Mineralization of Riluzole by Heterogeneous Fenton Oxidation Using Natural Iron Catalysts

Fenton (H2O2/Fe2+) system is a simple and efficient advanced oxidation technology (AOT) for the treatment of organic micropollutants in water and soil. However, it suffers from some drawbacks including high amount of the catalyst, acid pH requirement, sludge formation and slow regeneration of Fe2+ ions. If these drawbacks are surmounted, Fenton system can be the best choice AOT for the removal of persistent organics from water and soil. In this work, it was attempted to replace the homogeneous catalyst with a heterogeneous natural iron-based catalyst for the decomposition of H2O2 into oxidative radical species, mainly hydroxyl (HO•) and hydroperoxyl radicals (HO2•). The natural iron-based catalyst is hematite-rich (α-Fe2O3) and contains a nonnegligible amount of magnetite (Fe3O4) indicating the coexistence of Fe (III) and Fe(II) species. A pseudo-first order kinetics was determined for the decomposition of H2O2 by the iron-based solid catalyst with a rate constant increasing with the catalyst dose. The catalytic decomposition of H2O2 into hydroxyl radicals in the presence of the natural Fe-based catalyst was confirmed by the hydroxylation of benzoic acid into salicylic acid. The natural Fe-based catalyst/H2O2 system was applied for the degradation of riluzole in water. It was demonstrated that the smaller the particle size of the catalyst, the larger its surface area and the greater its catalytic activity towards H2O2 decomposition into hydroxyl radicals. The degradation of riluzole can occur at all pH levels in the range 3.0–12.0 with a rate and efficiency greater than H2O2 oxidation alone, indicating that the natural Fe-based catalyst can function at any pH without the need to control the pH by the addition of chemicals. An improvement in the efficiency and kinetics of the degradation of riluzole was observed under UV irradiation for both homogeneous and heterogeneous Fenton systems. The results chromatography analysis demonstrate that the degradation of riluzole starts by the opening of the triazole ring by releasing nitrate, sulfate, and fluoride ions. The reuse of the catalyst after heat treatment at 500 °C demonstrated that the heat-treated catalyst retained an efficiency >90% after five cycles. The results confirmed that the natural sources of iron, as a heterogeneous catalyst in a Fenton-like system, is an appropriate replacement of a Fe2+ homogeneous catalyst. The reuse of the heterogeneous catalyst after a heat-treatment represents an additional advantage of using a natural iron-based catalyst in Fenton-like systems

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.This research was funded by European Project TunTwin from the Horizon 2020 Framework program of the European Union under grant No. 952306. It was also funded by the French ANR EquiPex MARSS project with a contribution of the METROFOOD ESFRI project. This work was partially supported by the Euskadi/Nouvelle Aquitaine/Navarra Eurorregion through the research project ISOTOPO (with agreement no. 2020/3). The financial support of a Ph.D. grant for Emna G. Nasr has been provided by the “Excellence Eiffel” scholarship of Campus France, the European project “TunTwin” and the scholarship “bourse d’alternance” of University Tunis El Manar, Ministry of Higher Education and Scientific Research in Tunisia

Determination of 87Sr/86Sr isotopic ratio in olive oil and pomace using multicollector-ICPMS; analysis of pomace residues as a simpler approach for determination of 87Sr/86Sr ratio in olive oil with low Sr content

This study presents an analytical procedure for measuring the 87Sr/86Sr isotopic ratio in olive oil and pomace using multicollector-inductively coupled mass spectrometry (MC-ICPMS). The developed method combines liquid-liquid extraction with an acid solution and degradation of organic residues in the extract by dry ashing and oxidation by H2O2 and HNO3. The method enabled 87Sr/86Sr ratios to be obtained in olive oil with Sr content as low as 0.2 ng/g, with a precision of 54 ppm. The method’s validity was confirmed by an interlaboratory comparison using NIST SRM 2387, providing the first data on its elemental Sr (2380 ± 230 ng/g ; n = 10), and 87Sr/86Sr isotopic composition (0.70908 ± 0.00004 ; n = 14). The procedure was applied to olive oil and pomace samples, showing that they have an identical 87Sr/86Sr ratio, which was consistent with that determined in soils from the same orchards. The results thus revealed that Sr isotopic ratios of olive oil and pomace can both be used in geographical traceability studies of olive oil, which means that, instead of processing large volume of oil, characteristic 87Sr/86Sr signatures of olive oil can be more easily obtained by analyzing small quantities of pomace obtained by centrifuging the oil

Signatures inorganiques et isotopiques combinées pour la discrimination de l'origine géographique de l'huile d'olive

The globalization of the food industry has raised consumer interest in the geographical origin and the quality of food products. The global increase in food production and consumption, however, has led to fraudulent practices spreading. It threatens both the health of consumers and the economic balance of the food industry, which suffers huge financial loss every year. Olive oil is one of the most adulterated food products. As a result, a large array of analytical strategies was proposed for the geographical authentication of olive oil. The most reliable approaches that have demonstrated promising results for the geographical traceability of food products were based on the multi-elemental and isotopic fingerprinting. Nevertheless, trace elements, initially found at low to critically low concentrations in olive oil, are dissolved in a complex lipid matrix and thus the samples introduction in plasma-based instruments and the precise measurements of chemical components are challenging. This study presents a reliable analytical approach based on a three dimensional geographic information: (1) the mineral composition of the soil through the analysis of trace elements; (2) the geological background through the analysis of Sr isotopic composition; and (3) the pedo-climatic context through the determination of stable isotopes of carbon in olive oils. First, the trace elements were quantified in olive oils from Tunisia, Spain and France with high precision and accuracy by quadrupole ICP-MS following an optimized analytical procedure. The elemental concentrations combined with chemometrics allowed to classify olive oils according to their geographical provenance. Subsequently, an innovative method was developed and successfully applied for the quantitative extraction of Sr from olive oil matrix and accurate measurement of 87Sr/86Sr isotopic ratio by MC-ICP-MS. The conservation of 87Sr/86Sr isotopic ratios during the transfer of Sr from the soil to the plant and during olive oil extraction was demonstrated. The results were correlated with the geological characteristics of the bedrocks and thus highlighted that Sr isotopic composition of olive oil can be used as a reliable tool for fingerprinting olive oil geographic provenance. In last part of the manuscript, the stable isotopes of carbon were determined in olive oils by IRMS and allowed to trace the physiological processes of the olive tree to specific environmental characteristics. Each of the three studied single-parameter approaches provided reliable but limited geographic information. Therefore, they were combined together with chemometrics in order to establish an advanced geographical authentication tool able to overcome the most sophisticated fraudulent practices.La mondialisation de l'industrie alimentaire a suscité l'intérêt des consommateurs pour l'origine géographique et la qualité des produits alimentaires. L'augmentation de la production et de la consommation mondiale de denrées alimentaires a toutefois entraîné la propagation de pratiques frauduleuses. Celles-ci menacent à la fois la santé des consommateurs et l'équilibre économique de l'industrie alimentaire, qui subit chaque année d'énormes pertes financières. L'huile d'olive est l'un des produits alimentaires les plus fraudés. En conséquence, un large éventail de stratégies analytiques a été proposé pour l'authentification géographique de l'huile d'olive. Les approches les plus fiables qui ont démontré des résultats prometteurs pour la traçabilité géographique des produits alimentaires étaient basées sur l'empreinte multi-élémentaire et isotopique. Néanmoins, éléments traces, initialement présents à des concentrations faibles à très faibles dans l'huile d'olive, sont dissous dans une matrice lipidique complexe et donc l'introduction des échantillons dans les instruments basés sur le plasma et les mesures précises des composants chimiques sont difficiles. Cette étude présente une approche analytique fiable basée sur une information géographique tridimensionnelle : (1) la composition minérale du sol à travers l'analyse des éléments traces; (2) le contexte géologique par l'analyse de la composition isotopique du Sr; et (3) le contexte pédo-climatique à travers la détermination des isotopes stables du carbone dans les huiles d'olive. Tout d'abord, les éléments traces ont été quantifiés dans des huiles d'olive de Tunisie, d'Espagne et de France avec une grande précision et exactitude par ICP-MS quadripolaire suivant une procédure analytique optimisée. Les concentrations élémentaires combinées à la chimiométrie ont permis de classer les huiles d'olive en fonction de leur provenance géographique. Par la suite, une méthode innovante a été développée et appliquée avec succès pour l'extraction quantitative du Sr à partir de l'huile d'olive et la mesure précise du rapport isotopique 87Sr/86Sr par MC-ICP-MS. La conservation des rapports isotopiques 87Sr/86Sr pendant le transfert du Sr du sol à la plante et pendant l'extraction de l'huile d'olive a été démontrée. Les résultats ont été corrélés avec les caractéristiques géologiques des roches mères et ont ainsi mis en évidence que la composition isotopique Sr de l'huile d'olive peut être utilisée comme un outil fiable pour identifier la provenance géographique de l'huile d'olive. Dans la dernière partie du manuscrit, les isotopes stables du carbone ont été déterminés dans les huiles d'olive par IRMS et ont permis de retracer les processus physiologiques de l'olivier en fonction des caractéristiques environnementales spécifiques. Chacune des trois approches mono-paramètre étudiées a fourni des informations géographiques fiables mais limitées. C'est pourquoi elles ont été combinées avec la chimiométrie afin d'établir un outil d'authentification géographique avancé capable de faire face aux pratiques frauduleuses les plus sophistiquées

Combined inorganic and isotopic signatures for the geographical discrimination of olive oil

La mondialisation de l'industrie alimentaire a suscité l'intérêt des consommateurs pour l'origine géographique et la qualité des produits alimentaires. L'augmentation de la production et de la consommation mondiale de denrées alimentaires a toutefois entraîné la propagation de pratiques frauduleuses. Celles-ci menacent à la fois la santé des consommateurs et l'équilibre économique de l'industrie alimentaire, qui subit chaque année d'énormes pertes financières. L'huile d'olive est l'un des produits alimentaires les plus fraudés. En conséquence, un large éventail de stratégies analytiques a été proposé pour l'authentification géographique de l'huile d'olive. Les approches les plus fiables qui ont démontré des résultats prometteurs pour la traçabilité géographique des produits alimentaires étaient basées sur l'empreinte multi-élémentaire et isotopique. Néanmoins, éléments traces, initialement présents à des concentrations faibles à très faibles dans l'huile d'olive, sont dissous dans une matrice lipidique complexe et donc l'introduction des échantillons dans les instruments basés sur le plasma et les mesures précises des composants chimiques sont difficiles. Cette étude présente une approche analytique fiable basée sur une information géographique tridimensionnelle : (1) la composition minérale du sol à travers l'analyse des éléments traces; (2) le contexte géologique par l'analyse de la composition isotopique du Sr; et (3) le contexte pédo-climatique à travers la détermination des isotopes stables du carbone dans les huiles d'olive. Tout d'abord, les éléments traces ont été quantifiés dans des huiles d'olive de Tunisie, d'Espagne et de France avec une grande précision et exactitude par ICP-MS quadripolaire suivant une procédure analytique optimisée. Les concentrations élémentaires combinées à la chimiométrie ont permis de classer les huiles d'olive en fonction de leur provenance géographique. Par la suite, une méthode innovante a été développée et appliquée avec succès pour l'extraction quantitative du Sr à partir de l'huile d'olive et la mesure précise du rapport isotopique 87Sr/86Sr par MC-ICP-MS. La conservation des rapports isotopiques 87Sr/86Sr pendant le transfert du Sr du sol à la plante et pendant l'extraction de l'huile d'olive a été démontrée. Les résultats ont été corrélés avec les caractéristiques géologiques des roches mères et ont ainsi mis en évidence que la composition isotopique Sr de l'huile d'olive peut être utilisée comme un outil fiable pour identifier la provenance géographique de l'huile d'olive. Dans la dernière partie du manuscrit, les isotopes stables du carbone ont été déterminés dans les huiles d'olive par IRMS et ont permis de retracer les processus physiologiques de l'olivier en fonction des caractéristiques environnementales spécifiques. Chacune des trois approches mono-paramètre étudiées a fourni des informations géographiques fiables mais limitées. C'est pourquoi elles ont été combinées avec la chimiométrie afin d'établir un outil d'authentification géographique avancé capable de faire face aux pratiques frauduleuses les plus sophistiquées.The globalization of the food industry has raised consumer interest in the geographical origin and the quality of food products. The global increase in food production and consumption, however, has led to fraudulent practices spreading. It threatens both the health of consumers and the economic balance of the food industry, which suffers huge financial loss every year. Olive oil is one of the most adulterated food products. As a result, a large array of analytical strategies was proposed for the geographical authentication of olive oil. The most reliable approaches that have demonstrated promising results for the geographical traceability of food products were based on the multi-elemental and isotopic fingerprinting. Nevertheless, trace elements, initially found at low to critically low concentrations in olive oil, are dissolved in a complex lipid matrix and thus the samples introduction in plasma-based instruments and the precise measurements of chemical components are challenging. This study presents a reliable analytical approach based on a three dimensional geographic information: (1) the mineral composition of the soil through the analysis of trace elements; (2) the geological background through the analysis of Sr isotopic composition; and (3) the pedo-climatic context through the determination of stable isotopes of carbon in olive oils. First, the trace elements were quantified in olive oils from Tunisia, Spain and France with high precision and accuracy by quadrupole ICP-MS following an optimized analytical procedure. The elemental concentrations combined with chemometrics allowed to classify olive oils according to their geographical provenance. Subsequently, an innovative method was developed and successfully applied for the quantitative extraction of Sr from olive oil matrix and accurate measurement of 87Sr/86Sr isotopic ratio by MC-ICP-MS. The conservation of 87Sr/86Sr isotopic ratios during the transfer of Sr from the soil to the plant and during olive oil extraction was demonstrated. The results were correlated with the geological characteristics of the bedrocks and thus highlighted that Sr isotopic composition of olive oil can be used as a reliable tool for fingerprinting olive oil geographic provenance. In last part of the manuscript, the stable isotopes of carbon were determined in olive oils by IRMS and allowed to trace the physiological processes of the olive tree to specific environmental characteristics. Each of the three studied single-parameter approaches provided reliable but limited geographic information. Therefore, they were combined together with chemometrics in order to establish an advanced geographical authentication tool able to overcome the most sophisticated fraudulent practices

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

International audienceThe 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

<i>CDH1</i> Germline Variants in a Tunisian Cohort with Hereditary Diffuse Gastric Carcinoma

Mutational screening of the CDH1 gene is a standard treatment for patients who fulfill Hereditary Diffuse Gastric Cancer (HDGC) testing criteria. In this framework, the classification of variants found in this gene is a crucial step for the clinical management of patients at high risk for HDGC. The aim of our study was to identify CDH1 as well as CTNNA1 mutational profiles predisposing to HDGC in Tunisia. Thirty-four cases were included for this purpose. We performed Sanger sequencing for the entire coding region of both genes and MLPA (Multiplex Ligation Probe Amplification) assays to investigate large rearrangements of the CDH1 gene. As a result, three cases, all with the HDGC inclusion criteria (8.82% of the entire cohort), carried pathogenic and likely pathogenic variants of the CDH1 gene. These variants involve a novel splicing alteration, a missense c.2281G > A detected by Sanger sequencing, and a large rearrangement detected by MLPA. No pathogenic CTNNA1 variants were found. The large rearrangement is clearly pathogenic, implicating a large deletion of two exons. The novel splicing variant creates a cryptic site. The missense variant is a VUS (Variant with Uncertain Significance). With ACMG (American College of Medical Genetics and Genomics) classification and the evidence available, we thus suggest a revision of its status to likely pathogenic. Further functional studies or cosegregation analysis should be performed to confirm its pathogenicity. In addition, molecular exploration will be needed to understand the etiology of the other CDH1- and CTNNA1-negative cases fulfilling the HDGC inclusion criteria