Sperimentale della Puglia e della Basilicata, Via
Manfredonia, 20 - 71100 Foggia
3
Key Laboratory of Natural Resource of the Changbai Mountain and Functional
Molecular (Yanbian University), Ministry of Education, Park Road 977, Yanji
City, Jilin Province, China
Vitamins and carotenes represent important dietary components essential for
health, because of their involvement in vital metabolic processes and the potential
ability to decrease the risk for coronary heart disease, cancer and sight disorders.
Therefore, their content in food commodities can be used as an index of the
health-related quality of products. Established methods for analysis of vitamins
include the chromatographic ones that are typically designed for classes of
compounds, i.e. water- and fat-soluble vitamins, based on their different solubility
properties and chemical structures, ranging from small organic acids to large
conjugated complexes. The simultaneous determination of water and fat soluble
vitamins, in addition to highly lipophilic compounds, such as carotenes, increases
the complexity of an analytical method, including sample processing and storage,
as well as the choice of proper solubilization solvents, which must be in tune with
the chromatographic eluents. Moreover, the heterogeneity of food matrices and
the potential degradation of these classes of compounds during the analysis make
their quantitative determination even more demanding.
In this study, an improved LC method coupled to a multiple wavelength UV
detection is described for the determination of B group vitamins (B1, B2, B3, B6
and B9), ascorbic acid (vitamin C), retinol (vitamin A), tocopherol (vitamin E),
phylloquinone (vitamin K1), lycopene, β-carotene, and β-apo-80-carotenal, used
as an internal standard. Chromatographic separations have been performed by an
innovative core-shell C18 column packed with 2.6 µm particles; flow rates and
gradient elution programs have been carefully optimized for the total resolution of
all the target analytes. An on-line focusing step was required for column head
trapping of carotenes and fat-soluble vitamins, before the chromatographic run
starting from an aqueous mobile phase, necessary for the elution of scarcely
retained water-soluble vitamins. The potential of the proposed method has been
confirmed by the analysis of tomatoes and fresh fruits.
207
P22
AEROSOL PARTICULATE MATTER STUDY FOR THE
CONSERVATION OF URBAN MONUMENTAL HERITAGE: THE
CASES OF FLORENCE AND MILAN
P. Fermo1, A. Bonazza2, D. Gulotta3, L. Corbella1, L. Toniolo3
1
Università degli Studi di Milano, Dipartimento di Chimica, Via Golgi 19 -20133
Milano
2
ISAC-CNR, Istituto di Scienze dell’Atmosfera e del Clima, Via Gobetti 101 –
40129 Bologna
3
Politecnico di Milano, Dipartimento di Chimica, Materiali e Ingegneria Chimica,
Via Mancinelli 7 – 20131 Milano
Air pollution can cause a variety of environmental effects also on ecosystem and
cultural heritage. Aerosol particulate matter (PM), together with gases, is the main
responsible for atmospheric pollution and its effects. The damage induced by air
pollution on immovable and movable cultural heritage is nowadays a topic of
major concern in particular in highly polluted urban areas. To adopt mitigation
actions aimed to reduce pollutants, the chemical characterization of aerosol
particulate matter is mandatory. In the present studies two urban sites were
considered for PM monitoring: the Museum of San Marco, Florence, located in an
area of the city rather exposed to traffic and the Duomo of Milan. In Florence
TSP (total suspended particulate matter) was collected during different campaigns
while in Milan the deposited PM was collected by means of exposed filters. In
both sites specimens of local lithotypes (Carrara marble for Florence and
Candoglia marble for Milan) were exposed in parallel in order to study the
degradation induced by pollution on the stone surfaces. The blackening and the
yellowing of the surfaces have been also monitored. Inorganic ions (SO42-, NO3-,
Cl-, Ca2+, Mg2+, K+, Na+ and NH4+), short chain organic acids (acetate, propionate,
etc.), organic and elemental carbon were quantified in both PM and surface
deposits. From these data it is possible to draw some conclusion on the causes of
the surface deterioration processes.
208
P23
A MULTITECHNIQUE APPROACH ON ANTONINIAN COINS FROM
EGNATIA (SOUTHERN ITALY)
L.C. Giannossa1, R. Gaudiuso2, G. Giannelli1, A. De Giacomo1,2, R. Laviano3, A.
Mangone1,4
1
Dipartimento di Chimica, Università degli Studi Bari Aldo Moro, Via Orabona 4
– 70126 Bari
2
CNR-Nanotec Bari, Via Amendola 122/D – 70126 Bari
3
Dipartimento di Scienze della Terra e Geoambientali, Università degli Studi Bari
Aldo Moro, Via Orabona 4 – 70126 Bari
4
Centro Interdipartimentale, Laboratorio di Ricerca per la Diagnostica dei Beni
Culturali, Università degli Studi Bari Aldo Moro, Via Orabona 4 – 70126 Bari
We analyzed a collection of Antoninian coins coming from the archaeological site
of Egnatia (Southern Italy).
Antoninianus (III cent. bC) was initially in silver, but was slowly debased to
bronze. Each new coin had a lower amount of silver than the previous one,
contributing to increasing inflation.
In 274 AD Aurelian took a series of measures to solve the crisis: acting on the
nominal values, closing provincial mints and activating those under the direct
control of the emperor. Moreover, a new coin was introduced, heavier but still
lighter compared to the first Antoninian coins, and with a content of Ag –
apparently- higher than those produced in the recent past.
Six pre-reform, six post-reform and one non-ascribable coins were analyzed.
We aimed to estimate devaluation, i.e. the gradual decrease in silver content in the
alloy for pre-reform coins; to provide information on the actual effects of the
monetary reform of Aurelian, i.e. the supposed enhance in the amount of silver in
the reformed coins and to obtain knowledge on technological production.
Portable X Ray Fluorescence, Laser-Induced Breakdown Spectroscopy, Raman
Spectroscopy, Optical and Electron Scanning Microscopy with Energy Dispersive
Spectroscopy were use for the investigations.
The results revealed for all coins a Cu/Ag/Sn/Pb quaternary alloy, in which
copper is the main alloying element. It was not observed a substantial difference
in the amount of Ag in pre and post-reform coins.
The metallographic analysis of the microstructures highlighted a Cu/Ag biphasic
structure in all the coins, as well as information on the techniques used to the
manufacturing, implying a process of cold hammering of the dowels obtained by
melting, in some cases followed by warming up.
209
P24
PYROLYSIS-GC-MS OF MODERN INKS: THE FELT-TIP PENS USED
BY LINA BO BARDI
G. Germinario1, I.D. van der Werf1, A. Mirabile2, P. Moretti3, C. Miliani4,5, L.
Sabbatini1,6
1
Dipartimento di Chimica, Università degli Studi di Bari Aldo Moro, via Orabona,
4- 70125 Bari
2
Paper Conservator, 11 rue de Bellefond, 75009 Paris, France
3
Dipartimento di Chimica, Biologia e Biotecnologie, Università degli Studi di
Perugia, via Elce di Sotto, 8 - 06123 Perugia
4
Istituto CNR-ISTM, via Elce di Sotto, 8 - 06123 Perugia
5
Centro di eccellenza SMAArt, Università degli Studi di Perugia, via Elce di
Sotto, 8 - 06123 Perugia
6
Centro Interdipartimentale ‘‘Laboratorio di Ricerca per la Diagnostica dei Beni
Culturali’’, Università degli Studi di Bari Aldo Moro, Bari
Felt-tip pens have been employed for a wide range of objects, such as sketches,
drawings, copies, architectural drawings and other technical designs.
Unfortunately, the inks are usually very sensitive to light and chemical agents and
the exact knowledge of their composition may be important to define the optimal
conservation treatment and/or storage conditions. So far, few studies have been
addressed to the chemical characterization of these materials and information on
binders, fillers, dyes and pigments is still lacking.
Twenty felt-tip pens that were used by the Italian architect and designer Lina Bo
Bardi (1914, Rome - 1992, São Paulo) in architectural drawings, currently
subjected to conservation treatments, were investigated with a multi-technique
approach (scanning electron microscopy, X-ray fluorescence, infrared and Raman
spectroscopy, pyrolysis gas chromatography–mass spectrometry (Py-GC-MS)).
In this contribution the Py-GC-MS data are presented and the pyrolytic
fragmentation of some dyes was proposed. The combination of these results with
the previously obtained spectroscopic and elemental data [1] lead to the
characterization of the felt-tip pen inks.
This work was performed in the framework of PRIN 2010-11"Sustainability in
cultural heritage: from diagnosis to the development of innovative systems for
consolidation, cleaning and protection", code 2010329WPF, funded by MIUR.
[1] A. Mirabile, P. Moretti, F. Presciutti, N. Mancinelli, L. Cartechini, A.
Sgamellotti, C. Miliani, Diagnosis of modern tracing papers and felt-tip pen inks
for the conservation of architecture drawings: Lina Bo Bardi’s materials, Technart
2015, Catania 20-24 april 2015.
210
