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AbstractHuman biomonitoring (HBM) frameworks assess human exposure to hazardous chemicals. In this review, we discuss and summarize sample preparation procedures and analytical methodology for six groups of chemicals of emerging concern (CECs), namely diisocyanates, benzotriazoles, benzothiazoles, 4-methylbenzylidene camphor, isothiazolinones, fragrances, and non-phthalate plasticizers, which are increasingly detected in urine, however, are not yet widely included in HBM schemes, despite posing a risk to human health. The sample preparation procedures depend largely on the chemical group; however, solid-phase extraction (SPE) is most often used due to the minimized sample handling, lower sample volume, and generally achieving lower limits of quantification (LOQs) compared to other extraction techniques. In terms of sample analysis, LC-based methods generally achieve lower limits of quantification (LOQs) compared to GC-based methods for the selected six groups of chemicals owing to their broader chemical coverage. In conclusion, since these chemicals are expected to be more frequently included in future HBM studies, it becomes evident that there is a pressing need for rigorous quality assurance programs to ensure better comparability of data. These programs should include the reporting of measurement uncertainty and facilitate inter-laboratory comparisons among the reporting laboratories. In addition, high-resolution mass spectrometry should be more commonly employed to enhance the specificity and selectivity of the applied analytical methodology since it is underrepresented in HBM. Furthermore, due to the scarcity of data on the levels of these CECs in urine, large population HBM studies are necessary to gain a deeper understanding of the associated risks.

The present study reports one of the few cases in which organophosphate (OP) and pyrethroid (PYR) pesticide human exposure is evaluated in family contexts by the analysis of mother/child pair samples. Urinary concentrations of 6 organic metabolites of organophosphates and 2 pyrethroids were measured in mothers and their 7-to 8-year-old children (n = 168) in a general population from the central area of Slovenia. The results were adjusted for specific gravity and creatinine. The most abundant OP metabolite in children was 4-nitrophenol (PNP) (median 0.7 ng/ml) and in mothers (0.45 ng/ml), representing parathion exposure. 3-Phenoxibenzoic acid (3-PBA) (0.26 ng/ml), the general metabolite of pyrethroids, and 3,5,6-trichloro-2-pyridinol (TCPY) (0.16 ng/ml; chlorpyriphos) were the second most abundant compounds in children and mothers, respectively. The geometric mean specific gravity adjusted concentrations of OPs and PYRs were statistically significantly higher in children than in their mothers (between 3% and 24% higher), with the exception of TCPY (26% lower). All OP and PYR metabolites found in higher concentration in children showed significant positive correlations with the metabolite concentrations found in the mothers (p < 0.05 and 0.01), involving the fact that higher maternal concentrations were associated with higher children levels. These differential mother-children distributions and significant correlations were observed for the 2 types of pesticides studied, OPs and PYRs, which have different chemical properties. This agreement is consistent with the incorporation of the pesticides because of the general activities developed in the family context, instead of pesticide-dependent specific inputs. Comparison of the estimated daily intakes with the acceptable daily intakes of all detected metabolites revealed no significant risk of adverse health effects from exposure to these pesticides. © 2019 The Authors ; The authors are grateful to all women who participated in the study, the participating hospital for the data sampling and all the field workers for their enthusiastic efforts. This paper was supported by the European Union project CROME (LIFE12 ENV/GR/001040 ). Additional funding was received from the European Union projects: HEALS ( FP7-ENV-2013-603946 ), PHIME ( FOOD-CT-2006-016253 ), Neurosome ( H2020-MSCA-ITN-2017 SEP-210411486 ) and EDC-MET ( H2020-HEALTH/0490-825762 ) and the Slovenian Research Agency–ARRS (program P1-0143 ; project NEURODYS–contract no. JZ-9400 ). Appendix A ; Peer reviewed

AbstractThe number of atmospheric mercury (Hg) monitoring stations is growing globally. However, there are still many regions and locations where Hg monitoring is limited or non-existent. Expansion of the atmospheric Hg monitoring network could be facilitated by the use of cost-effective monitoring methods. As such, biomonitoring and passive monitoring offer a unique alternative to well-established monitoring by active measurements, since they do not require a power supply and require minimal workload to operate. The use of biomonitoring (lichens and mosses) and passive air samplers (PASs) (various designs with synthetic materials) has been reported in the literature, and comparisons with active measurement methods have also been made. However, these studies compared either biomonitoring or PASs (not both) to only one type of active measurement. In our work, we used transplanted (7 sampling sites) and in situ lichens (8 sampling sites) for biomonitoring, two PASs from different producers (3 sampling sites), and two different active measurement types (continuous and discontinuous active measurements, 1 and 8 sampling sites, respectively) to evaluate their effectiveness as monitoring methods. In the 9-month sampling campaign, 3 sampling locations with different characteristics (unpolluted, vicinity of a cement plant, and vicinity of a former Hg mine) were used. The results obtained with lichens and PASs clearly distinguished between sampling locations with different Hg concentrations; using both PASs and lichens together increased the confidence of our observations. The present work shows that biomonitoring and passive sampling can be effectively used to identify areas with elevated atmospheric Hg concentrations. The same can be said for discontinuous active measurements; however, the discrepancy between atmospheric Hg concentrations derived from PASs and discontinuous active measurements should be further investigated in the future.
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23 pages, 7 figures, 1 table, supporting Information https://doi.org/10.1021/acs.est.1c03044 ; Mercury (Hg) and especially its methylated species (MeHg) are toxic chemicals that contaminate humans via the consumption of seafood. The most recent UNEP Global Mercury Assessment stressed that Mediterranean populations have higher Hg levels than people elsewhere in Europe. The present Critical Review updates current knowledge on the sources, biogeochemical cycling, and mass balance of Hg in the Mediterranean and identifies perspectives for future research especially in the context of global change. Concentrations of Hg in the Western Mediterranean average 0.86 ± 0.27 pmol L–1 in the upper water layer and 1.02 ± 0.12 pmol L–1 in intermediate and deep waters. In the Eastern Mediterranean, Hg measurements are in the same range but are too few to determine any consistent oceanographical pattern. The Mediterranean waters have a high methylation capacity, with MeHg representing up to 86% of the total Hg, and constitute a source of MeHg for the adjacent North Atlantic Ocean. The highest MeHg concentrations are associated with low oxygen water masses, suggesting a microbiological control on Hg methylation, consistent with the identification of hgcA-like genes in Mediterranean waters. MeHg concentrations are twice as high in the waters of the Western Basin compared to the ultra-oligotrophic Eastern Basin waters. This difference appears to be transferred through the food webs and the Hg content in predators to be ultimately controlled by MeHg concentrations of the waters of their foraging zones. Many Mediterranean top-predatory fish still exceed European Union regulatory Hg thresholds. This emphasizes the necessity of monitoring the exposure of Mediterranean populations, to formulate adequate mitigation strategies and recommendations, without advising against seafood consumption. This review also points out other insufficiencies of knowledge of Hg cycling in the Mediterranean Sea, including temporal variations in air–sea exchange, hydrothermal and cold seep inputs, point sources, submarine groundwater discharge, and exchanges between margins and the open sea. Future assessment of global change impacts under the Minamata Convention Hg policy requires long-term observations and dedicated high-resolution Earth System Models for the Mediterranean region ; This research has been funded by the Global Mercury Observation System (GMOS, N-265113 European Commission project) and the European Research Council (ERC-2010-StG-20091028). The authors acknowledge the financial support from the project Integrated Global Observing Systems for Persistent Pollutants (IGOSP) funded by the European Commission in the framework "The European network for observing our changing planet (ERA-PLANET)" program, Grant Agreement: 689443. This work also received support from the Mistrals transversal action on pollutants and contaminants (INSU-CNRS) ; With the institutional support of the 'Severo Ochoa Centre of Excellence' accreditation (CEX2019-000928-S) ; Peer reviewed

Derivatives of polycyclic aromatic hydrocarbons (PAHs) such as nitrated- and oxygenated-PAHs (NPAHs and OPAHs) could be even more toxic and harmful for the environment and humans than PAHs. We assessed the spatial and seasonal variations of NPAHs and OPAHs atmospheric levels, their cancer risks and their gas-to-particle partitioning. To this end, about 250 samples of fine particulate matter (PM2.5) and 50 gaseous samples were collected in 2017 in central Europe in the cities of Brno and Ljubljana (two traffic and two urban background sites) as well as one rural site. The average particulate concentrations were ranging from below limit of quantification to 593 pg m-3 for Σ9NPAHs and from 1.64 to 4330 pg m-3 for Σ11OPAHs, with significantly higher concentrations in winter compared to summer. In winter, the particulate levels of NPAHs and OPAHs were higher at the traffic site compared to the urban background site in Brno while the opposite was found in Ljubljana. NPAHs and OPAHs particulate levels were influenced by the meteorological parameters and co-varied with several air pollutants. The significance of secondary formation on the occurrence of some NPAHs and OPAHs is indicated. In winter, 27-47% of samples collected at all sites were above the acceptable lifetime carcinogenic risk. The gas-particle partitioning of NPAHs and OPAHs was influenced by their physico-chemical properties, the season and the site-specific aerosol composition. Three NPAHs and five OPAHs had higher particulate mass fractions at the traffic site, suggesting they could be primarily emitted as particles from vehicle traffic and subsequently partitioning to the gas phase along air transport. This study underlines the importance of inclusion of the gas phase in addition to the particulate phase when assessing the atmospheric fate of polycyclic aromatic compounds and also when assessing the related health risk. ; This project was supported by the European Union's H2020 Framework Programme (ICARUS project) under grant agreement No – 690105, by ...

Human biomonitoring (HBM) depends on high-quality human samples to identify status and trends in exposure and ensure comparability of results. In this context, much effort has been put into the development of standardized processes and quality assurance for sampling and chemical analysis, while effects of sample storage and shipment on sample quality have been less thoroughly addressed. To characterize the currently applied storage and shipment procedures within the consortium of the European Human Biomonitoring Initiative (HBM4EU), which aims at harmonization of HBM in Europe, a requirement analysis based on data from an online survey was conducted. In addition, the online survey was addressed to professionals in clinical biobanking represented by members of the European, Middle Eastern and African Society for Biopreservation and Biobanking (ESBB) to identify the current state-of-the-art in terms of sample storage and shipment. Results of this survey conducted in these two networks were compared to detect processes with potential for optimization and harmonization. In general, many similarities exist in sample storage and shipment procedures applied by ESBB members and HBM4EU partners and many requirements for ensuring sample quality are already met also by HBM4EU partners. Nevertheless, a need for improvement was identified for individual steps in sample storage, shipment, and related data management with potential impact on sample and data quality for HBM purposes. Based on these findings, recommendations for crucial first steps to further strengthen sample quality, and thus foster advancement in HBM on a pan-European level are given. ; This project has received funding from the European Union's Horizon 2020 research and innovation program under grant agreement No. 733032 HBM4EU. ; Sí