Matteo Perini

Isotopic and Elemental Data for Tracing the Origin of European Olive Oils

H, C, and O stable isotope ratios and the elemental profile of 267 olive oils and 314 surface waters collected from 8 European sites are presented and discussed. The aim of the study was to investigate if olive oils produced in areas with different climatic and geological characteristics could be discriminated on the basis of isotopic and elemental data. The stable isotope ratios of H, C, and O of olive oils and the ratios of H and O of the relevant surface waters correlated to the climatic (mainly temperature) and geographical (mainly latitude and distance from the coast) characteristics of the provenance sites. It was possible to characterize the geological origin of the olive oils by using the content of 14 elements (Mg, K, Ca, V, Mn, Zn, Rb, Sr, Cs, La, Ce, Sm, Eu, U). By combining the 3 isotopic ratios with the 14 elements and applying a multivariate discriminant analysis, a good discrimination between olive oils from 8 European sites was achieved, with 95% of the samples correctly classified into the production site.

Influence of dietary composition on the carbon, nitrogen, oxygen and hydrogen stable isotope ratios of milk

The stable isotope ratios ((13)C/(12)C, (15)N/(14)N, (18)O/(16)O, D/H) of animal feed and milk were investigated, considering cows stabled in two farms and fed with diets made up of different kinds of C(3) plants and different amounts of maize. Maize was characterised by delta(13)C, delta(18)O and deltaD values significantly higher than those of the C(3) plants, while, for the C(3) plants, Festuca arudinacea had significantly higher content of (13)C and (15)N. The delta(13)C and delta(18)O values of the overall diet and the delta(13)C of milk casein and lipids were shown to be significantly correlated with the percentage of maize in the animal diet. On the other hand, the delta(18)O values of milk water and the delta(18)O, deltaD and delta(15)N values of casein were shown to be only slightly influenced by the amount of maize in the feed, being probably more closely correlated with the geo-climatic and pedological characteristics of the area of origin and with the presence of fresh plant or silage in the ration. The delta(13)C value of casein was shown to be a suitable parameter for evaluating the amount of maize in the diet: each 10% increase in the maize content corresponded to a shift of 0.7 per thousand to 1.0 per thousand in the delta(13)C of casein. A threshold value of -23.5 per thousand for delta(13)C in milk casein, above which it is not possible to exclude the presence of maize in the diet, was suggested. The results obtained could be useful for determining mislabelling of dairy products declared to have been produced by pastured animals or of PDO cheeses with an established amount of maize in the diet and for verifying the unpermitted addition of exogenous components to milk.

Multielement (H, C, N, O, S) stable isotope characteristics of lamb meat from different Italian regions

The study focuses on the (2)H/H, (13)C/(12)C, (15)N/(14)N, (18)O/(16)O and (34)S/(32)S values of defatted dry matter (DFDM) and on the (2)H/H, (13)C/(12)C and (18)O/(16)O values of the fat fraction of meat samples from various lamb types reared in seven Italian regions, following different feeding regimes (forage, concentrate, milk). The (13)C/(12)C (r = 0.922), (2)H/H (r = 0.577) and (18)O/(16)O (r = 0.449) values of fat and DFDM are significantly correlated, the fat values being significantly lower for C and H and higher for O than for DFDM values and the differences between the two fractions not being constant for different lamb types. The feeding regime significantly affected the (13)C/(12)C, (15)N/(14)N, (18)O/(16)O and (2)H/H of fat. The DFDM (2)H/H, and (18)O/(16)O values, excluding an outlier, are significantly correlated with the corresponding values in meteoric waters, thus allowing us to trace the variability of geoclimatic factors. (15)N/(14)N is influenced by pedoclimatic conditions, whereas (34)S/(32)S is influenced by the sea spray effect and the surface geology of the provenance area. By applying stepwise linear discriminant analysis only the (2)H/H of fat was found not to be significant and 97.7% of the samples were correctly assigned to the lamb type and more than 90% cross-validated. With the feeding regime, 97.7% of the samples were both correctly assigned and cross-validated using a predictive model including (13)C/(12)C, (15)N/(14)N, (18)O/(16)O, (34)S/(32)S of DFDM and (18)O/(16)O of fat.

H, C, N and S stable isotopes and mineral profiles to objectively guarantee the authenticity of grated hard cheeses.

In compliance with the European law (EC No. 510/2006), geographical indications and designations of origin for agricultural products and foodstuffs must be protected against mislabelling. This is particularly important for PDO hard cheeses, as Parmigiano Reggiano, that can cost up to the double of the no-PDO competitors. This paper presents two statistical models, based on isotopic and elemental composition, able to trace the origin of cheese also in grated and shredded forms, for which it is not possible to check the logo fire-marked on the rind. One model is able to predict the origin of seven types of European hard cheeses (in a validation step, 236 samples out of 240 are correctly recognised) and the other specifically to discriminate the PDO Parmigiano Reggiano cheese from 9 European and 2 extra-European imitators (260 out of 264 correct classifications). Both models are based on Random Forests. The most significant variables for cheese traceability common in both models are δ(13)C, δ(2)H, δ(15)N, δ(34)S and Sr, Cu, Mo, Re, Na, U, Bi, Ni, Fe, Mn, Ga, Se, and Li. These variables are linked not only to geography, but also to cow diet and cheese making processes.

Coast and year effect on H, O and C stable isotope ratios of Tyrrhenian and Adriatic italian olive oils

The paper discusses the (2)H/(1)H, (18)O/(16)O and (13)C/(12)C ratios of 196 authentic Italian extra-virgin olive oils produced in 3 years on the Tyrrhenian and Adriatic coasts. The (2)H/(1)H and (18)O/(16)O ratios were linearly and positively correlated. The year of production influenced mainly (18)O/(16)O in relation to the amount of rainfall and the atmospheric humidity in the period of oil accumulation in the olives. The (2)H/(1)H ratio significantly distinguished the olive oils produced on the Adriatic coast from those on the Tyrrhenian coast in each year. This coast effect is a consequence of the different sources and isotopic compositions of the rainfall and the different climatic conditions on the two coasts. The paper contributes towards understanding the influence of climatic factors on isotopic variability and towards improving the traceability of the geographical origin of olive oils, using (2)H/(1)H as a more innovative parameter.

Using elemental profiles and stable isotopes to trace the origin of green coffee beans on the global market

A broad elemental profile incorporating 54 elements (Li, Be, B, Na, Mg, Al, P, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y, Mo, Pd, Ag, Cd, Sn, Sb, Te, Cs, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Er, Tm, Yb, Re, Ir, Pt, Au, Hg, Tl, Pb, Bi and U) in combination with δ(2) H, δ(13) C, δ(15) N and δ(18) O was used to characterise the composition of 62 green arabica (Coffea arabica) and robusta (Coffea canephora) coffee beans grown in South and Central America, Africa and Asia, the four most internationally renowned areas of production. The δ(2) H, Mg, Fe, Co and Ni content made it possible to correctly assign 95% of green coffee beans to the appropriate variety. Canonical discriminant analysis, performed using δ(13) C, δ(15) N, δ(18) O, Li, Mg, P, K, Mn, Co, Cu, Se, Y, Mo, Cd, La and Ce correctly traced the origin of 98% of coffee beans.

Use of Near-Infrared Spectroscopy for Fast Fraud Detection in Seafood: Application to the Authentication of Wild European Sea Bass (Dicentrarchus labrax)

The possibility of using near-infrared spectroscopy (NIRS) for the authentication of wild European sea bass ( Dicentrarchus labrax ) was investigated in this study. Three different chemometric techniques to process the NIR spectra were developed, and their ability to discriminate between wild and farmed sea bass samples was evaluated. One approach used spectral information to directly build the discrimination model in a latent variable space; the second approach first used wavelets to transform the spectral information and subsequently derived the discrimination model using the transformed spectra; in the third approach a cascaded arrangement was proposed whereby very limited chemical information was first estimated from spectra using a regression model, and this estimated information was then used to build the discrimination model in a latent variable space. All techniques showed that NIRS can be used to reliably discriminate between wild and farmed sea bass, achieving the same classification performance as classification methods that use chemical properties and morphometric traits. However, compared to methods based on chemical analysis, NIRS-based classification methods do not require reagents and are simpler, faster, more economical, and environmentally safer. All proposed techniques indicated that the most predictive spectral regions were those related to the absorbance of groups CH, CH(2), CH(3), and H(2)O, which are related to fat, fatty acids, and water content.

Stable Isotope Ratio Analysis for Assessing the Authenticity of Food of Animal Origin

The main elemental constituents (H, C, N, O, and S) of bio-organic material have different stable isotopes (2 H, 1 H; 13 C,12 C; 15 N,14 N; 18 O,17 O,16 O; 36 S, 34 S, 33 S, and 32 S). Isotopic ratios can be measured precisely and accurately using dedicated analytical techniques such as isotope ratio mass spectrometry (IRMS). Analysis of these ratios shows potential for assessing the authenticity of food of animal origin. In this review, IRMS analysis of food of animal origin and variability factors related to stable isotope ratios in animals are described. The study also lists examples of application of stable isotope ratio analysis to meat, dairy products, fish, and shellfish and emphasizes the strengths and weaknesses of the technique. Geographical, climatic, pedological, geological, botanical, and agricultural factors affect the stable isotope ratios (SIR) of bio-elements, and SIR variations are ultimately incorporated into animal tissue through eating, drinking, breathing, and exchange with the environment, being recorded in the resulting foods. SIR analysis was capable of determining geographical origin, animal diet, and the production system (such as organic/conventional or wild/farmed) for pork, beef, lamb, poultry, milk, butter, cheese, fish, and shellfish. In the case of the hard PDO (protected designations of origin) cheeses Grana Padano and Parmigiano Reggiano it is also used in real-life situations to assess the authenticity of grated and shredded cheese on the market.

δ18O of Ethanol in Wine and Spirits for Authentication Purposes

Since 1986 the European Union has established official isotopic analysis methods for detecting the illegal addition of sugar and water to wine and to enable geographical traceability. In this paper we investigate the possibility of using analysis of the 18O/16O stable isotope ratio (expressed as δ 18O) of ethanol to improve detection of the watering of wine and to determine the origin of ethanol. Sixty-nine authentic wine samples from all over Italy, 59 spirits from fruit and cereals, 5 chemically synthesized ethanols, one concentrated and rectified must, one beet and one cane sugar, one fresh must, and 6 waters with increasing δ 18O values were considered. Ethanol was recovered by distillation, using a Cadiot spinning band column, following the official OIV methods. The residual water was trapped by storing the distillate for at least 24 h on a molecular sieve. The 18O/16O ratio was measured using a pyrolyser interfaced with an isotope ratio mass spectrometer. The δ (-18)O of ethanol is significantly related to the δ 18O of the fermentation water and can be considered as a reliable internal reference. The values ranged from +24‰ to +36‰ in wine (years 2008 to 2012), +10‰ to +26‰ in fruit and cereal distillates, and from -2‰ to +12‰ in synthetic ethanol. The method was shown to be effective in improving detection of the watering of wine and determining the origin of ethanol (from grapes, other fruit, or synthesis), but not in detecting the addition of cane or beet sugar to wine.

Validation of methods for H, C, N and S stable isotopes and elemental analysis of cheese: results of an international collaborative study.

RATIONALE PDO cheeses, such as Parmigiano Reggiano and Grana Padano, which cost more than double generic similar cheeses, must be protected against mislabelling. The aim of this study was to validate the methods for the isotopic and elemental analysis of cheese, in order to support official recognition of their use in authenticity assessment. METHODS An international collaborative study based on blind duplicates of seven hard cheeses was performed according to the IUPAC protocol and ISO Standards 5725/2004 and 13528/2005. The H, C, N and S stable isotope ratios of defatted cheese determined using Isotope Ratio Mass Spectrometry (IRMS) and the content of Li, Na, Mn, Fe, Cu, Se, Rb, Sr, Mo, Ba, Re, Bi, U in cheese after acid microwave digestion using Inductively Coupled Plasma Mass Spectrometry or Optical Emission Spectrometry (ICP-MS or -OES) were measured in 13 different laboratories. RESULTS The average standard deviations of repeatability (sr) and reproducibility (sR) were 0.1 and 0.2 ‰ for δ(13)C values, 0.1 and 0.3 ‰ for δ(15)N values, 2 and 3 ‰ for δ(2)H values, and 0.4 and 0.6 ‰ for δ(34)S values, thus comparable with results of official methods and the literature for other food matrices. For elemental data, the average RSDr and RSDR values ranged between 2 and 11% and between 9 and 28%, respectively, consistent with methods reported by the FDA and in the literature for cheese. CONCLUSIONS The validation data obtained here can be submitted to the standardisation agencies to obtain official recognition for the methods, which is fundamental when they are used in commercial disputes and legal debates.