An analytical method for determination of GC-amenable pesticides in complex matrices, was validated based on QuEChERS sample preparation and gas chromatography tandem mass spectrometry. Performance of the method was tested according to the EU SANTE guidelines for 172 pesticides belonging to different chemical classes, in three representative complex matrices. Three concentration levels were tested in order to establish the lowest limit of quantification possible. For some matrix/pesticide combination, careful selection of the quantification/ confirmation transitions was key to avoid interferences. Accurate quantification was achieved by standard addition. The number of compounds fulfilling EU SANTE criteria at 10 mu g/kg and 100 mu g/kg were 93 and 148 for roasted coffee, 93 and 112 for green tea and 98 and 111 for curry respectively. The method was further evaluated in different matrices (chili, clove, cumin, paprika and rosemary) with 50-90 % of the compounds fulfilling the validation criteria depending on the matrix.

Fluorotelomer alcohols (FTOHs) and acrylates (FTACs) have been reported as precursors of perfluoroalkyl acids and are known to contaminate biotic and abiotic compartments. Here, a detailed study was carried out for assessing the capability of dielectric barrier discharge ionization (DBDI) to be used as soft ionization technique, as alternative to the more energetic electron ionization (EI), for the quantitative determination of four FTOHs and two FTACs in environmental, biological or food samples by gas chromatography-mass spectrometry. While gas chromatography-EI-mass spectrometry (GC-EI-MS) shows significant fragmentation of the compounds, the ionization obtained by gas chromatography-DBDI-high resolution mass spectrometry (GC-DBDI-HRMS) affords dominant molecular adducts on the spectra. In the positive ion mode, the ion [M + H3O]+ and, of lower intensity, [M + H]+ are observed in the spectra of FTOHs, while the ion [M + H]+ is the most abundant in the spectra of FTACs and accompanied by a lower signal attributed to the ion [M + NO]+. In the negative ion mode, the FTOHs give rise to carbon dioxide and oxygen adducts observed with ions [M - H + CO2]- and [M + O2]-. Structure assignments were confirmed with stable isotope-labelled FTOH analogs and 13CO2. Gas chromatographic separation of the six compounds reveals room for development of methods applicable to soils, plants, water, food and biological materials.

To enable the monitoring of a wide scope of per- and polyfluoroalkyl substances (PFAS) in the ng/kg level in foodstuffs, an LC-MS/MS method comprising 57 analytes was developed and validated in seven different matrices (milk powder, milk-based infant formula, meat-based baby food puree, fish and fish oil, fresh egg, and soluble coffee). The analytical approach was based on an acetonitrile:water extraction followed by solid phase extraction clean-up with subsequent quantification of the extracted analytes either by isotope dilution (55 compounds) or by standard addition (2 compounds) mass spectrometry. The validation criteria followed the guidance document for the analysis of PFAS issued by the European Union Reference Laboratory for Halogenated Persistent Organic Pollutants. The lowest limits of quantification (LOQs) for the four recently regulated compounds (L-PFOS, PFOA, PFNA, L-PFHxS) were set at 0.010 µg/kg in baby and infant foods (as sold) but also in dairy ingredients. Exception was for PFOA in milk powder due to too large variability in the repeatability. Applicability of the method was further demonstrated in 37 commodity check matrices. Overall validation data demonstrated the robustness of the method for most of the compounds and the LOQs achieved were low enough to ensure compliance with Commission Regulation EU 2022/2388 but also to support future collection of occurrence data in ng/kg level in food.

Liquid chromatography-tandem mass spectrometry (LC-MS/MS) is a widespread technology used for the quantitative determination of per- and polyfluoroalkyl substances (PFAS) in foodstuff. Specifically, LC-MS/MS offers an attractive performance by combining the sensitivity and selectivity required by the European Union for testing perfluorooctane sulfonic acid, perfluorooctanoic acid, perfluorononanoic acid, and perfluorohexane sulfonic acid with maximum limits of quantification (LOQ) in the sub-parts-per-billion (μg/kg) or the parts-per-trillion (ng/kg) domains. In this article, we highlight the important diversity in LOQ definitions applied in LC-MS/MS methods described in the literature that raise concerns about the capability of some of those to generate reliable data requested by the European regulation. Here, we point out the risk of false response or misquantification if the criteria for assessing LOQ suffer from a lack of rigor. We emphasize the need to use PFAS-free samples spiked with the analyte(s) of interest and the application of identification criteria according to official documents for a sound measurement of the LOQ.

ADVERTISEMENT RETURN TO ISSUEViewpointNEXTDetermination of Poly- and Perfluoroalkylated Substances in Food: How Consistent Are Results across Laboratories?Thierry Delatour*Thierry DelatourSociété des Produits Nestlé S.A., Nestlé Research, Vers-chez-les-Blanc, CH-1000 Lausanne 26, Switzerland*E-mail: [email protected]More by Thierry Delatourhttps://orcid.org/0000-0003-1540-9645, Xanthippe TheurillatXanthippe TheurillatSociété des Produits Nestlé S.A., Nestlé Research, Vers-chez-les-Blanc, CH-1000 Lausanne 26, SwitzerlandMore by Xanthippe Theurillat, Claudia MujahidClaudia MujahidSociété des Produits Nestlé S.A., Nestlé Research, Vers-chez-les-Blanc, CH-1000 Lausanne 26, SwitzerlandMore by Claudia Mujahid, Bjo̷rn EriksenBjo̷rn EriksenSociété des Produits Nestlé S.A., Nestlé Research, Vers-chez-les-Blanc, CH-1000 Lausanne 26, SwitzerlandMore by Bjo̷rn Eriksen, and Pascal MottierPascal MottierSociété des Produits Nestlé S.A., Nestlé Research, Vers-chez-les-Blanc, CH-1000 Lausanne 26, SwitzerlandMore by Pascal MottierCite this: J. Agric. Food Chem. 2023, 71, 12, 4767–4768Publication Date (Web):March 14, 2023Publication History Received2 March 2023Published online14 March 2023Published inissue 29 March 2023https://pubs.acs.org/doi/10.1021/acs.jafc.3c01306https://doi.org/10.1021/acs.jafc.3c01306article-commentaryACS PublicationsCopyright © 2023 American Chemical Society. This publication is available under these Terms of Use. Request reuse permissions This publication is free to access through this site. Learn MoreArticle Views1314Altmetric-Citations-LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail PDF (2 MB) Get e-AlertscloseSUBJECTS:Animal derived food,Composites,Food,Testing and assessment,Toxins Get e-Alerts

This study presents the applicability of monochromatic wavelength dispersive X-ray fluorescence spectrometry (MWD-XRF) to quantify low range of concentrations, from 0.2 to 10 mg/kg of total chlorine in vegetable oils and bleaching clays effluents. The combination of total chlorine analysis by MWD-XRF and monochloropropanediol fatty acid esters (MCPDE) analysis by LC-MS of vegetable oils at different steps of the refining process allows to identify clays and technical aids used for bleaching as entry points of chlorine, potentially resulting in MCPDE formation during heat treatment of vegetable oils. Efficient washing of clays and technical aids monitored by chlorine measurement in successive effluents by MWD-XRF demonstrates the impact of washing by keeping total 3- MCPD content at low level in bleached vegetable oil. Further investigation on pH of the bleaching clays effluents shows that acidity is a key parameter during the formation of MCPD.

This talk will discuss synergistic opportunities between the effects of recently explored MCPD mitigation concepts in palm oil and sunflower oil. The discussed laboratory concepts will include dry versus wet removal of residual sediments, various degumming conditions and the role the bleaching clay in mitigating or catalyzing the formation of MCPD. The effects of the discussed mitigation concepts were studied by integrating them into the physical refining of crude oil, including water-based degumming and sealed ampoule tests mimicking the thermal conditions of edible oil deodorization. Key experiments were also reproduced in laboratory benchtop deodorizer. The MCPD levels were monitored by both direct LC-HRMS and indirect GC-MS based approaches. Beyond reviewing the MCPD mitigation effects and pros/cons of the investigated concepts, particular emphasis will be put on assessing whether the observed effects are due to correlation or causality between the refining parameters and the MCPD levels.

A QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) based multi-residue method has been developed and validated for the extraction and determination of pesticides in fatty matrices by gas chromatography tandem mass spectrometry. Extraction and clean-up were performed according to QuEChERS principles widely used for non-fatty matrices, with main difference, a higher solvent/sample- ratio followed by a 6-fold preconcentration step, ensuring good extractability and sensitivity. A validation according to SANTE guidelines was performed using a olive and sunflower oils mixture 1:1, w/w as representative matrix, at 2 concentration levels (5 and 50 mu g/kg) targeting 176 GC-amenable pesticides. Most compounds fulfilled the validation criteria, with a limit of quantification of 5 mu g/kg for 137 compounds , and of 50 mu g/kg for 24 compounds. Afterwards, the method performance was tested in six different fatty matrices with 73-90% of the analytes fulfilling the performance criteria at 5 mu g/kg depending on the matrix.

This study reports the benefits of auxiliary degumming (Aux.D) and pressurized high temperature (165 degrees C) water washing (PHTW) to mitigate the formation of monochloropropanediols (MCPD) during labscale physical refining of palm oil. Water-based degumming in combination with bleaching and deodorization are performed as the selected physical refining process. The mitigation concepts Aux.D and PHTW are integrated into the refining protocol and the ultimately observed MCPD levels in the fully refined oils are determined. Aux.D is performed by extracting the hydratable gum from pressed sunflower oil and using it as a degumming agent to further purify palm oil that has been previously subjected to centrifugation and water degumming. This approach enables the mitigation of 3-MCPD from the water washed reference 2.4-0.9 mg kg(-1) in ampoules. Even stronger mitigation is obtained when Aux.D is combined with bleaching and executed twice allowing a mitigation from the reference 1.9-0.6 mg kg(-1), in ampoules. PHTW is shown to decrease the 3-MCPD content of the refined oil from the reference 2.4-1 mg kg(-1), in ampoules and when combined with bleaching and executed twice showing a decrease from the reference 1.9-0.9 mg kg(-1). Practical applications: The benefits of these mitigation concepts are confirmed both in sealed ampoule tests and in deodorizer experiments at the lab scale. A combined application of Aux.D or PHTW with physical refining may represent new insights that can help to potentially further mitigate the formation of MCPD in physically refined palm oil beyond the limits achievable with current refining practices.

The aim of this study was to identify the chlorine source during sunflower oil production and propose mitigation strategies in order to prevent monochloropropane-diol ester (MCPDE) formation. Whole sunflower seeds, the separated kernel, hulls, and pressed cake were studied to pinpoint the location of chlorine donors originating from the crop. Acid-water-based degumming, bleaching, cooling, and heat treatment were performed to mimic the current refining process practices. Various oil extraction and refining scenarios were tested. MCPDE and total monochloropropane-diol (MCPD) content of the heat-treated samples were determined by liquid chromatography-HRMS and by an AOCS Official method. The results show that the oil produced from crop hulls and the bleaching clay used are the strongest chlorine sources boosting the MCPDE formation. Using a mixture of pressed and solvent extracted cake oil as model, total 3-MCPD decreased by a factor of 2 when applying static cooling in combination with a washed bleaching clay.

This study investigates whether the formation of monochloropropane diol fatty acid esters (MCPDE) can be mitigated by removing the residual sediments from vegetable oils. Settling and centrifugation were conducted in crude sunflower and palm oil and the purified oils and their sediment-rich fractions were heated and analyzed for their MCPDE content. Increased MCPDE levels by factors of x2 to x6 were found in the sediment-rich fractions of settled sunflower oils compared to the sediment-free oil. The sediment-containing fraction could be however purified by ultracentrifugation resulting in the mitigation of MCPDE levels by a factor of 10. The effect of residual sediment on the MCPDE formation was also confirmed in the case of palm oil showing x2 to x10 more MCPDE formation in the sediment containing fractions compared to the purified oil. These results confirm that the mechanical removal of the trace sediments from crude vegetable oils results in reduced MCPDE levels.

The aim of this study is to assess the synergy of mitigating main chlorine sources in palm oil and the oil refining conditions in a lab-scale physical refining process. Mitigation concepts including centrifugation and washing steps are integrated into the physical refining protocol and the MCPD levels in the fully refined oils are determined. The endogenous chlorine content of the crude oil and that of the bleaching clay is confirmed to predominantly impact MCPD formation in this refining process. Residual sediments are shown to induce up to 1 ppm MCPD in the fully refined oils. Residual chlorine content of bleaching clay is shown to increase MCPD content of the oil twofold.t-Test statistical analysis confirms significant effect of centrifugation, phosphoric acid content, clay type and clay washing on the formation of MCPD. Centrifugation is shown to effectively reduce the chlorine source coming from the sediments, while clay washing is shown to effectively reduce the chlorine source coming from the bleaching clay. These mitigation effects are confirmed both in sealed ampoule tests and in deodorizer experiments. Practical Applications: A combined application of strong centrifugation and clay washing is recommended to potentially improve the MCPD content of physically refined palm oil.

This study reports the heat-induced formation of furan by decarboxylation of 2-furoic acid, and 2-methylfuran by dehydration of furfuryl alcohol under dry conditions. Model systems were incubated at temperatures up to 190 degrees C, followed by quantitative determination of furan and 2-methylfuran performed by isotope dilution headspace gas chromatography-mass spectrometry. Results show that 2-furoic acid decarboxylation and furfuryl alcohol dehydration are activated as from about 140-160 degrees C. Furfuryl alcohol and 2-furoic acids were measured in a selection of roasted coffee products by isotope dilution liquid chromatography-high resolution mass spectrometry, and the data evidenced a strong correlation between the two compounds, suggesting an intimate mechanistic relationship between them. The possible oxidation of furfuryl alcohol to furfural and 2-furoic acid in heated food is raised with particular emphasis on coffee roasting. These findings are relevant for better understanding the formation of furan and alkylfurans in food, and ultimately opening avenues for mitigation.