LebensmittelchemieVolume 78, Issue S1 p. S1-078-S1-079 Abstract Bestimmung von perfluorierten Alkylsubstanzen (PFAS) in Muttermilchproben aus NRW Norina Aßhoff, Norina Aßhoff Chemisches und Veterinäruntersuchungsamt Münsterland-Emscher-Lippe (CVUA MEL), JosephKönig-Straße 40, 48143 Münster Institut für Lebensmittelchemie, Westfälische Wilhelms-Universität Münster, Corrensstraße 45, 48149 MünsterSearch for more papers by this authorThorsten Bernsmann, Thorsten Bernsmann Chemisches und Veterinäruntersuchungsamt Münsterland-Emscher-Lippe (CVUA MEL), JosephKönig-Straße 40, 48143 MünsterSearch for more papers by this authorMelanie Esselen, Melanie Esselen Institut für Lebensmittelchemie, Westfälische Wilhelms-Universität Münster, Corrensstraße 45, 48149 MünsterSearch for more papers by this authorThorsten Stahl, Thorsten Stahl Chemisches und Veterinäruntersuchungsamt Münsterland-Emscher-Lippe (CVUA MEL), JosephKönig-Straße 40, 48143 MünsterSearch for more papers by this author Norina Aßhoff, Norina Aßhoff Chemisches und Veterinäruntersuchungsamt Münsterland-Emscher-Lippe (CVUA MEL), JosephKönig-Straße 40, 48143 Münster Institut für Lebensmittelchemie, Westfälische Wilhelms-Universität Münster, Corrensstraße 45, 48149 MünsterSearch for more papers by this authorThorsten Bernsmann, Thorsten Bernsmann Chemisches und Veterinäruntersuchungsamt Münsterland-Emscher-Lippe (CVUA MEL), JosephKönig-Straße 40, 48143 MünsterSearch for more papers by this authorMelanie Esselen, Melanie Esselen Institut für Lebensmittelchemie, Westfälische Wilhelms-Universität Münster, Corrensstraße 45, 48149 MünsterSearch for more papers by this authorThorsten Stahl, Thorsten Stahl Chemisches und Veterinäruntersuchungsamt Münsterland-Emscher-Lippe (CVUA MEL), JosephKönig-Straße 40, 48143 MünsterSearch for more papers by this author First published: 01 March 2024 https://doi.org/10.1002/lemi.202452058AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Literatur 1Kärrman A., Ericson I., van Bavel B., Darnerud PO., Aune M., Glynn A., Lignell S., Lindström Environ G. Health Perspect, 115, 2007 226-230. 10.1289/ehp.9491 Google Scholar 2Bernsmann, T, Fürst, Organohalogen P. Compounds, Volume 70, 2008 718-721. Google Scholar 3Guomao Zheng, Erika Schreder, Jennifer Dempsey C., Nancy Uding, Valerie Chu, Gabriel Andres, Sheela Sathyanarayana, and Amina Salamova; Environmental Science & Technology, 55 (11), 2021 7510-7520. Google Scholar Volume78, IssueS1Supplement: Abstracts der Vorträge der Regionalverbände und die der Posterflashtalks der AG JLCMarch/April 2024Pages S1-078-S1-079 ReferencesRelatedInformation

Dietary intake is the major pathway of human exposure to per- and polyfluoroalkyl substances (PFAS). Due to their generally very low concentrations in food, especially for foods of plant origin, and their toxicological relevance, demand is growing for improved selective and sensitive analytical methods for the determination of PFAS in the lower ng/kg range. The relevance is pointed out due to the fact that the European Commission has published limits of quantification (LOQs) in the lower ng/kg range for different food matrices in Recommendation (EU) 2022/1431 on the monitoring of perfluoroalkyl substances in food. For example, LOQs of 2 ng/kg for perfluorooctanesulfonic acid (PFOS), 1 ng/kg for perfluorooctanoic acid (PFOA), 1 ng/kg for perfluorononanoic acid (PFNA) and 4 ng/kg for perfluorohexanesulfonic acid (PFHxS) in fruit, vegetables and baby foods are required. A new, very sensitive method is presented here for the determination of 22 PFAS in food and food contact materials. The method is based on liquid-solid extraction and automated clean-up using two solid phase extraction techniques. The analytes are separated and detected by HPLC-MS/MS. A limit of detection (LOD) of 0.33 ng/kg and an LOQ of 1.0 ng/kg are attained for plant foods such as fruits and vegetables as well as for milk and baby food. For foods of animal origin such as egg, meat, fish and paper-based food contact materials an LOD of 1.6 ng/kg as well as an LOQ of 5.0 ng/kg are attained. PFOS and PFOA were the most abundant compounds in the food samples with concentration as high as 1,051 ng/kg of PFOA in sea weed samples and 772 ng/kg of PFOS in eggs samples. In food contact material samples, higher levels were found with a maximum of 310,000 ng/kg PFHxA. In sum the presented method firstly allows determination of PFAS in a wide variety of foodstuffs and paper-based food contact materials at EU-required concentration ranges.

The industrial hemp sector is growing and, in recent years, has launched many novel hemp-derived products, including animal feed. It is, however, unclear to what extent individual cannabinoids from industrial hemp transfer from the feed into products of animal origin and whether they pose a risk for the consumer. Here we present the results of a feeding experiment with industrial hemp silage in dairy cows. Hemp feeding included changes in feed intake, milk yield, respiratory and heart rates, and behaviour. We combined liquid chromatography–tandem mass spectrometry-based analyses and toxicokinetic computer modelling to estimate the transfer of several cannabinoids (Δ 9 -tetrahydrocannabinol (Δ 9 -THC), Δ 8 -THC, Δ 9 -tetrahydrocannabinolic acid, Δ 9 -tetrahydrocannabivarin, 11-OH-Δ 9 -THC, 11-nor-9-carboxy-Δ 9 -THC, cannabidiol, cannabinol and cannabidivarin) from animal feed to milk. For Δ 9 -THC, which has a feed-to-milk transfer rate of 0.20% ± 0.03%, the acute reference dose for humans was exceeded in several consumer groups in exposure scenarios for milk and dairy product consumption when using industrial hemp to feed dairy cows.

This study presents a comprehensive two-dimensional gas chromatography with negative chemical ionization quadrupole time-of-flight mass spectrometry (GC × GC-NCI-QTOF/MS) method, which allows for a precise chromatographic separation of short-chain chlorinated paraffins (SCCPs) and medium-chain chlorinated paraffins (MCCPs). A new reversed-phase column setup was used, which allows for more accurate separation of MCCPs compared to known GC × GC methods. In a pilot study, 25 freshwater fish samples were analyzed with this method to characterize chlorinated paraffin (CP) compositions. The CP composition was similar in the samples, an observation that is important for the development of a suitable routine method. MCCP contamination was considerably higher than SCCP contamination, with concentrations of 1.3-410 ng/g of wet weight and 0.67-6.5 ng/g of wet weight, respectively. These results were compared to those obtained using a second method, direct injection-atmospheric pressure chemical ionization (APCI)-Orbitrap/mass spectrometry (MS). GC × GC separation was considered to be advantageous for accurate quantification of CP contamination.

Non-dioxin-like polychlorinated biphenyls (ndl-PCBs) are a subclass of persistent bioaccumulative pollutants able to enter the food chain. We investigated the transfer of ndl-PCBs from contaminated feed into meat and liver of fattening chickens. A total of 48 chicks were divided into five treatment and one control groups. Treated animals were fed with contaminated diets (11.7 ± 0.4 μg/kg sum of indicator ndl-PCBs; 88% dry matter (DM)) before slaughter for different subperiods of time: 16, 23, 28, 32, and 36 days for groups 1-5, respectively. One day after the end of each subperiod, three animals per group were slaughtered to determine the congener-specific ndl-PCB content. All remaining animals were fed the control feed until slaughter on day 37 to probe depuration. We used these data to generate congener-specific physiologically based toxicokinetic (PBTK) models for indicator ndl-PCBs. The models show that PCBs 28, 138, 153, and 180 form a more slowly eliminated cluster (with an observed transfer rate into meat over 74% and observed half-lives over 8.7 days) than PCBs 52 and 101 (with a transfer rate under 13% and half-lives under 2.6 days). Our simulations show that ndl-PCB levels in feed lower than 3.9 (long 56-day) or 4.4 μg/kg (short 37-day fattening period) would be necessary to ensure the current maximum level in muscle meat (fat basis), according to EU Regulations 1881/2006 and 1259/2011. The PBTK models are made available in the Python and Food Safety Knowledge Exchange formats.

Recent European regulations have indicated the need for new bioanalytical screening methods capable of monitoring dioxin and dioxin-like compounds in foodstuffs and environmental samples, cost-effectively and with a quicker turnaround. Cryo-cells of the hepatic H4IIE line preserved in 96-well plates were exposed to sample extracts prepared from various foodstuffs and analysed for their content of dioxins and dioxin-like compounds by means of the 7-Ethoxyresorufin-O-Deethylase (EROD)-assay in two laboratories. Assay data were compared between both laboratories and results from instrumental analysis used as a confirmatory method. Additionally, cut-off values for the different studied matrices were derived. The current European regulation regarding methods of analysis for the control of foodstuffs was applied with the aim of determining the feasibility of the cryo-methodology. Results obtained in both laboratories were in congruence with the required validation parameters of the Commission Regulation (EU) No 2017/644. Cut-off values should be established matrix-dependent to reduce the rate of false compliant results and to keep the rate of false non-compliant results under control. In summary, the ready-to-use cryo-assay method for the bioanalytical screening of foodstuffs in control laboratories without cell-culture facilities has successfully proven to be accurate, far quicker and more cost effective than current methods.

Until recently, the analysis of dioxins and dioxin-like PCBs in feed and food was generally performed by gas chromatography coupled to high resolution mass spectrometry (GC-HRMS) due to its superior resolution and sensitivity compared to the then available gas chromatographic techniques with other detectors. However, in the past few years the technology of GC coupled to tandem mass spectrometry (GC-MS/MS) has made great progress and modern GC-MS/MS systems nowadays reach similar limits of detection as GC-HRMS systems. This paper describes the step-wise optimization of GC-MS/MS variables for the sensitive and selective measurement of dioxins and PCBs in feed and food to comply with the performance criteria set by the EU Commission for confirmatory methods. The developed method was shown to give linear response over the required concentration range and good repeatability. Analyses of samples from official feed and food control demonstrated that a surveillance of the legal limits for dioxins and PCBs in feed and food is easily achievable. The generated quantitative results for dioxins and PCBs are compared with those data obtained for the same samples by GC-HRMS and show good agreement. As the purchase and running costs for GC-MS/MS systems constitute only a fractional amount compared to GC-HRMS instruments, the application of GC-MS/MS represents a cost-effective alternative for GC-HRMS to reliably and unequivocally confirm low levels of dioxins and PCBs in feed and food.

1 CART, Chemistry Department, University of Liege, Belgium 2 Istituto Zooprofilattico Sperimentale dell'Abruzzo e del Molise G. Caporale, Teramo, Italy 3 The Food and Environment Research Agency (FERA), York, YO41 1LZ, United Kingdom 4 European Union Reference Laboratory for Dioxins and PCBs in Feed and Food, Freiburg, Germany 5 SGS Environmental Services, Wilmington, NC, USA 6 National Institute of Nutrition and Seafood research, Bergen, Norway 7 Istituto Superiore di Sanita (ISS), Roma, Italy 8 LABoratoire d’Etude des Residus et Contaminants dans les Aliments (LABERCA), Nantes, France 9 Federal Environment Agency Ltd, Austria 10 Chemical and Veterinary Analytical Institute Munsterland-Emscher-Lippe, Munster, Germany 11 It's About Purpose, LLC, Carolina Beach, NC, USA 12 RIKILT, Wageningen, The Netherlands

UVB radiation-induced signaling in mammalian cells involves two major pathways: one that is initiated through the generation of DNA photoproducts in the nucleus and a second one that occurs independently of DNA damage and is characterized by cell surface receptor activation. The chromophore for the latter one has been unknown. Here, we report that the UVB response involves tryptophan as a chromophore. We show that through the intracellular generation of photoproducts, such as the arylhydrocarbon receptor (AhR) ligand 6-formylindolo[3,2-b]carbazole, signaling events are initiated, which are transferred to the nucleus and the cell membrane via activation of the cytoplasmatic AhR. Specifically, AhR activation by UVB leads to (i) transcriptional induction of cytochrome P450 1A1 and (ii) EGF receptor internalization with activation of the EGF receptor downstream target ERK1/2 and subsequent induction of cyclooxygenase-2. The role of the AhR in the UVB stress response was confirmedin vivoby studies employing AhR KO mice.