Analytical strategies for sensitive and precise determination of 87Sr/86Sr in olive oil through ion extraction, chromatographic separation, and multicollector inductively-coupled plasma mass-spectrometry.

Several food regulatory bodies regard olive oil as highly susceptible to food fraud, largely due to its substantial economic worth. Precise analytical tools are being developed to uncover these types of fraud. This study examines an innovative approach to extract strontium (Sr) from the olive oil matrix (via EDTA complexation and ion-exchange chromatography) and to determine its isotope composition by MC-ICP-MS. This technique was compared to a commonly used technique (i.e. acid extraction and extraction chromatography), and then validated. Three olive oils that are sold in France were prepared and analyzed by two methods: 1) acid extraction prior to Sr purification by Sr-spec resin and 2) complexation by EDTA prior to Sr purification by AG50W-X8. These methods were applied for the determination of the 87Sr/86Sr isotope ratio of 23 olive oils from various countries. We also demonstrated the feasibility of the method for the detection of olive oil mixtures.

Combined use of 87Sr/86Sr and carbon isotopes with multielemental analysis for the geographical authentication of Tunisian and European olive oils.

The geographical authentication in the agrifood industry has become a major issue to guarantee the quality of food products. Olive oil (OO) is particularly a complex matrix and establishing a reliable approach for linking OO samples to their origin is an analytical challenge. In this study, the isotopic composition of carbon, strontium and the concentrations of seventeen elements were determined in OOs from Tunisia, Southern France and the South Basque country. The preliminary results overlapped and showed that, taken individually, the isotopic and elemental approaches were not discriminant. A linear discriminant analysis applied to δ13C, 87Sr/86Sr and to the concentrations of 4 selected trace elements (Fe, Mn, V and Cr) allowed to classify, with high resolution, olive oils into 3 groups according to their provenance. The combination of the plant growing environment, the geological background, the mineral composition of the soil and the production process lead to a novel approach to deal with fraudulent practices in OO sector.

Olive Oil Traceability Studies Using Inorganic and Isotopic Signatures: A Review.

The olive oil industry is subject to significant fraudulent practices that can lead to serious economic implications and even affect consumer health. Therefore, many analytical strategies have been developed for olive oil's geographic authentication, including multi-elemental and isotopic analyses. In the first part of this review, the range of multi-elemental concentrations recorded in olive oil from the main olive oil-producing countries is discussed. The compiled data from the literature indicates that the concentrations of elements are in comparable ranges overall. They can be classified into three categories, with (1) Rb and Pb well below 1 µg kg-1; (2) elements such as As, B, Mn, Ni, and Sr ranging on average between 10 and 100 µg kg-1; and (3) elements including Cr, Fe, and Ca ranging between 100 to 10,000 µg kg-1. Various sample preparations, detection techniques, and statistical data treatments were reviewed and discussed. Results obtained through the selected analytical approaches have demonstrated a strong correlation between the multi-elemental composition of the oil and that of the soil in which the plant grew. The review next focused on the limits of olive oil authentication using the multi-elemental composition method. Finally, different methods based on isotopic signatures were compiled and critically assessed. Stable isotopes of light elements have provided acceptable segregation of oils from different origins for years already. More recently, the determination of stable isotopes of strontium has proven to be a reliable tool in determining the geographical origin of food products. The ratio 87Sr/86Sr is stable over time and directly related to soil geology; it merits further study and is likely to become part of the standard tool kit for olive oil origin determination, along with a combination of different isotopic approaches and multi-elemental composition.

Trace Elements Analysis of Tunisian and European Extra Virgin Olive Oils by ICP-MS and Chemometrics for Geographical Discrimination.

The aim of this study was to investigate the levels of trace elements in olive oils from different locations and their use for geographical authentication. Concentrations of seventeen elements were determined in a total of 42 olive oils from Tunisia, Spain (Basque country), and southern France, and in nine soil samples from Tunisia by quadrupole inductively plasma mass spectrometry. The compilation of appropriate techniques integrated into the analytical procedure achieved a precision (RSD) between 2% and 15% and low limits of detection (between 0.0002 and 0.313 µg kg-1). The accuracy of the analytical method applied for olive oil analysis was evaluated using SRM NIST 2387 Peanut butter. The recoveries obtained after microwave-assisted digestion for the certified elements ranged between 86% and 102%. Concentrations of non-certified elements (V, Cr, Co, Ni, Ba, Rb, Sr, Cd, Pb, and As) were presented. The use of Pearson correlation applied on paired Tunisian oil/soil samples has shown that several elements (Mg, Mn, Ni, and Sr) were significantly correlated. The multivariate statistics using principal component analysis have successfully discriminated against three studied origins. The most significant variables were the elemental concentrations of Cu, Cr, Fe, Mn, Sr, V, and Zn. This study shows the potential of applying trace elements profiles for olive oil geographical discrimination.

Phosphoric acid purification sludge: Potential in heavy metals and rare earth elements.

The present study was carried out to show the potential in heavy metals (HM) and the rare earth elements (REE) which presents the residues of phosphoric-acid(PA) purification. Three different cadmiferous solid residues (according to the nature of the purification process of the PA: BG, BC and BS) were collected from an industrial site located in the south of Tunisia. The mineralogical study showed the predominance of anhydrite, accompanied by quartz, malladrite; calcium sulfate hemihydrate and fluorapophyllite. The microanalysis showed (i) the association of cadmium and zinc, (ii) as well as the presence of associated REEs. The chemical analysis showed that (i) the calcium sulfate concentrations are majority in samples BS, BG and BC (44, 34 and 44%, respectively), (ii) significant concentrations of phosphoric acid (28, 18 and 21% P2O5, respectively), (iii) the HM: Cd, Zn, Cr, Ni, V, Cu, Pb, Co, Mo, Mn and U have proportion in the order of 0.1%. The concentrations of Cd, Zn and Cr are respectively in the order of: 230, 149 and 189 mg/kg for BS, 346, 243 and 153 mg/kg for BG and 183, 129 and 440 mg/kg for BC and (iv) the REEs: La, Ce, Nd, Eu, Y et Yb present considerable mass percentages able to reach 0.2%. A series of extraction tests was led on the cadmiferous sludges to evaluate the rates of HM (Cd, Zn) and REE dissolution, using two solvents (deionized water (DW) and aqueous sodium based alkaline metal solution). The results showed that the dissolution rates of Cd and Zn are respectively in the order of (12-29% and 41-45% for DW; 67-86% and 83-93% for Na2SO4 solution). The extractability of HM and REE is strongly influenced by pH, solvent nature and mineral load in the cadmiferous sludges. The water-soluble metals represent a significant mobile fraction, making the toxic elements more sensitive to mobilization processes, such as leaching and erosion. Whereas, the metals extractable by the Na2SO4 solution represent a very important exchangeable and "co-crystallization" fraction, which reflects the bioavailability of these metals.