Polychlorinated Naphthalenes in Foods from the French Market: Occurrence, Dietary Exposure, and Evaluation of Relative Contributions to Dioxin-like Contaminants.

Despite the growing interest in PCNs and the dioxin-like toxicity exhibited by a number of congeners, a comprehensive assessment of their contribution to the cocktail of dioxin-like contaminants is still lacking. To address such a shortcoming, this study investigated the PCN contamination in foodstuffs recently acquired in France, together with that of the regulatory polychlorinated dibenzodioxins/furans (PCDD/Fs) and polychlorinated biphenyls (PCBs). PCNs were ubiquitous at levels (∑70 PCNs = 2.5-150 pg g-1 wet weight) similar to those reported in other countries, with maximum concentrations observed in fish and fishery products from the North-East Atlantic Ocean. Their congener patterns further suggested unintentional releases of PCNs, while those of the other foodstuffs were correlated to the historical PCN profiles. Low risk from dietary exposure was estimated (∑70 PCNs-EDIs of 60-360 pg kg-1 bw d-1, ∑24 PCNs-TEQ-EDIs of 8 × 10-3-2.2 × 10-2 pg TEQ kg-1 bw d-1), with milk and dairy products being the highest contributors, followed by meat and meat products. Finally, the rather high contributions of PCNs to the total PCNs+PCDD/Fs+PCBs concentrations (0.9-50%, average of 9%) and the toxic equivalents (0.2-24%, average of 5%) show that these substances are not minor components of the PCNs+PCDD/Fs+PCBs cocktail.

Trace elements, dioxins and PCBs in different fish species and marine regions: Importance of the taxon and regional features.

Chemical contaminant concentrations in wild organisms are used to assess environmental status under the European Marine Strategy Framework Directive. However, this approach is challenged by the complex intra- and inter-species variability, and the different regional features. In this study, concentrations in trace elements (As, Cd, Hg and Pb), polychlorinated biphenyls (PCBs), polychlorodibenzo-para-dioxines (PCDDs) and polychlorodibenzofuranes (PCDFs) were monitored in 8 fish species sampled on the continental shelf of three French regions: the Eastern English Channel (EEC) and Bay of Biscay (BoB) in the Northeast Atlantic Ocean, and the Gulf of Lions (GoL) in Western Mediterranean Sea. Our objectives were to identify species or regions more likely to be contaminated and to assess how to take this variability into account in environmental assessment. While concentrations were higher in benthic and demersal piscivores, PCB and PCDD/F concentrations (lipid-weight) were similar in most teleost species. For Cd, Hg and Pb, the trophic group accumulating the highest concentrations depended on the contaminant and region. Concentrations in Hg, PCBs and PCDD/Fs were higher in the EEC and/or GoL than in BoB. Cadmium and Pb concentrations were highest in the BoB. Lipid content accounted for 35%-84% of organic contaminant variability. Lipid normalisation was employed to enhance robustness in the identification of spatial patterns. Contaminant patterns in chondrichthyans clearly differed from that in teleosts. In addition, trophic levels accounted for ≤1% and ≤33% of the contaminant variability in teleost fishes in the EEC and BoB, respectively. Therefore, developing taxa-specific thresholds might be a more practical way forward for environmental assessment than normalisation to trophic levels.

Proficiency and Interlaboratory Variability in the Determination of Phthalate and DINCH Biomarkers in Human Urine: Results from the HBM4EU Project.

A quality assurance/quality control program was implemented in the framework of the EU project HBM4EU to assess and improve the comparability of biomarker analysis and to build a network of competent laboratories. Four rounds of proficiency tests were organized for 15 phthalate and two DINCH urinary biomarkers (0.2-138 ng/mL) over a period of 18 months, with the involvement of 28 laboratories. A substantial improvement in performance was observed after the first round in particular, and by the end of the program, an average satisfactory performance rate of 90% was achieved. The interlaboratory reproducibility as derived from the participants' results varied for the various biomarkers and rounds, with an average of 24% for the biomarkers of eight single-isomer phthalates (e.g., DnBP and DEHP) and 43% for the more challenging biomarkers of the mixed-isomer phthalates (DiNP, DiDP) and DINCH. When the reproducibility was based only on the laboratories that consistently achieved a satisfactory performance, this improved to 17% and 26%, respectively, clearly demonstrating the success of the QA/QC efforts. The program thus aided in building capacity and the establishment of a network of competent laboratories able to generate comparable and accurate HBM data for phthalate and DINCH biomarkers in 14 EU countries. In addition, global comparability was ensured by including external expert laboratories.

European interlaboratory comparison investigations (ICI) and external quality assurance schemes (EQUAS) for the analysis of bisphenol A, S and F in human urine: Results from the HBM4EU project.

The Human Biomonitoring for Europe initiative (HBM4EU) aims to study the exposure of citizens to chemicals and potentially associated health effects. One objective of this project has been to build a network of laboratories able to answer to the requirements of European human biomonitoring studies. Within the HBM4EU quality assurance and quality control scheme (QA/QC), a number of interlaboratory comparison investigations (ICIs) and external quality assurance schemes (EQUASs) were organized to ensure data consistency, comparability and reliability. Bisphenols are among the prioritized substance groups in HBM4EU, including bisphenol A (BPA), bisphenol S (BPS) and bisphenol F (BPF) in human urine. In four rounds of ICI/EQUAS, two target concentration levels were considered, related to around P25 and P95 of the typical exposure distribution observed in the European general population. Special attention was paid to the conjugated phase II metabolites known to be most dominant in samples of environmentally exposed individuals, through the analysis of both native samples and samples fortified with glucuronide forms. For the low level, the average percentage of satisfactory results across the four rounds was 83% for BPA, 71% for BPS and 62% for BPF. For the high level, the percentages of satisfactory results increased to 93% for BPA, 89% for BPS and 86% for BPF. 24 out of 32 participating laboratories (75%) were approved for the analyses of BPA in the HBM4EU project according to the defined criterion of Z-scores for both low and high concentration levels in at least two ICI/EQUAS rounds. For BPS and BPF, the number of qualified laboratories was 18 out of 27 (67%) and 13 out of 28 (46%), respectively. These results demonstrate a strong analytical capability for BPA and BPS in Europe, while improvements may be needed for BPF.

Interlaboratory comparison investigations (ICIs) and external quality assurance schemes (EQUASs) for flame retardant analysis in biological matrices: Results from the HBM4EU project.

The European Human Biomonitoring Initiative (HBM4EU) is coordinating and advancing human biomonitoring (HBM). For this purpose, a network of laboratories delivering reliable analytical data on human exposure is fundamental. The analytical comparability and accuracy of laboratories analysing flame retardants (FRs) in serum and urine were investigated by a quality assurance/quality control (QA/QC) scheme comprising interlaboratory comparison investigations (ICIs) and external quality assurance schemes (EQUASs). This paper presents the evaluation process and discusses the results of four ICI/EQUAS rounds performed from 2018 to 2020 for the determination of ten halogenated flame retardants (HFRs) represented by three congeners of polybrominated diphenyl ethers (BDE-47, BDE-153 and BDE-209), two isomers of hexabromocyclododecane (α-HBCD and γ-HBCD), two dechloranes (anti-DP and syn-DP), tetrabromobisphenol A (TBBPA), decabromodiphenylethane (DBDPE), and 2,4,6-tribromophenol (2,4,6-TBP) in serum, and four metabolites of organophosphorus flame retardants (OPFRs) in urine, at two concentration levels. The number of satisfactory results reported by laboratories increased during the four rounds. In the case of HFRs, the scope of the participating laboratories varied substantially (from two to ten) and in most cases did not cover the entire target spectrum of chemicals. The highest participation rate was reached for BDE-47 and BDE-153. The majority of participants achieved more than 70% satisfactory results for these two compounds over all rounds. For other HFRs, the percentage of successful laboratories varied from 44 to 100%. The evaluation of TBBPA, DBDPE, and 2,4,6-TBP was not possible because the number of participating laboratories was too small. Only seven laboratories participated in the ICI/EQUAS scheme for OPFR metabolites and five of them were successful for at least two biomarkers. Nevertheless, the evaluation of laboratory performance using Z-scores in the first three rounds required an alternative approach compared to HFRs because of the small number of participants and the high variability of experts' results. The obtained results within the ICI/EQUAS programme showed a significant core network of comparable European laboratories for HBM of BDE-47, BDE-153, BDE-209, α-HBCD, γ-HBCD, anti-DP, and syn-DP. On the other hand, the data revealed a critically low analytical capacity in Europe for HBM of TBBPA, DBDPE, and 2,4,6-TBP as well as for the OPFR biomarkers.

The European human biomonitoring platform - Design and implementation of a laboratory quality assurance/quality control (QA/QC) programme for selected priority chemicals.

A fundamental objective of the human biomonitoring for Europe initiative (HBM4EU) is to progress toward comparable and robust exposure data for a wide variety of prioritized chemicals in human samples. A programme for Quality Assurance/Quality Control (QA/QC) was designed in HBM4EU with the purpose of creating a network of European laboratories providing comparable analytical data of high quality. Two approaches were chosen for two sets of prioritized chemicals with different timelines: (i) Scheme 1, where interested candidate laboratories participated in multiple rounds of proficiency tests (ii) Scheme 2, where selected expert laboratories participated in three rounds of interlaboratory comparison investigations. In both cases, the results were used to identify laboratories capable of generating consistent and comparable results for sample analysis in the frame of HBM4EU. In total, 84 laboratories from 26 countries were invited to participate in Scheme 1 that covered up to 73 biomarkers from Hexamoll® DINCH, phthalates, bisphenols, per- and polyfluoroalkyl substances, halogenated flame retardants (HFRs), organophosporous flame retardants (OPFRs), polycyclic aromatic hydrocarbons (PAH), cadmium, chromium and aromatic amines. 74 of the participants were successful for at least one biomarker in Scheme 1. Scheme 2 involved 22 biomarkers and successful results were obtained by 2 expert laboratories for arsenic, 5 for acrylamide, 4 for mycotoxins, 2 for pesticides and 2 for UV-filters in skin care products. The QA/QC programme allowed the identification of major difficulties and needs in HBM analysis as well of gaining insight in the analytical capacities of European laboratories. Furthermore, it is the first step towards the establishment of a sustainable European network of HBM laboratories.

Interlaboratory comparison investigations (ICI) and external quality assurance schemes (EQUAS) for cadmium in urine and blood: Results from the HBM4EU project.

Human biomonitoring (HBM) of cadmium is essential to assess and prevent toxic exposure. Generally, low cadmium levels in urine and blood of the general population place particularly high demands on quality assurance and control measures (QA/QC) for cadmium determination. One of the aims of the HBM4EU project is to harmonize and advance HBM in Europe. Cadmium is one of the chemicals selected as a priority substance for HBM implementation in the 30 European countries under HBM4EU. For this purpose, analytical comparability and accuracy of the analytical laboratories of participating countries was investigated in a QA/QC programme comprising interlaboratory comparison investigations (ICI) and external quality assurance schemes (EQUAS). This paper presents the evaluation process and discusses the results of four ICI/EQUAS rounds for the determination of cadmium in urine and blood. The majority of the 43 participating laboratories achieved satisfactory results, although low limits of quantification were required to quantify Cd concentrations at general population exposure levels. The relative standard deviation of the participants' results obtained from all ICI and EQUAS runs ranged from 8 to 36% for cadmium in urine and 8-28% for cadmium in blood. Applying inductively-coupled plasma mass spectrometry (ICP-MS), using an internal standard, and eliminating molybdenum oxide interferences was favourable for the accurate determination of cadmium in urine and blood. Furthermore, the analysis of cadmium in urine was found to have a critical point at approximately 0.05 µg/l, below which variability increased and laboratory proficiency decreased. This QA/QC programme succeeded in establishing a network of laboratories with high analytical comparability and accuracy for the analysis of cadmium across 20 European countries.

Levels of persistent organic pollutants (POPs) in foods from the first regional Sub-Saharan Africa Total Diet Study.

For the first time, a multi-centre Total Diet Study was carried out in Benin, Cameroon, Mali and Nigeria. We collected and prepared as consumed 528 typical fatty foods from those areas and pooled these subsamples into 44 composites samples. These core foods were tested for a wide spectrum of POPs, including polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), polychlorinated biphenyls (PCBs), brominated flame-retardants (BFRs), organochlorine compounds (OCs), perfluoro alkyl substances (PFAS) and chlorinated flame retardants (CFRs). The POPs contamination levels were similar or lower than those reported in total diet studies previously conducted worldwide. In most cases, core foods belonging to fish food group presented higher POPs concentrations than the other food groups. Interestingly, we observed a difference in both contamination profile and concentration for smoked fish compared to non-smoked fish. Such finding suggests that the smoking process itself might account for a large proportion of the contamination. Further investigation would require the assessment of combustion materials used to smoke fish as a potential vehicle, which may contribute to the dietary exposure of the studied populations to POPs.

Simultaneous analysis of historical, emerging and novel brominated flame retardants in food and feed using a common extraction and purification method.

Brominated Flame Retardants (BFRs) are still widely used for industrial purposes. These contaminants may enter the food chain where they mainly occur in food of animal origin. The aim of our work was to provide a unique method able to quantify the widest range of BFRs in feed and food items. After freeze-drying and grinding, a pressurized liquid extraction was carried out. The extract was purified on acidified silica, Florisil® and carbon columns, the four separated fractions were analyzed by gas and liquid chromatography coupled to high resolution and tandem mass spectrometry. Isotopic dilution was preferentially used when commercial labelled compounds were available. Analytical sensitivity was in accordance with the expectations of Recommendation 2014/118/EU for PBDEs, HBCDDs, TBBPA, TBBPA-bME, EHTBB, BEHTEBP and TBBPA-bME. Additional BFRs were included in this analytical method with the same level of performances (LOQs below 0.01 ng g-1 ww). These are PBBs, pTBX, TBCT, PBBz, PBT, PBEB, HBBz, BTBPE, OBIND and T23BPIC. However, some of the BFRs listed in Recommendation 2014/118/EU are not yet covered by our analytical method, i.e. TBBPA-bOHEE, TBBPA-bAE, TBBPA-bGE, TBBPA-bDiBPrE, TBBPS, TBBPS-bME, TDBPP, EBTEBPI, HBCYD and DBNPG. The uncertainty measurement was fully calculated for 21 of the 31 analytes monitored in the method. Reproducibility uncertainty was below 23% in isotopic dilution. Certified reference materials are now required to better characterize the trueness of this method, which was applied in the French National Control Plans.

Field investigation to determine the environmental source of PCBs in a pig farm.

During a national monitoring plan, a pork fat sample was declared non-compliant for the sum of dioxins and PCB-DL (EU regulation). The National Reference Laboratory together with competent authorities conducted extended investigations to determine rapidly the contamination source at the farm level. A range of samples (n = 129), representative of potential contamination sources, was selected for further characterization (fat, feed, materials, dust, soil) and was analyzed for PCDD/Fs and DL-PCBs by GC-HRMS. A hot spot was localized in the farm, which corresponded to a pre-feed storage tank, the paints of which presented huge DL-PCB concentrations (>1 × 106 pg g-1), responsible for the contamination. The present case report describes a new source of PCB contamination, previously undescribed.