A Review of the Occurrence of Metals and Xenobiotics in European Hedgehogs (Erinaceus europaeus).

Monitoring data from several European countries indicate that European hedgehog (Erinaceus europaeus) populations are declining, and research exploring the causes of the decline, including exposure to potentially harmful xenobiotics and metals, may inform conservation initiatives to protect this species in the wild. Hedgehogs are ground-dwelling mammals, feeding on a range of insects, slugs, snails, and earthworms, as well as eggs, live vertebrates, and carrion, including carcasses of apex predator species representing higher levels of the food chain. Consequently, hedgehogs come into close contact with contaminants present in their habitats and prey. This review investigated the studies available on the subject of the occurrence of metals and organic xenobiotics in hedgehogs. This study found that a vast range of different pesticides; persistent organic pollutants (POPs), including organochlorine compounds and brominated flame retardants (BFRs); as well as toxic heavy metals could be detected. Some compounds occurred in lethal concentrations, and some were associated with a potential adverse effect on hedgehog health and survival. Due to their ecology, combined with the opportunity to apply non-invasive sampling techniques using spines as sampling material, we suggest that the European hedgehog is a relevant bioindicator species for monitoring the exposure of terrestrial wildlife to potential toxicants in urban and rural environments.

What is in the fish? Collaborative trial in suspect and non-target screening of organic micropollutants using LC- and GC-HRMS.

A collaborative trial involving 16 participants from nine European countries was conducted within the NORMAN network in efforts to harmonise suspect and non-target screening of environmental contaminants in whole fish samples of bream (Abramis brama). Participants were provided with freeze-dried, homogenised fish samples from a contaminated and a reference site, extracts (spiked and non-spiked) and reference sample preparation protocols for liquid chromatography (LC) and gas chromatography (GC) coupled to high resolution mass spectrometry (HRMS). Participants extracted fish samples using their in-house sample preparation method and/or the protocol provided. Participants correctly identified 9-69 % of spiked compounds using LC-HRMS and 20-60 % of spiked compounds using GC-HRMS. From the contaminated site, suspect screening with participants' own suspect lists led to putative identification of on average ∼145 and ∼20 unique features per participant using LC-HRMS and GC-HRMS, respectively, while non-target screening identified on average ∼42 and ∼56 unique features per participant using LC-HRMS and GC-HRMS, respectively. Within the same sub-group of sample preparation method, only a few features were identified by at least two participants in suspect screening (16 features using LC-HRMS, 0 features using GC-HRMS) and non-target screening (0 features using LC-HRMS, 2 features using GC-HRMS). The compounds identified had log octanol/water partition coefficient (KOW) values from -9.9 to 16 and mass-to-charge ratios (m/z) of 68 to 761 (LC-HRMS and GC-HRMS). A significant linear trend was found between log KOW and m/z for the GC-HRMS data. Overall, these findings indicate that differences in screening results are mainly due to the data analysis workflows used by different participants. Further work is needed to harmonise the results obtained when applying suspect and non-target screening approaches to environmental biota samples.

Suspect and non-target screening of semi-volatile emerging contaminants in indoor dust from Danish kindergartens.

Indoor dust is a sink of hundreds of organic chemicals, and humans may potentially be exposed to these via indoor activities. This study investigated potentially harmful semi-volatile organic contaminants in indoor dust from Danish kindergartens using suspect and non-target screening on gas chromatography (GC)-Orbitrap, supported by target analyses using GC-low resolution mass spectrometry (LRMS). A suspect list of 41 chemicals with one or more toxicological endpoints, i.e. endocrine disruption, carcinogenicity, neurotoxicity and allergenicity, known or suspected to be present in indoor dust, was established including phthalate and non-phthalate plasticizers, flame retardants, bisphenols, biocides, UV filters and other plastic additives. Of these, 29 contaminants were detected in the indoor dust samples, also including several compounds that had been banned or restricted for years. In addition, 22 chemicals were tentatively identified via non-target screening. Several chemicals have not previously been detected in Danish indoor dust. Most of the detected chemicals are known to be potentially harmful for human health while hazard assessment of the remaining compounds indicated limited risks to human. However, children were not specifically considered in this hazard assessment.

Long-Term Influence of PCB- and PBDE-Spiked Microplastic Spheres Fed through Rotifers to Atlantic Cod (Gadus morhua) Larvae.

Omnipresent microplastics (MPs) in marine ecosystems are ingested at all trophic levels and may be a vector for the transfer of persistent organic pollutants (POPs) through the food web. We fed rotifers polyethylene MPs (1-4 µm) spiked with seven congeners of polychlorinated biphenyls (PCBs) and two congeners of polybrominated diphenyl ethers (PBDEs). In turn, these rotifers were fed to cod larvae from 2-30 days post-hatching (dph), while the control groups were fed rotifers without MPs. After 30 dph, all the groups were fed the same feed without MPs. Whole-body larvae were sampled at 30 and 60 dph, and four months later the skin of 10 g juveniles was sampled. The PCBs and PBDEs concentrations were significantly higher in MP larvae compared to the control larvae at 30 dph, but the significance dissipated at 60 dph. Expression of stress-related genes in cod larvae at 30 and 60 dph showed inconclusive minor random effects. The skin of MP juveniles showed disrupted epithelial integrity, fewer club cells and downregulation of a suite of genes involved in immunity, metabolism and the development of skin. Our study showed that POPs were transferred through the food web and accumulated in the larvae, but that the level of pollutants decreased once the exposure was ceased, possibly related to growth dilution. Considering the transcriptomic and histological findings, POPs spiked to MPs and/or MPs themselves may have long-term effects in the skin barrier defense system, immune response and epithelium integrity, which may potentially reduce the robustness and overall fitness of the fish.

Coordination of chemical analyses under the European Human Biomonitoring Initiative (HBM4EU): Concepts, procedures and lessons learnt.

The European Human Biomonitoring Initiative (HBM4EU) ran from 2017 to 2022 with the aim of advancing and harmonizing human biomonitoring in Europe. More than 40,000 analyses were performed on human samples in different human biomonitoring studies in HBM4EU, addressing the chemical exposure of the general population, temporal developments, occupational exposure and a public health intervention on mercury in populations with high fish consumption. The analyses covered 15 priority groups of organic chemicals and metals and were carried out by a network of laboratories meeting the requirements of a comprehensive quality assurance and control system. The coordination of the chemical analyses included establishing contacts between sample owners and qualified laboratories and monitoring the progress of the chemical analyses during the analytical phase, also addressing status and consequences of Covid-19 measures. Other challenges were related to the novelty and complexity of HBM4EU, including administrative and financial matters and implementation of standardized procedures. Many individual contacts were necessary in the initial phase of HBM4EU. However, there is a potential to develop more streamlined and standardized communication and coordination in the analytical phase of a consolidated European HBM programme.

External Quality Assurance Schemes (EQUASs) and Inter-laboratory Comparison Investigations (ICIs) for human biomonitoring of polycyclic aromatic hydrocarbon (PAH) biomarkers in urine as part of the quality assurance programme under HBM4EU.

Polycyclic aromatic hydrocarbons (PAHs) were included as priority substances for human biomonitoring (HBM) in the European Human Biomonitoring Initiative (HBM4EU), which intended to harmonise and advance HBM across Europe. For this project, a specific Quality Assurance and Quality Control (QA/QC) programme applying Inter-laboratory Comparison Investigations (ICIs) and External Quality Assurance Schemes (EQUASs) was developed to ensure the comparability and accuracy of participating analytical laboratories. This paper presents the results of four ICI/EQUAS rounds for the determination of 13 PAH metabolites in urine, i.e. 1-naphthol, 2-naphthol, 1,2-dihydroxynaphthalene, 2-, 3- and 9-hydroxyfluorene, 1-, 2-, 3-, 4- and 9-hydroxyphenanthrene, 1-hydroxypyrene and 3-hydroxybenzo(a)pyrene. However, 4 PAH metabolites could not be evaluated as the analytical capacity of participating laboratories was too low. Across all rounds and biomarkers, 86% of the participants achieved satisfactory results, although low limits of quantification were required to quantify the urinary metabolites at exposure levels of the general population. Using high-performance liquid or gas chromatography coupled with mass spectrometry (HPLC-MS; GC-MS) and isotope dilution for calibration as well as performing an enzymatic deconjugation step proved to be favourable for the accurate determination of PAHs in urine. Finally, the HBM4EU QA/QC programme identified an international network of laboratories providing comparable results in the analysis of urinary PAH biomarkers, although covering all parameters initially selected was still too challenging.

Berlin statement on legacy and emerging contaminants in polar regions.

Polar regions should be given greater consideration with respect to the monitoring, risk assessment, and management of potentially harmful chemicals, consistent with requirements of the precautionary principle. Protecting the vulnerable polar environments requires (i) raising political and public awareness and (ii) restricting and preventing global emissions of harmful chemicals at their sources. The Berlin Statement is the outcome of an international workshop with representatives of the European Commission, the Arctic Council, the Antarctic Treaty Consultative Meeting, the Stockholm Convention on Persistent Organic Pollutants (POPs), environmental specimen banks, and data centers, as well as scientists from various international research institutions. The statement addresses urgent chemical pollution issues in the polar regions and provides recommendations for improving screening, monitoring, risk assessment, research cooperation, and open data sharing to provide environmental policy makers and chemicals management decision-makers with relevant and reliable contaminant data to better protect the polar environments. The consensus reached at the workshop can be summarized in just two words: "Act now!" Specifically, "Act now!" to reduce the presence and impact of anthropogenic chemical pollution in polar regions by. •Establishing participatory co-development frameworks in a permanent multi-disciplinary platform for Arctic-Antarctic collaborations and establishing exchanges between the Arctic Monitoring and Assessment Program (AMAP) of the Arctic Council and the Antarctic Monitoring and Assessment Program (AnMAP) of the Scientific Committee on Antarctic Research (SCAR) to increase the visibility and exchange of contaminant data and to support the development of harmonized monitoring programs. •Integrating environmental specimen banking, innovative screening approaches and archiving systems, to provide opportunities for improved assessment of contaminants to protect polar regions.

Endocrine disrupting chemicals in indoor dust: A review of temporal and spatial trends, and human exposure.

Several chemicals with widespread consumer uses have been identified as endocrine-disrupting chemicals (EDCs), with a potential risk to humans. The occurrence in indoor dust and resulting human exposure have been reviewed for six groups of known and suspected EDCs, including phthalates and non-phthalate plasticizers, flame retardants, bisphenols, per- and polyfluoroalkyl substances (PFAS), biocides and personal care product additives (PCPs). Some banned or restricted EDCs, such as polybrominated diphenyl ethers (PBDEs), di-(2-ethylhexyl) phthalate (DEHP), bisphenol A (BPA), perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA), are still widely detected in indoor dust in most countries, even as the predominating compounds of their group, but generally with decreasing trends. Meanwhile, alternatives that are also potential EDCs, such as bisphenol S (BPS), bisphenol F (BPF), decabromodiphenyl ethane (DBDPE) and organophosphate flame retardants (OPFRs), and PFAS precursors, such as fluorotelomer alcohols, have been detected in indoor dust with increasing frequencies and concentrations. Associations between some known and suspected EDCs, such as phthalate and non-phthalate plasticizers, FRs and BPs, in indoor dust and paired human samples indicate indoor dust as an important human exposure pathway. Although the estimated daily intake (EDI) of most of the investigated compounds was mostly below reference values, the co-exposure to a multitude of known or suspected EDCs requires a better understanding of mixture effects.

Implementation and coordination of an ethics framework in HBM4EU - Experiences and reflections.

Human biomonitoring involves the use of human samples and data to investigate exposure to environmental chemicals and their impact on human health. HBM4EU developed a coordinated and harmonized approach involving 29 countries in Europe plus Israel. Addressing ethical issues has been an indispensable prerequisite, from the application phase, grant agreement, project performance to the closing of the project. HBM4EU has established a better understanding of the ethics in such projects and the need for a standardised way of reporting and handling of ethics and data exchange, securing compliance with ethics standards, transparency, transferability and sustainability. The main reflections were: KNOWLEDGE: Ethics awareness, norms and practices are dynamic and increased throughout the project, much learning and experience is achieved by practice and dialogue. ATTITUDE: Rules and standards were very diversely known and needed to adhere to local practices. ASSISTANCE: Good results achieved from webinars, training, help desk, and individual consultations. STANDARDISATION: Was achieved by templates and naming convention across documents. MANAGEMENT: The establishment of the SharePoint directory with uploading of all requested documents assisted collaboration and exchange. Also, a designated task for ethics within the management/coordination work package and the enthusiasm of the task leader were essential. COMPLIANCE: Some, but not all partners were very good at complying with deadlines and standards. TRANSFERABILITY AND SUSTAINABILITY: All documents are archived in the SharePoint directory while a system assuring updating is recommended. TRANSPARENCY: Assured by public access to annual ethics reports. The ethics reports bridged to the annual work plans (AWPs). EVALUATION: The Ethics Check by the Commission was successful.

Mercury contamination of two e-waste recycling sites in Ghana: an investigation into mercury pollution at Dagomba Line (Kumasi) and Agbogbloshie (Accra).

This study investigated mercury pollution at two e-waste recycling sites in Ghana-Dagomba Line in Kumasi and Agbogbloshie in Accra. A total of 129 soil samples taken at 100 m and 50 m resolutions, respectively, for Dagomba Line and Agbogbloshie, were analysed for mercury using a Zeeman atomic absorption spectrometry. Mercury concentrations from the recycling sites (ranging from 0.11 to 7.57 mg/kg Dagomba Line, and 0.01-4.36 mg/kg at Agbogbloshie) were significantly higher than that of the surrounding areas (0.01-0.17 mg/kg in Kumasi and 0.01-2.18 mg/kg in Accra) and unpolluted control sites (0.05 mg/kg in Kumasi and 0.02 mg/kg in Accra). The dismantling sites at both locations had the highest mercury concentrations. Furthermore, the concentrations were significantly higher at the Dagomba Line site in Kumasi than at Agbogbloshie, even though the Dagomba Line site is relatively recent. The mercury concentrations at both sites exceeded the pollution prevention and abatement level of 0.1 mg/kg. However, the estimated human health risk showed no potential human health effects. Moreover, the mercury concentrations in water and sediment (0.12-7.69 ng/L and 0.02-0.28 ng/L for Dagomba Line and Agbogbloshie, respectively) were below the US EPA standards. Findings from this study show that e-waste recycling can contaminate the topsoil with mercury, irrespective of the scale of the activity.

Influences of climate change on long-term time series of persistent organic pollutants (POPs) in Arctic and Antarctic biota.

Time series of contaminants in the Arctic are an important instrument to detect emerging issues and to monitor the effectiveness of chemicals regulation, based on the assumption of a direct reflection of changes in primary emissions. Climate change has the potential to influence these time trends, through direct physical and chemical processes and/or changes in ecosystems. This study was part of an assessment of the Arctic Monitoring and Assessment Programme (AMAP), analysing potential links between changes in climate-related physical and biological variables and time trends of persistent organic pollutants (POPs) in Arctic biota, with some additional information from the Antarctic. Several correlative relationships were identified between POP temporal trends in freshwater and marine biota and physical climate parameters such as oscillation indices, sea-ice coverage, temperature and precipitation, although the mechanisms behind these observations remain poorly understood. Biological data indicate changes in the diet and trophic level of some species, especially seabirds and polar bears, with consequences for their POP exposure. Studies from the Antarctic highlight increased POP availability after iceberg calving. Including physical and/or biological parameters in the POP time trend analysis has led to small deviations in some declining trends, but did generally not change the overall direction of the trend. In addition, regional and temporary perturbations occurred. Effects on POP time trends appear to have been more pronounced in recent years and to show time lags, suggesting that climate-related effects on the long time series might be gaining importance.

Silicone wristbands as personal passive samplers of exposure to polychlorinated biphenyls in contaminated buildings.

Polychlorinated biphenyls (PCBs) were used in a number of industrial products from 1950 to 80s, including building materials. As a result, some buildings exhibit high levels of PCBs in the indoor environment. The aim of this study was to test silicone wristbands as a method for estimating personal exposure to PCBs in buildings both in controlled experiments and field settings. In the controlled study, the sampling kinetics of silicone wristbands were investigated in a 31-day uptake study. The field study focused on the application of wristbands as a personal exposure measure. It included 71 persons in a contaminated housing estate and 23 persons in a reference group. The linear uptake of PCBs ranged from 2 to 24 days for PCB-8, 18, 28, 31, 40, 44, 49, 52, 66, 99, and 101 under controlled conditions. A generic sampling rate (Rk) of 2.3 m3 d-1 corresponding to a mass transfer coefficient of 17 m h-1 was found in the controlled kinetic study. Partitioning coefficients were also determined for the nine congeners. In the field study, an apparent generic field sampling rate (Rf) of 2.6 m3 d-1 was found; when adjusted to reported hours exposed, it increased to 3.5 m3 d-1. The wristbands were shown to be a good tool for predicting airborne exposure, as there was a highly significant difference between the exposed and reference group as well as a clear trend when used for ranking of exposure. In correlation analyses, highly significant correlations were observed between air and wristband levels, though adjusting by self-reported exposure time only increased the correlation marginally in the field study. The obtained kinetic data can be used for estimating the magnitude of external exposure. The advantages provided by the wristbands in the form of easy use and handling are significant, though the limitations should also be acknowledged.

Interlaboratory Comparison Investigations (ICIs) and External Quality Assurance Schemes (EQUASs) for human biomonitoring of perfluoroalkyl substances (PFASs) in serum as part of the quality assurance programme under HBM4EU.

Perfluoroalkyl substances (PFASs) are of very high concern due to their persistence and accumulative behaviour as well as their manifold adverse health effects. Human biomonitoring (HBM) based on the determination of PFASs in serum samples is an adequate and established strategy for exposure and risk assessment of the population. The suspected health risks associated with exposure levels in the general population call for reliable HBM data verified by Quality Assurance and Quality Control (QA/QC) measures. PFASs were among the chemicals selected as priority substances in HBM4EU, a pan-European project to harmonize and advance HBM within 30 European countries. For this purpose, the analytical comparability and accuracy of PFASs-analysing laboratories was assessed in a QA/QC programme 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 for the determination of eight perfluoroalkyl carboxylic acids and four perfluoroalkyl sulfonic acids (PFBS, PFHxS, PFHpS, PFOS) in serum. All 21 participating laboratories achieved satisfactory results for at least six of these biomarkers, although low limits of quantification (of about 0.1 µg/L) were required to quantify serum PFAS levels at general population exposure levels. The mean relative standard deviation of the participants' results (study RSDR) significantly improved from 22 % to 13 % over all PFAS biomarkers in the course of the four rounds. This QA/QC programme succeeded in establishing a network of laboratories with high analytical comparability and accuracy for the analysis of PFASs across 12 European countries.

Residual additives in marine microplastics and their risk assessment - A critical review.

This review summarizes the current state of knowledge regarding the risk assessment of plastic-associated residual additives, i.e. residual monomers, degradation products and additives, in the marine environment, also considering effects of weathering and bioavailability. Experimental studies have found a number of organic and metal additive compounds in leachates from plastics, and the analysis of weathered plastic particles, such as polyethylene, polypropylene and polystyrene particles sampled on beaches and shorelines, has identified residual additives, such as flame retardants, plasticizers, UV stabilizers and antioxidants. While the transfer of e.g. PBDEs to organisms upon ingestion has been demonstrated, studies on uptake and bioaccumulation of plastic-associated chemicals are inconclusive. Studies on hazard and risk assessments are few, and focus on monomers and/or a limited number of high concentration additives, such as phthalates and flame retardants. The risk assessment results vary between low, moderate and high risks of specific additives, and are not necessarily consistent for the same compound. Given the large number of chemicals potentially introduced into the marine environment with plastic particles and the challenges associated with the correct quantification of exposure concentrations and toxicity thresholds, the question arises whether new risk assessment concepts may be needed.

Persistent organic pollutant exposures among Greenlandic adults in relation to lifestyle and diet: New data from the ACCEPT cohort.

High concentrations of persistent organic pollutants (POPs) in blood of the Greenlandic population are well known. The exposure is mainly through traditional food intake, including marine mammals and seabirds. The present study aimed to follow up on POP concentrations (organochlorine pesticides, polychlorinated biphenyls, per- and polyfluoroalkyl substances, and halogenated flame retardants (HFRs)) and relations to lifestyle and diet of the mothers included in the Greenlandic ACCEPT cohort (3-5 years after inclusion in 2013-15) and to include the children's fathers. This new data collection in 2019-20 included blood samples for measurement of POP concentrations and lifestyle and food frequency questionnaires from 101 mothers and 76 fathers aged 24-55 years living in Nuuk, Sisimiut, and Ilulissat, Greenland. The mothers' intra-individual median percentage decrease in POP concentrations from inclusion to this follow-up (3-5 years later) was 16-58%, except for mirex (0% change). Median concentrations of POPs were 1.4-4.6 times higher in fathers than in mothers. The POPs differed by residential town with generally higher concentrations in Ilulissat compared to Sisimiut and Nuuk. We report, for the first time, novel HFRs in human samples from Greenland. However, concentrations were low and only dechlorane plus (with its anti-isomer) was detected in >50% of the samples. Most POPs correlated positively with age and n-3/n-6 fatty acid ratio. The lipophilic POPs correlated positively with the percentage of life lived in Greenland, whereas few POPs correlated positively with BMI, income (personal and household), education, and alcohol intake. The POPs generally associated positively with the intake of marine mammals, seabirds, and dried fish, while few POPs associated positively with Greenlandic fish intake. In contrast, POPs generally associated negatively with imported meat products intake. The study findings may be of interest for future dietary recommendations in Greenland. We discuss the potential explanations for the findings and suggestions for future research.

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.

Influence of climate change on persistent organic pollutants and chemicals of emerging concern in the Arctic: state of knowledge and recommendations for future research.

Persistent organic pollutants (POPs) have accumulated in polar environments as a result of long-range transport from urban/industrial and agricultural source regions in the mid-latitudes. Climate change has been recognized as a factor capable of influencing POP levels and trends in the Arctic, but little empirical data have been available previously. A growing number of recent studies have now addressed the consequences of climate change for the fate of Arctic contaminants, as reviewed and assessed by the Arctic Monitoring and Assessment Programme (AMAP). For example, correlations between POP temporal trends in air or biota and climate indices, such as the North Atlantic Oscillation Index, have been found. Besides the climate indices, temperature, precipitation and sea-ice were identified as important climate parameters influencing POP levels in the Arctic environment. However, the physical changes are interlinked with complex ecological changes, including new species habitats and predator/prey relationships, resulting in a vast diversity of processes directly or indirectly affecting levels and trends of POPs. The reviews in this themed issue illustrate that the complexity of physical, chemical, and biological processes, and the rapid developments with regard to both climate change and chemical contamination, require greater interdisciplinary scientific exchange and collaboration. While some climate and biological parameters have been linked to POP levels in the Arctic, mechanisms underlying these correlations are usually not understood and need more work. Going forward there is a need for a stronger collaborative approach to understanding these processes due to high uncertainties and the incremental process of increasing knowledge of these chemicals. There is also a need to support and encourage community-based studies and the co-production of knowledge, including the utilization of Indigenous Knowledge, for interpreting trends of POPs in light of climate change.

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.

Critical review of analytical methods for the determination of flame retardants in human matrices.

Human biomonitoring is a powerful approach in assessing exposure to environmental pollutants. Flame retardants (FRs) are of particular concern due to their wide distribution in the environment and adverse health effects. This article reviews studies published in 2009-2020 on the chemical analysis of FRs in a variety of human samples and discusses the characteristics of the analytical methods applied to different FR biomarkers of exposure, including polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD), novel halogenated flame retardants (NHFRs), bromophenols, incl. tetrabromobisphenol A (TBBPA), and organophosphorous flame retardants (PFRs). Among the extraction techniques, liquid-liquid extraction (LLE) and solid phase extraction (SPE) were used most frequently due to the good efficiencies in the isolation of the majority of the FR biomarkers, but with challenges for highly lipophilic FRs. Gas chromatography-mass spectrometry (GC-MS) is mainly applied in the instrumental analysis of PBDEs and most NHFRs, with recent inclusions of GC-MS/MS and high resolution MS techniques. Liquid chromatography-MS/MS is mainly applied to HBCD, bromophenols, incl. TBBPA, and PFRs (including metabolites), however, GC-based analysis following derivatization has also been used for phenolic compounds and PFR metabolites. Developments are noticed towards more universal analytical methods, which enable widening method scopes in the human biomonitoring of FRs. Challenges exist with regard to sensitivity required for the low concentrations of FRs in the general population and limited sample material for some human matrices. A strong focus on quality assurance/quality control (QA/QC) measures is required in the analysis of FR biomarkers in human samples, related to their variety of physical-chemical properties, low levels in most human samples and the risk of contamination.