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This paper is focused on study of the concentration of the basic catalyst in methanol on the yield of the derivatization transesterification reaction of triacyglycerols. Potassium hydroxide and sodium hydroxide solutions were used as basic catalysts. Triacylglycerols were transesterified, rapeseed oil was used as a sample. Triacylglycerols were converted to methyl esters of fatty acids, which were subsequently determined by GC-MS where the peak areas were monitored, because they represent the yield of the formed fatty acid methyl esters, namely palmitic, oleic, linoleic and stearic acids. The highest yield of transesterification of the oil to methylesters of fatty acids was found for a concentration of 3.0 mol dm–3 for KOH and 2.0 mol dm–3 for NaOH. At higher catalyst concentrations, a predominant side-reaction, saponification, was observed, which decreased the overall yield of fatty acid methyl esters.

Thirdhand smoke (THS) persists in locations where smoking previously occurred and can be transported into non-smoking environments, leading to non-smoker exposure. Laboratory experiments using high-resolution mass spectrometry demonstrate that deposited particulate matter (PM) and smoke-exposed surrogate lung lining fluid (LLF) are substantial, chemically-complex reservoirs of gas-phase THS emissions, including hazardous air pollutants, polycyclic aromatic compounds, and nitrogen/oxygen-containing species. Both PM and LLF are persistent real-world THS reservoirs that chemically evolve over time, and can act as vehicles for the transport and emission of reactive pollutants and their reaction byproducts (e.g., acrolein). Deposited PM on clothes, furnishings, bodies, and/or airways will emit volatile to semi-volatile gases over long lifetimes, which can re-partition to other indoor materials and increase their overall persistence. On the other hand, LLF off-gassing consists predominantly of volatile organic compounds in amounts influenced by their aqueous solubilities, and their persistence in breath will be prolonged by re-distribution across internal aqueous reservoirs, as corroborated by multicompartment modeling in this study.

Passive air sampling (PAS) has been used to monitor semivolatile organic compounds (SVOCs) for the past 20 years, but limitations and uncertainties persist in the derivation of effective sampling volumes, sampling rates, and concentrations. As a result, the comparability of atmospheric levels measured by PAS and concentrations measured by active air sampling (AAS) remains unclear. Long-term PAS data, without conversion into concentrations, provide temporal trends that are similar to, and consistent with, trends from AAS data. However, for more comprehensive environmental and human health assessments of SVOCs, it is also essential to harmonize and pool air concentration data from the major AAS and PAS monitoring networks in Europe. To address this need, we calculated and compared concentration data for 28 SVOCs (including organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and polycyclic aromatic hydrocarbons (PAHs)) at the six monitoring sites in Europe with 10 years of co-located AAS (EMEP) and PAS (MONET) data: Birkenes, Kosetice, Pallas, Rao, Storhofoi, and Zeppelin. Atmospheric SVOC concentrations were derived from PAS data using the two most common computation models. Long-term agreement between the AAS and PAS data was strong for most SVOCs and sites, with 79% of the median PAS-derived concentrations falling within a factor of 3 of their corresponding AAS concentrations. However, in both models it is necessary to set a sampler-dependent correction factor to prevent underestimation of concentrations for primarily particle-associated SVOCs. In contrast, the models overestimate concentrations at sites with wind speeds that consistently exceed 4 m s(-1). We present two recommendations that, if followed, allow MONET PAS to provide sufficiently accurate estimates of SVOC concentrations in air so that they can be deployed together with AAS in regional and global monitoring networks., Environmental Science: Processes & Impacts, 24 (6), ISSN:2050-7887, ISSN:2050-7895

Many legacy and emerging flame retardants (FRs) have adverse human and environmental health effects. This study reports legacy and emerging FRs in children from nine European countries from the HBM4EU aligned studies. Studies from Belgium, Czech Republic, Germany, Denmark, France, Greece, Slovenia, Slovakia, and Norway conducted between 2014 and 2021 provided data on FRs in blood and urine from 2136 children. All samples were collected and analyzed in alignment with the HBM4EU protocols. Ten halogenated FRs were quantified in blood, and four organophosphate flame retardants (OPFR) metabolites quantified in urine. Hex-abromocyclododecane (HBCDD) and decabromodiphenyl ethane (DBDPE) were infrequently detected (< 16% of samples). BDE-47 was quantified in blood from Greece, France, and Norway, with France (0.36 ng/g lipid) having the highest concentrations. BDE-153 and-209 were detected in < 40% of samples. Dechlorane Plus (DP) was quantified in blood from four countries, with notably high median concentrations of 16 ng/g lipid in Slovenian children. OPFR metabolites had a higher detection frequency than other halogenated FRs. Diphenyl phosphate (DPHP) was quantified in 99% of samples across 8 countries at levels similar to 5 times higher than other OPFR metabolites (highest median in Slovenia of 2.43 ng/g lipid). FR concentrations were associated with lifestyle factors such as cleaning frequency, employment status of the father of the household, and renovation status of the house, among others. The concentrations of BDE-47 in children from this study were similar to or lower than FRs found in adult matrices in previous studies, suggesting lower recent exposure and effectiveness of PBDE restrictions.

Polycyclic aromatic hydrocarbons (PAHs) and their alkylated (RPAHs), nitrated (NPAHs) and oxygenated (OPAHs) derivatives are air pollutants. Many of these substances are long-lived, can undergo long-range atmospheric transport and adversely affect human health upon exposure. However, the occurrence and fate of these air pollutants have hardly been studied in the marine atmosphere. In this study, we report the atmospheric concentrations over the Mediterranean Sea, the Red Sea, the Arabian Sea, the Gulf of Oman and the Arabian Gulf, determined during the AQABA (Air Quality and Climate Change in the Arabian Basin) project, a comprehensive ship-borne campaign in summer 2017. The average concentrations of ∑26PAHs, ∑19RPAHs, ∑11OPAHs and ∑17NPAHs, in the gas and particulate phases, were 2.99 ± 3.35 ng m−3, 0.83 ± 0.87 ng m−3, 0.24 ± 0.25 ng m−3 and 4.34 ± 7.37 pg m−3, respectively. The Arabian Sea region was the cleanest for all substance classes, with concentrations among the lowest ever reported. Over the Mediterranean Sea, we found the highest average burden of ∑26PAHs and ∑11OPAHs, while the ∑17NPAHs were most abundant over the Arabian Gulf (known also as the Persian Gulf). 1,4-Naphthoquinone (1,4-O2NAP) followed by 9-fluorenone and 9,10-anthraquinone were the most abundant studied OPAHs in most samples. The NPAH composition pattern varied significantly across the regions, with 2-nitronaphthalene (2-NNAP) being the most abundant NPAH. According to source apportionment investigations, the main sources of PAH derivatives in the region were ship exhaust emissions, residual oil combustion and continental pollution. All OPAHs and NPAHs except 2-nitrofluoranthene (2-NFLT), which were frequently detected during the campaign, showed elevated concentrations in fresh shipping emissions. In contrast, 2-NFLT and 2-nitropyrene (2-NPYR) were highly abundant in aged shipping emissions due to secondary formation. Apart from 2-NFLT and 2-NPYR, benz(a)anthracene-7,12-dione and 2-NNAP also had significant photochemical sources. Another finding was that the highest concentrations of PAHs, OPAHs and NPAHs were found in the sub-micrometre fraction of particulate matter (PM1).

Oceans have remained the least well-researched reservoirs of persistent organic pollutants (POPs) globally, due to their vast scale, difficulty of access, and challenging (trace) analysis. Little data on POPs exists along South America and the effect of different currents and river plumes on aqueous concentrations. Research cruise KN210-04 (R/V Knorr) offered a unique opportunity to determine POP gradients in air, water, and their air-water exchange along South America, covering both hemispheres. Compounds of interest included polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polybrominated diphenylethers (PBDEs), and polycyclic aromatic hydrocarbons (PAHs). Remote tropical Atlantic Ocean atmospheric concentrations varied little between both hemispheres; for HCB, BDEs 47 and 99, they were ∼5 pg/m3, PCBs were ∼1 pg/m3, α-HCH was ∼0.2 pg/m3, and phenanthrene and other PAHs were in the low 100s pg/m3. Aqueous concentrations were dominated by PCB 52 (mean 4.1 pg/L), HCB (1.6 pg/L), and β-HCH (1.9 pg/L), with other compounds

International audience; For decades pesticides have been used in agriculture, however, the occurrence of legacy organochlorine pesticides (OCPs) and current-use pesticides (CUPs) is poorly understood in Africa. This study investigates air concentrations of OCPs and CUPs in three South African agricultural areas, their spatial/seasonal variations and mixture profiles.Between 2017 and 2018, 54 polyurethane foam-disks passive air-samplers (PUF-PAS) were positioned in three agricultural areas of the Western Cape, producing mainly apples, table grapes and wheat. Within areas, 25 CUPs were measured at two sites (farm and village), and 27 OCPs at one site (farm). Kruskal-Wallis tests investigated area differences in OCPs concentrations, and linear mixed-effect models studied differences in CUPs concentrations between areas, sites and sampling rounds.In total, 20 OCPs and 16 CUPs were detected. A median of 16 OCPs and 10 CUPs were detected per sample, making a total of 11 OCPs and 24 CUPs combinations. Eight OCPs (trans-chlordane, o,p’-/p,p’-dichlorodiphenyldichloroethylene (DDE)/dichlorodiphenyltrichloroethane (DDT), endosulfan sulfate, γ-hexachlorocyclohexane and mirex) and two CUPs (carbaryl and chlorpyrifos) were quantified in all samples. p,p’-DDE (median 0.14 ng/m3) and chlorpyrifos (median 0.70 ng/m3) showed the highest concentrations throughout the study. Several OCPs and CUPs showed different concentrations between areas and seasons, although CUPs concentrations did not differ between sites. OCPs ratios suggest ongoing chlordane use in the region, while DDT and endosulfan contamination result from past-use.Our study revealed spatial and seasonal variations of different OCPs and CUPs combinations detected in air. Further studies are needed to investigate the potential cumulative or synergistic risks of the detected pesticides.

Though many persistent organic pollutants (POPs) are closely regulated the human population is still exposed to these ubiquitous chemicals from the environment and diet. Safe management and human biomonitoring of POPs is necessary to understand the risk of exposure. Within human biomonitoring the mass of sample is often limited, therefore robust methods using smaller sample amounts are necessary. This study developed a 96-well plate solid phase extraction (SPE) method for determination of selected POPs: polychlorinated biphenyls (PCBs), organo-chlorine pesticides (OCPs), polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD) and non-persistent novel flame retardants (NFRs) in low volume blood serum. Non-destructive clean-up coupling Oasis HLB extraction plate with Phree phospholipid removal plate was employed. Extraction efficiency was determined at low and high concentrations in certified reference materials NIST SRM 1957 and 1958, respec-tively. Target compounds deviated from certified values on average by 15% and 21% for SRM 1957 and SRM 1958, respectively. Observed limit of detections (LODs) ranged from 0.36 pg/mL (PCB 180) to 66.07 pg/mL (delta-HCH). The applicability for real samples is demonstrated on 48 samples from pregnant women enrolled in the pilot phase of the CELSPAC: TNG study. In total, 30 target compounds were detected in at least one sample. The method developed here provides a fast and reliable analysis of human blood serum with possibility to introduce automation for the sample preparation procedure.

Pollution of indoor environment, where people spend much of their time, comprises complex mixtures of compounds with vastly understudied hazard potential. This study examined several important specific toxic effects and pollutant levels (177 compounds) of indoor samples (air gas phase, PM10 and dust) from different microenvironments after two extractions with focus on their gas/particle/dust distribution and polarity. The endocrine disruptive (ED) potential was assessed by human cell-based in vitro bioassays addressing anti-/estrogenicity, anti-/androgenicity, aryl hydrocarbon, thyroid and peroxisome proliferator-activated receptor-mediated activities. Potential toxicity to respiratory tract tissue was assessed using human bronchial cell line. The toxicological analyses pointed out the relevance of both inhalation and ingestion exposure, with significant effects detected after exposure to extracts from all three studied matrices with distinct gas/particle distribution patterns. Chemical analyses document the high complexity of indoor pollutant mixtures with greatest levels of phthalates, their emerging alternatives, and PAHs in dust. Despite the detection of up to 108 chemicals, effects were explained only to low extent. This emphasizes data gaps regarding ED potencies of many detected abundant indoor contaminants, but also potential presence of other unidentified ED compounds. The omnipresent ED potentials in indoor environment rise concern regarding associated human health risk.

Long-term exposure to polycyclic aromatic hydrocarbons (PAHs) and their nitrated (NPAHs) and oxygenated (OPAHs) derivatives can cause adverse health effects due to their carcinogenicity, mutagenicity and oxidative potential. The distribution of PAH derivatives in the terrestrial environment has hardly been studied, although several PAH derivatives are ubiquitous in air and long-lived in soil and water. We report the multi-annual variations in the concentrations of NPAHs, OPAHs and PAHs in soils sampled at a semi-urban (Mokrá, Czech Republic) and a regional background site (Košetice, Czech Republic) in central Europe. The concentrations of the Σ18NPAHs and the Σ11+2OPAHs and O-heterocycles were 0.31 ± 0.23 ng g−1 and 4.03 ± 3.03 ng g−1, respectively, in Košetice, while slightly higher concentrations of 0.54 ± 0.45 ng g−1 and 5.91 ± 0.45 ng g−1, respectively, were found in soil from Mokrá. Among the 5 NPAHs found in the soils, 1-nitropyrene and less so 6-nitrobenzo(a)pyrene were most abundant. The OPAHs were more evenly distributed. The ratios of the PAH derivatives to their parent PAHs in Košetice indicate that they were long-range transported to the background site. Our results show that several NPAHs and OPAHs are abundant in soil and that gas-particle partitioning is a major factor influencing the concentration of several semi-volatile NPAHs and OPAHs in the soils. Complete understanding of the long-term variations of NPAH and OPAH concentrations in soil is limited by the lack of kinetic data describing their formation and degradation.

Endocrine-disrupting chemicals (EDCs) in diet are a health concern and their monitoring in food has been introduced in the European Union. In developing countries, EDC dietary exposure data are scarce, especially from areas perceived as pollution hotspots, including industrialized countries like India. Several persistent organic pollutants (POPs) act as EDCs and pose a pressure to human health mainly through dietary exposure. In the present study, a range of organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), dioxins and furans were measured in several food items collected from Indian urban (Delhi) and peri-urban (Dehradun) areas. Food basket contamination data were used to estimate EDC dietary exposure and compare it with that of the average European population estimated from available monitoring data. All the target contaminants were found in most food items, especially in dairies and meat products. OCPs were the main contributers to the measured EDC contamination. Food supplied to Delhi's markets had higher EDC contamination than that supplied to the peri-urban market in Dehradun. Despite lax compliance and control measures, Indian dietary exposure of OCPs and PBDEs were comparable with that of Europe and were lower for PCBs and dioxins. Higher meat consumption in Europe only partly explained this pattern which was driven also by the higher EDC residues in some European food items. A substantial part of endocrine disrupting potential in the diet derives from food and animal feeds internationally traded between developed and developing countries. With increasingly globalized food systems, internationally harmonized policies on EDC content in food can lead to better protection of health in both these contexts.

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., Graphical abstract Unlabelled Image, Highlights • NOPAH particulate levels were generally correlated with PM, OC, EC, CO, Cu and Zn. • In winter, NOPAH levels generally increased with NO2 but decreased with O3. • Significant cancer risks from the inhalation of PAHs, NPAHs and OPAHs were found. • Cancer risks might be significantly underestimated if the gas phase is not sampled.

Nitrated and oxygenated polycyclic aromatic hydrocarbons (NPAHs, OPAHs) are abundant in the atmosphere and contribute significantly to the health risk associated with inhalation of polluted air. Despite the health hazard they pose, NPAHs and OPAHs were rarely included in monitoring. The aim of this study is to provide the first multi-year temporal trends of the concentrations, composition pattern and fate of NPAHs and OPAHs in air from a site representative of background air quality conditions in central Europe. Samples were collected every second week at a rural background site in the Czech Republic during 2015 -2017. Concentrations ranged from 1.3 to 160 pg m(-3) for Sigma(17)NPAHs, from 32 to 2600 pg m-3 for Sigma(10)OPAHs and from 5.1 to 4300 pg m(-3) for Sigma O-2-heterocycles. The average particulate mass fraction (q) ranged from 0.01 +/- 0.02 (2-nitronaphthalene) to 0.83 +/- 0.22 (1-nitropyrene) for individual NPAHs and from

Among the nitrated and oxygenated polycyclic aromatic hydrocarbons (NPAHs and OPAHs) are some of the most hazardous substances to public health, mainly because of their carcinogenicity and oxidative potential. Despite these concerns, the concentrations and fate of NPAHs and OPAHs in the atmospheric environment are largely unknown. Ambient air concentrations of 18 NPAHs, 5 quinones, and 5 other OPAHs were determined at two urban and one regional background sites in central Europe. At one of the urban sites, the total (gas and particulate) concentrations of Sigma(10)OPAHs were 10.0 +/- 9.2 ng/m(3) in winter and 3.5 +/- 1.6 ng/m(3) in summer. The gradient to the regional background site exceeded 1 order of magnitude. Sigma(18)NPAH concentrations were typically 1 order of magnitude lower than OPAHs. Among OPAHs, 9-fluorenone and (9,10)-anthraquinone were the most abundant species, accompanied by benzanthrone in winter. (9,10)-Anthraquinone represented two-thirds of quinones. We found that a large fraction of the target substance particulate mass was carried by submicrometer particles. The derived inhalation bioaccessibility in the PM10 size fraction is found to be approximate to 5% of the total ambient concentration of OPAHs and up to approximate to 2% for NPAHs. For 9-fluorenone and (9,10)-anthraquinone, up to 86 and 18%, respectively, were found at the rural site. Our results indicate that water solubility could function as a limiting factor for bioaccessibility of inhaled particulate NPAHs and OPAHs, without considerable effect of surfactant lipids and proteins in the lung lining fluid.

Though many persistent organic pollutants (POPs) are closely regulated the human population is still exposed to these ubiquitous chemicals from the environment and diet. Safe management and human biomonitoring of POPs is necessary to understand the risk of exposure. Within human biomonitoring the mass of sample is often limited, therefore robust methods using smaller sample amounts are necessary. This study developed a 96-well plate solid phase extraction (SPE) method for determination of selected POPs: polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD) and non-persistent novel flame retardants (NFRs) in low volume blood serum. Non-destructive clean-up coupling Oasis HLB extraction plate with Phree phospholipid removal plate was employed. Extraction efficiency was determined at low and high concentrations in certified reference materials NIST SRM 1957 and 1958, respectively. Target compounds deviated from certified values on average by 15% and 21% for SRM 1957 and SRM 1958, respectively. Observed limit of detections (LODs) ranged from 0.36 pg/mL (PCB 180) to 66.07 pg/mL (δ-HCH). The applicability for real samples is demonstrated on 48 samples from pregnant women enrolled in the pilot phase of the CELSPAC: TNG study. In total, 30 target compounds were detected in at least one sample. The method developed here provides a fast and reliable analysis of human blood serum with possibility to introduce automation for the sample preparation procedure.

This study presents multi-year monitoring data on atmospheric polybrominated diphenyl ethers (PBDEs) in central Europe. Air was sampled on a weekly basis at a background site in the central Czech Republic from 2011 to 2014 (N = 114). Σ8PBDEs (without BDE209) total (gas and particulate) concentrations ranged from 0.084 to 6.08 pg m−3, while BDE209 was at 0.05–5.01 pg m−3. BDE47, BDE99 and BDE183 were the major contributors to Σ8PBDEs.Overall, the atmospheric concentrations of individual PBDEs were controlled by deposition processes, meteorological parameters and long-range atmospheric transport. Regarding gas–particle partitioning, with the exception of BDE28 (gaseous) and BDE209 (particulate), all congeners were consistently detected in both phases. Clear seasonal variations with significantly higher measured particulate fraction (θmeasured) in winter compared to summer was found for all PBDEs except BDE209. For example, while the average θmeasured of BDE47 was 0.53±0.19 in winter, this was only 0.01±0.02 in summer. Similarly, for BDE99, θmeasured was 0.89±0.13 in winter, while it was only 0.12±0.08 in summer. The observed gas–particle partitioning coefficient (Kp, in m3 µg−1) was compared with three model predictions, assuming equilibrium or a steady state. None of the models could provide a satisfactory prediction of the partitioning, suggesting the need for a universally applicable model.Statistically significant decreases of the atmospheric concentrations during 2011–2014 were found for BDE99, 100, 153 and 209. Estimated apparent atmospheric halving times for these congeners ranged from 2.8 (BDE209) to 4.8 (BDE153) years. The results suggest that photolytic debromination to lower brominated congeners may significantly influence PBDE concentration levels and patterns in the atmosphere.

Passive air sampling of semivolatile organic compounds (SVOCs) is a relatively inexpensive method that facilitates extensive campaigns with numerous sampling sites. An important question in the design of passive-sampling networks concerns the number and location of samplers. We investigate this question with the example of 17 SVOCs sampled at 14 background sites across the Czech Republic. More than 200 time series (length 5-11 years) were used to characterize SVOC levels and trends in air between 2003 and 2015. Six polychlorinated biphenyls (PCBs), 6 polyaromatic hydrocarbons (PAHs), and 5 organochlorine pesticides (OCPs) at 14 sites were assessed using data from the MONET passive sampling network. Significant decreases were found for most PCBs and OCPs whereas hexachlorobenzene (HCB) and most PAHs showed (mostly insignificant) increases. Spatial variability was rather low for PCBs and OCPs except for dichlorodiphenyltrichloroethane (DDT) and rather high for PAHs. The variability of the SVOC levels and trends depends on characteristics of the sites including their remoteness, landscape, population, and pollution sources. The sites can be grouped in distinct clusters, which helps to identify similar and, thereby, potentially redundant sites. This information is useful when monitoring networks need to be optimized regarding the location and number of sites.

Persistent organic pollutants that have accumulated in soils can be remobilised by volatilisation in response to chemical equilibrium with the atmosphere. Clean air masses from the Indian Ocean, advected with the onset of the summer monsoon, are found to reduce concentrations of hexachlorocyclohexane (HCH), dichlorodiphenyltrichloroethane (DDT) and its derivatives, endosulfan and polychlorinated biphenyls (PCBs) in air at a mountain site (all in the range 5–20 pg m−3) by 77 %, 70 %, 82 % and 45 %, respectively. The analysis of fugacities in soil and air suggest that the arrival of summer monsoon triggers net volatilisation or enhances ongoing revolatilisation of the now-banned chemicals HCH and PCBs from background soils in southern India. The response of the air–soil exchange was modelled using a regional air pollution model, WRF-Chem PAH/POP. The results suggest that the air is increasingly polluted during transport by the south-westerly monsoon winds across the subcontinent. Using a multidecadal multimedia mass balance model, it is found that air–surface exchange of HCH and DDT have declined since the ban of these substances from agriculture, but remobilisation of higher chlorinated PCBs may have reached a historical high, 40 years after peak emission.

The objective of this study was to develop and validate a 96-well plate solid phase extraction method for analysis of 23 lipophilic persistent organic pollutants (POPs) in low-volume plasma and serum samples which is applicable for biomonitoring and epidemiological studies. The analysis of selected markers for internal exposure: 16 polychlorinated biphenyls (PCBs), 5 organochlorine pesticides (OCPs), octachlorinated dibenzo-p-dioxin (OCDD), and polybrominated diphenylether 47 (BDE 47) was evaluated by comparing two SPE sorbents and GC-HRMS or GC-MS/MS detection. The final method extracted 23 POPs from 150 μL of serum and plasma using a 96-well extraction plate containing 60 mg Oasis HLB sorbent per well prior to GC-HRMS magnetic sector analysis. The extraction method was applied to 40 plasma samples collected for an epidemiological study. The recovery of selected POPs ranged from 31% to 63% (n = 48), and detection limits ranged from 2.2 to 45 pg/mL for PCBs, 4.2 to 167 pg/mL for OCPs, 7.8 pg/mL for OCDD and 6.1 pg/mL for BDE 47. This method showed good precision with relative standard deviations of selected POP concentrations in quality control samples (n = 48) ranging from 11% to 25%. The trueness was determined with standard reference material serum (n = 48) and the deviation from certified values ranged from 1 to 27%. Of the 23 POPs analyzed, 18 were detected in 43% to 100% of plasma samples collected for the epidemiological study. The method showed good robustness with low inter-well plate variation (11-31%) determined by twelve 96-well plate extractions, and can extract 96 samples, including quality controls and procedural blanks in 2-3 days. Comparison with GC-MS/MS analysis showed that similar concentrations (within 0.5% to 30%) of most POPs could be obtained with GC-APCI-MS/MS. Larger deviations were observed for PCB 194 (60%) and trans-nonachlor (43%). The developed method produces accurate concentrations of low-level marker POPs in plasma and serum, providing a suitable high-throughput sample preparation procedure for biomonitoring and epidemiological studies involving large sample size and limited sample volume. GC-HRMS was chosen over GC-MS/MS, however the latter showed promising results, and could be used as an alternative to GC-HRMS analysis for most POPs.

In this study, 10 polybrominated diphenyl ethers (PBDEs) and 19 alternative halogenated flame retardants (AFRs) were determined in >450 human milk samples across three European countries, representing northern, western and eastern Europe. This study provides first insights into the occurrence of selected AFRs in mother milk samples and compares them among three European countries. Sums of median concentrations of the most frequently detected PBDEs were 2.16, 0.88 and 0.45ngg−1 lipid weight (lw) in Norway, the Netherlands and Slovakia, respectively. The sum of the concentrations of AFRs ranged from 0.14 to 0.25ngg−1lw in all countries, which was 2 to 15 times less compared to Σ7PBDEs. The Penta-BDE replacement, bis(2-ethylhexyl) tetrabromophthalate, BEH-TEBP, was present at the greatest concentrations of any of the AFRs and in some samples exceeded concentrations of BDE 47 and BDE 153. Four AFRs including bromobenzenes (hexabromobenzene, pentabromobenzene, pentabromotoluene) and another Penta-BDE replacement (2-ethylhexyl-2,3,4,5-tetrabromobenzoate, EH-TBB) were detected in >42% of all human milk samples. Because of the potential developmental neurotoxicity of the halogenated flame retardants, infant dietary intakes via breastfeeding were estimated; in four cases the intakes of BDE 47 exceeded the reference dose indicating that the present concentrations may pose a risk for children. Keywords: Alternative flame retardants, Developmental neurotoxicants, Human milk, Infant exposure, Polybrominated diphenyl ethers

Degradation of semivolatile organic compounds (SVOCs) occurs naturally in ambient air due to reactions with reactive trace gases (e.g., ozone, NOx). During air sampling there is also the possibility for degradation of SVOCs within the air sampler, leading to underestimates of ambient air concentrations. We investigated the possibility of this sampling artifact in commonly used active and passive air samplers for seven classes of SVOCs, including persistent organic pollutants (POPs) typically covered by air monitoring programs, as well as SVOCs of emerging concern. Two active air samplers were used, one equipped with an ozone denuder and one without, to compare relative differences in mass of collected compounds. Two sets of passive samplers were also deployed to determine the influence of degradation during longer deployment times in passive sampling. In active air samplers, comparison of the two sampling configurations suggested degradation of particle-bound polycyclic aromatic hydrocarbons (PAHs), with concentrations up to 2× higher in the denuder-equipped sampler, while halogenated POPs did not have clear evidence of degradation. In contrast, more polar, reactive compounds (e.g., organophosphate esters and current use pesticides) had evidence of losses in the sampler with denuder. This may be caused by the denuder itself, suggesting sampling bias for these compounds can be created when typical air sampling apparatuses are adapted to limit degradation. Passive air samplers recorded up to 4× higher concentrations when deployed for shorter consecutive sampling periods, suggesting that within-sampler degradation may also be relevant in passive air monitoring programs.

Many attempts have been made to quantify the relationship between the amount of persistent organic pollutants sequestered by passive air sampling devices and their actual concentrations in ambient air. However, this information may not be necessary for some applications. In this study, two sets of 30 ten-year-long time series of simultaneous passive and high-volume active air sampling carried out at the Košetice observatory in the Czech Republic were used for a comparison of temporal trends. Fifteen polyaromatic hydrocarbons, seven polychlorinated biphenyls and eight organochlorine pesticides were investigated. In most cases, a good agreement was observed between the trends derived from passive and active monitoring with the exception of several compounds obviously affected by sampling artifacts. Two sampling artifacts were observed: breakthrough of high-volume sampler filters for penta- and hexachlorobenzene and semiquantitative values for PAHs with a high molecular weight. It has been suggested before that annually aggregated results of passive air monitoring may be used directly for the assessment of the long-term behavior of these compounds. The extensive set of long-term data used in this study allowed us to confirm this finding and to demonstrate that it is also possible to derive temporal trends and the compounds' half-lives in air from the passive-sampling time series.

In this study passive air samplers containing polyurethane foam (PUF) disks were deployed in three cities across Chile; Santiago (STG) (n=5, sampling sites), Concepciόn (CON) (n=6) and Temuco (TEM) (n=6) from 2008 to 2009. Polychlorinated biphenyls (PCBs) (7 indicator congeners), chlorinated pesticides hexachlorocyclohexanes (HCHs), dichlorodiphenyl trichloroethanes (DDTs) and flame retardants such as polybrominated diphenyl ethers (PBDEs) were determined by gas chromatography coupled mass spectrometry (GC/MS). A sampling rate (R) typical of urban sites (4m3/day) was used to estimate the atmospheric concentrations of individual compounds. PCB concentrations in the air (pg/m3) ranged from ~1-10 (TEM), ~1-40 (STG) and 4-30 (CON). Higher molecular weight PCBs (PCB-153, -180) were detected at industrial sites (in Concepcion). The HCHs showed a prevalence of γ-HCH across all sites, indicative of inputs from the use of lindane but a limited use of technical HCHs in Chile. DDTs were detected with a prevalence of p,p'-DDE accounting for ~50% of the total DDTs. PBDE concentrations in air (pg/m3) ranged from 1 to 55 (STG), 0.5 to 20 (CON) and from 0.4 to 10 (TEM), and were generally similar to those reported for many other urban areas globally. The pattern of PBDEs was different among the three cities; however, PBDE-209 was dominant at most of the sites. These results represent one of the few assessments of air concentrations of POPs across different urban areas within the same country. These data will support Chilean commitments as a signatory to the Stockholm Convention on POPs and for reporting as a member country of the Group of Latin America and Caribbean Countries (GRULAC) region.

To fulfill national and international fire safety standards, flame retardants (FRs) are being added to a wide range of consumer products and building materials consisting of flammable materials like plastic, wood and textiles. While the FR composition of some products and materials has been identified in recent years, the limited global coverage of the data and the large diversity in consumer products necessitates more information for an overall picture of the FR composition in common products/materials. To address this issue, 137 individual samples of various consumer products, building materials and wastes were collected. To identify and characterize potential sources of FRs in indoor environment, all samples were analyzed for content of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDDs) and novel flame retardants (NFRs). The most frequently detected were HBCDDs (85%), with the highest median concentration of Σ4HBCDDs of 300 mg kg−1 in polystyrenes. The highest median concentration of Σ10PBDEs was found in recycled plastic materials, reaching 4 mg kg−1. The lowest concentrations were observed for NFRs, where the median of Σ12NFRs reached 0.4 mg kg−1 in the group of electrical & electronic equipment wastes. This suggests that for consumer products and building materials that are currently in-use, legacy compounds still contribute to the overall burden of FRs. Additionally, contrasting patterns of FR composition in recycled and virgin plastics, revealed using principle component analysis (PCA), suggest that legacy flame retardants are reentering the market through recycled products, perpetuating the potential for emissions to indoor environments and thus for human exposure.

The comparability of data from active (ACT) and passive sampling (PAS) of persistent organic pollutants (POPs) in air is hindered by uncertainties related to the derivation of sampling rates and concentrations, as well as differences in the duration, volume and frequency of sampling. Although data from ACT have been used extensively in short-term PAS calibration studies, no attempts have been made to evaluate the comparability of long-term trends calculated from PAS to established ACT trends. This is crucial, as continuous long-term ACT is unfeasible in most regions of the world. To address these challenges, we calculated and compared trends for organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) at the six sites in Europe with at least 5 years of co-located ACT and PAS data (2012–2016): Birkenes, Košetice, Pallas, Råö, Stórhöfði and Zeppelin. Strong agreement of ACT and PAS trends was observed for most OCPs and PCBs. Apart from two PCBs at Stórhöfði, all pairs of ACT and PAS trends followed the same direction. However, differences in the magnitude, significance and confidence intervals of their slopes were observed for some compounds and were primarily attributed to the short duration of the PAS time series. Despite some limitations, our results suggest that the comparability of ACT and PAS POP trends will continue to improve with additional years of data. This study confirms the suitability of PAS for the calculation of long-term POP trends in air, and highlights the importance of continuous sampling at established monitoring sites with consistent analytical methods. ISSN:2050-7887 ISSN:2050-7895

Polycyclic aromatic hydrocarbons (PAHs) and some of their nitrated derivatives, NPAHs, are seemingly ubiquitous in the atmospheric environment. Atmospheric lifetimes may nevertheless vary within a wide range, and be as short as a few hours. The sources and sinks of NPAH in the atmosphere are not well understood. With a Lagrangian field experiment and modeling, we studied the conversion of the semivolatile PAHs fluoranthene and pyrene into the 2-nitro derivatives 2-nitrofluoranthene and 2-nitropyrene in a cloud-free marine atmosphere on the time scale of hours to 1 day between a coastal and an island site. Chemistry and transport during several episodes was simulated by a Lagrangian box model i.e., a box model coupled to a Lagrangian particle dispersion model, FLEXPART-WRF. It is found that the chemical kinetic data do capture photochemical degradation of the 4-ring PAHs under ambient conditions on the time scale of hours to 1 day, while the production of the corresponding NPAH, which sustained 2-nitrofluoranthene/fluoranthene and 2-nitropyrene/pyrene yields of (3.7 ± 0.2) and (1.5 ± 0.1)%, respectively, is by far underestimated. Predicted levels of NPAH come close to observed ones, when kinetic data describing the reactivity of the OH-adduct were explored by means of theoretically based estimates. Predictions are also underestimated by 1-2 orders of magnitude, when NPAH/PAH yields reported from laboratory experiments conducted under high NOx conditions are adopted for the simulations. It is concluded that NPAH sources effective under low NOx conditions, are largely underestimated., Grant Agency of the Czech Republic (P503 16-115375); Izmir Institute of Technology Research Fund (2013IYTE-14); Max Planck Society; European Union (262254); Ministry of Education, Youth & Sports - Czech Republic (LM2015051/CZ.02.1.01/0.0/0.0/16_013/0001761)

Polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) are ubiquitous and toxic contaminants. Their atmospheric deposition fluxes on the regional scale were quantified based on simultaneous sampling during 1 to 5 years at 1 to 6 background/rural sites in the Czech Republic and Austria. The samples were extracted and analysed by means of gas chromatography coupled to mass spectrometry. For all seasons and sites, total deposition fluxes for Σ15PAHs ranged 23–1100 ng m−2 d−1, while those for Σ6PCBs and Σ12OCPs ranged 64–4400 and 410–7800 pg m−2 d−1, respectively. Fluoranthene and pyrene were the main contributors to the PAH deposition fluxes, accounting on average for 19% each, while deposition fluxes of PCBs and OCPs were dominated by PCB153 (26%) and γ-hexachlorobenzene (30%), respectively. The highest deposition flux of Σ15PAHs was generally found in spring, while no seasonality was found for PCB deposition. For deposition fluxes for Σ12OCPs, no clear spatial trend was found, confirming the perception of long-lived regional pollutants. Although most OCPs and PCBs hardly partition to the particulate phase in ambient air, on average, 42% of their deposition fluxes were found on filters, confirming the perception that particle deposition is more efficient than dry gaseous deposition. Due to methodological constraints, fluxes derived from bulk deposition samplers should be understood as lower estimates, in particular with regard to those substances which in ambient aerosols mostly partition to the particulate phase. Electronic supplementary material The online version of this article (10.1007/s11356-019-05464-9) contains supplementary material, which is available to authorized users.

This study is a systematic assessment of different houses and apartments, their ages and renovation status, indoors and outdoors, and in summer vs. winter, with a goal of bringing some insight into the major sources of semivolatile organic compounds (SVOCs) and their variability. Indoor and outdoor air concentrations of polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and novel flame retardants (NFRs) were determined at 17-20 homes in Czech Republic in winter and summer. Indoor concentrations were consistently higher than outdoor concentrations for all compounds; indoor/outdoor ratios ranged from 2-20, with larger differences for the current use NFRs than for legacy PCBs. Seasonal trends differed according to the use status of the compounds: the PCBs had higher summer concentrations both indoors and outdoors, suggesting volatilization as a source of PCBs to air. PBDEs had no seasonal trends indoors, but higher summer concentrations outdoors. Several NFRs (TBX, PBT, PBEB) had higher indoor concentrations in winter relative to summer. The seasonal trends in the flame retardants suggest differences in air exchange rates due to lower building ventilation in winter could be driving the concentration differences. Weak relationships were found with building age for PCBs, with higher concentrations indoors in buildings built before 1984, and with the number of electronics for PBDEs, with higher concentrations in rooms with three or more electronic items. Indoor environments are the primary contributor to human inhalation exposure to these SVOCs, due to the high percentage of time spent indoors (>90%) combined with the higher indoors levels for all the studied compounds. Exposure via the indoor environment contributed ∼96% of the total chronic daily intake via inhalation in summer and ∼98% in winter.

Pinus mugo Turra is a typical pine tree from mountain habitats. It is ideal as a bioindicator for air quality monitoring, but, to the best of our knowledge, has never been implemented to determine organic compound concentrations. This study presents the initial methodology for the use of pine needles to measure contamination levels and evaluate genotoxicity potentials caused by long-range transport of pollutants at sites in the Slovak mountains in comparison to an industrial urban area. Pinus mugo needles have many positive attributes, particularly the five-year lifetime of needles compared with other species of pine. The presence of epicuticular wax on the surface of needles allows accumulation of lipophilic organic compounds. Pine needles were analyzed for POP compounds (PCBs, OCPs, PBDEs), PAHs, PFCs and lead. A pollen grain abortion assay with Pinus mugo species was also tested as a method to identify contamination of high mountain habitats. The concentration of organic compounds increased proportionally with needle age. Concentrations along the mountain transect were heavily influenced by atmospheric transport and proximity to potential sources of contamination from industry and residential areas from north and south of the mountain. The slope exposure direction had a large impact on concentrations of PBDEs (mainly for BDE 209). High concentrations of PFCs were discovered near a ski resort, where the use of these substances is high due to fluorinated ski waxes and personal outdoor clothing. A positive correlation between pollen grain abortivity and elevation was observed, with the strongest effect on pollutants at the top of the mountains. The results showed the highest genotoxicity at the site near a pulp mill (Zilina), where the frequency of abortive pollen grains was 3.1 times higher than at the control site. Lead content increased gradually with needle age, and a correlation was found between Pb levels in needles and pollen abortivity. It can be concluded that Pinus mugo is a suitable bioindicator species for assessment of long-term trends of atmospheric contamination in high mountain habitats.

Seven types of indoor samples, covering five indoor matrices, were collected in a residential room, and analyzed for five classes of semivolatile organic compounds (SVOCs). The goal was to improve the understanding of the relationship between indoor air, surface films and dust, based on differences in sources, physicochemical properties, and indoor environmental characteristics. Comparisons of the five matrices (gas- and particle-phase air, floor dust, surface dust/films and window films) demonstrated that within our test room a semi-quantitative measurement of the SVOC distributions and concentrations could be obtained by air, and composite dust or furniture surface wipes. Dust concentrations varied within the room, and spot samples were not necessarily representative of the average room conditions. Polyurethane foam passive air samplers (PUF-PAS) successfully quantified the total air concentrations of the studied SVOC compound groups, as indoor air concentrations were dominated by gas-phase compounds, however air concentrations of individual particle-bound compounds had higher uncertainty. Measured concentrations of dust/surfaces could be used to estimate air concentrations of legacy SVOCs, demonstrating equilibrium in the room. However, air concentrations of current-use compounds (flame retardants, polycyclic aromatic hydrocarbons (PAHs)) could not be estimated from dust/surface concentrations, demonstrating the influence of ongoing primary emissions and non-equilibrium status in the room.

As a consequence of long-range transported pollution, air–sea exchange can become a major source of persistent organic pollutants in remote marine environments. The vertical gradients in the air were quantified for 14 species, i.e. four parent polycyclic aromatic hydrocarbons (PAHs), three polychlorinated biphenyls (PCBs), three organochlorine pesticides (OCPs) and two polybrominated diphenylethers (PBDEs) in the gas-phase at a remote coastal site in the southern Aegean Sea in summer. Most vertical gradients were positive (Δc∕Δz > 0), indicating downward (net depositional) flux. Significant upward (net volatilisational) fluxes were found for three PAHs, mostly during daytime, and for two OCPs, mostly during night-time, as well as for one PCB and one PBDE during part of the measurements. While phenanthrene was deposited, fluoranthene (FLT) and pyrene (PYR) seem to undergo flux oscillation, hereby not following a day–night cycle. Box modelling confirms that volatilisation from the sea surface has significantly contributed to the night-time maxima of OCPs. Fluxes were quantified based on eddy covariance. Deposition fluxes ranged from −28.5 to +1.8 µg m−2 day−1 for PAHs and −3.4 to +0.9 µg m−2 day−1 for halogenated compounds. Dry particle deposition of FLT and PYR did not contribute significantly to the vertical flux.

This study presents four years ambient monitoring data of seventeen 2,3,7,8-chlorine substituted polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs), twelve dioxin-like polychlorinated biphenyls (dl-PCBs) and sixteen polycyclic aromatic hydrocarbons (PAHs) designed by the US EPA at a background site in central Europe during 2011–2014. The concentrations expressed as toxic equivalents (TEQs) using the WHO2005-scheme for PCDD/Fs (0.2 fg m−3-61.1 fg m−3) were higher than for dl-PCBs (0.01 fg m−3-2.9 fg m−3), while the opposite was found in terms of mass concentrations. ΣPAHs ranged from 0.20 ng m−3 to 134 ng m−3. The mass concentration profile of PCDD/Fs, dl-PCBs and PAHs was similar throughout the four years. PCDD/Fs and PAHs concentrations were dominated by primary sources peaking in winter, while those of dl-PCBs were controlled by secondary sources characterized by a spring-summer peak. During 2011–2014, no significant decrease in the atmospheric levels of ΣPCDD/Fs was observed. On the other hand, the concentrations of Σdl-PCBs and ΣPAHs were decreasing, with halving times of 5.7 and 2.7 years, respectively. We estimated that 422 pg m−2 year−1-567 pg m−2 year−1 TEQ PCDD/Fs and 3.48 pg m−2 year−1-15.8 pg m−2 year−1 TEQ dl-PCBs were transferred from the air to the ground surfaces via dry particulate deposition during 2011–2014.

Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) are restricted compounds that are ubiquitously detected in the environment, including indoor matrices such as air and residential dust. We report concentrations of PCBs and selected OCPs in indoor air and dust from homes in Canada (23 homes) and Czech Republic (20 homes). Indoor air concentrations of PCBs and OCPs were ∼10 times higher than that outdoors. PCB concentrations of ∼450 ng/m3 were similar in both countries, higher in homes built before the restrictions on PCBs, and had congener profiles consistent with PCB mixtures manufactured or used in each country. All OCP air concentrations were higher in the Czech Republic than in the Canadian samples, suggesting greater indoor use of, for example, DDT and HCH. These data emphasize the persistence of these organochlorine compounds indoors and their presence in homes even decades after new usage was prohibited. Indoor levels of these legacy POPs remain at similar concentrations to compounds of current concern, such as brominated flame retardants and perfluorinated alkyl substances, emphasizing that they deserve ongoing attention in view of knowledge of PCB and OCP toxicity.

The central and eastern Mediterranean is a receptor area for persistent organic pollutants (POPs) emitted in western, central and eastern Europe, particularly during summer. Atmospheric concentrations of PCBs, DDXs, PBDEs, penta- and hexachlorobenzene were measured during a ship-borne survey in the summer of 2010. The concentration of PCBs (sum of 7 congeners) was 3.61 (2.08-7.72) pg m(-3), of which 6.7% was associated with the particulate phase. The mean concentration of DDT isoi-ners and their metabolites, DDE and DDD, was 2.60 (0.46-7.60) pg m(-3) (particulate mass fraction theta = 0.097), of penta- and hexachlorobenzene 0.22 (

PBDEs (10 congeners) were analyzed using GC-MS in superficial sediments and organisms of the Concepcion Bay after the 2010 Tsunami. From all congeners analyzed PBDE-47, -99, -100 and -209 were the most frequently detected. Concentrations (ng g(-1) d.w.) in sediments for Sigma PBDE-47, -99, -100 were low (0.02-0.09). However, PBDE-209 showed significantly higher values similar to 20 ng g-, d.w. This result were similar to 10 times lower than those reported in a previous study of the 2010 Tsunami. The high result might be influenced by the massive urban debris dragged by the 2010 Tsunami. In organisms, concentrations of PBDE-47, -99, -100 (similar to 0.4 ng g(-1) d.w.) were higher than those found in sediments (similar to 0.04 ng g(-1) d.w.). Differences in PBDE pattern were also observed between different levels of the trophic food chain (primary and secondary consumers). This is the first attempt to assess the current status of Concepcitin Bay after the 2010 Tsunami.

Aerobic composting and anaerobic digestion plays an important role in reduction of organic waste by transforming the waste into humus, which is an excellent soil conditioner. However, applications of chemical-contaminated composts on soils may have unwanted consequences such as accumulation of persistent compounds and their transfer into food chains. The present study investigated burden of composts and digestates collected in 16 European countries (88 samples) by the compounds causing dioxin-like effects as determined by use of an in vitro transactivation assay to quantify total concentrations of aryl hydrocarbon receptor-(AhR) mediated potency. Measured concentrations of 2,3,7,8-Tetrachlorodibeno-p-dioxin (2,3,7,8-TCDD) equivalents (TEQbio) were compared to concentrations of polycyclic aromatic hydrocarbons (PAHs) and selected chlorinated compounds, including polychlorinated dibenzo-p-dioxins/furans (PCDD/ Fs), co-planar polychlorinated biphenyls (PCBs), indicator PCB congeners and organochlorine pesticides (OCPs). Median concentrations of TEQbio (dioxin-like compounds) determined by the in vitro assay in crude extracts of various types of composts ranged from 0.05 to 1.2 with a maximum 8.22 lg (TEQbio )k g 1 dry mass. Potencies were mostly associated with less persistent compounds such as PAHs because treatment with sulfuric acid removed bioactivity from most samples. The pan-European investigation of contamination by organic contaminants showed generally good quality of the composts, the majority of which were in compliance with conservative limits applied in some countries. Results demonstrate performance and added value of rapid, inexpensive, effect-based monitoring, and points out the need to derive corresponding effect-based trigger values for the risk assessment of complex contaminated matrices such as composts.

Polybrominated diphenyl ethers (PBDEs) are toxic contaminants with a persistent character and adverse effects on humans and wildlife. Therefore, the deposition of these chemicals in vegetation must be carefully controlled. Our objective was to determine PBDE concentrations (BDEs 28, 47, 66, 85, 99, 100, 153, 154, 183 and 209) in Pleurozium schreberi collected in a heavily industrialized urban agglomeration. High PBDE concentrations in the moss confirm the presence of active sources of atmospheric pollution in an area tested. The distribution of these xenobiotics was related to the vegetation cover being lower in sites surrounded by forests which indicates that PBDEs may have a tendency to be trapped from the air by tree leaves and needles. Congener profiles in P. schreberi were dominated by BDE 209 which was for 79% (in case of the coke smelter) to 95% (in case of the chemical plant) part of the total PBDE burden in this moss. The principal component and classification analysis classifying the concentration of PBDEs in P. schreberi allowed us to distinguish the pattern of these compounds characteristic for the origin of pollution. P. schreberi may be used as a bioindicator for PBDEs in areas contaminated with these chemicals.

The occurrence and atmospheric behavior of tri- to deca-polybrominated diphenyl ethers (PBDEs) were investigated during a 2-week campaign concurrently conducted in July 2012 at four background sites around the Aegean Sea. The study focused on the gas/particle (G/P) partitioning at three sites (Ag. Paraskevi/central Greece/suburban, Finokalia/southern Greece/remote coastal, and Urla/Turkey/rural coastal) and on the size distribution at two sites (Neochorouda/northern Greece/rural inland and Finokalia/southern Greece/remote coastal). The lowest mean total (G + P) concentrations of ∑7PBDE (BDE-28, BDE-47, BDE-66, BDE-99, BDE-100, BDE-153, BDE-154) and BDE-209 (0.81 and 0.95 pg m−3, respectively) were found at the remote site Finokalia. Partitioning coefficients, KP, were calculated, and their linear relationships with ambient temperature and the physicochemical properties of the analyzed PBDE congeners, i.e., the subcooled liquid pressure (PL°) and the octanol-air partition coefficient (KOA), were investigated. The equilibrium adsorption (PL°-based) and absorption (KOA-based) models, as well as a steady-state absorption model including an equilibrium and a non-equilibrium term, both being functions of log KOA, were used to predict the fraction Φ of PBDEs associated with the particle phase. The steady-state model proved to be superior to predict G/P partitioning of BDE-209. The distribution of particle-bound PBDEs across size fractions < 0.95, 0.95–1.5, 1.5–3.0, 3.0–7.2, and > 7.2 μm indicated a positive correlation between the mass median aerodynamic diameter and log PL° for the less brominated congeners, whereas a negative correlation was observed for the high brominated congeners. The potential source regions of PBDEs were acknowledged as a combination of long-range transport with short-distance sources., Granting Agency of the Czech Republic (312334); Czech Ministry of Education, Youth, and Sports (LO1214--LM2015051); Izmir Institute of Technology Scientific Research Foundation (2013IYTE14); European Union FP7 (262254 ACTRIS)

The increasing number of children suffering from developmental disorders has raised questions regarding their association with the presence of environmental contaminants in mothers and children. We therefore developed a new method for the determination of 78 proven and potential developmental neurotoxicants, including polychlorinated biphenyls, legacy pesticides, pyrethroids, and old and new halogenated flame retardants in breast milk. The essential part of sample preparation was dialysis as a non-destructive clean-up step which was newly used at 10 °C and showed more efficient lipid removal (up to 96%) than the conventional methods such as gel permeation chromatography or freezing-lipid filtration and thus ensured low limits of detection (LOD) by reducing the sample volume prior to injection. Next advantages were significant solvent reduction and no risk of sample cross-contamination. Gas chromatography coupled with high resolution mass spectrometry (GC-HRMS) was subsequently used for the separation and compound quantification. The method was validated using breast milk samples fortified with the analyzed compounds. Recoveries for most of the compounds ranged from 63 to 121% with a relative standard deviation of 2-25%, and LODs ranged between 0.001 and 0.87 ng g(-1) lipid weight. The method was applied to breast milk samples from a Dutch birth cohort where 35 out of the 78 compounds were quantified in more than 60% of the samples. For novel flame retardants, the method provides unique results regarding their occurrence in human matrices in Europe. Overall, the analysis of a complex mixture of developmental neurotoxicants could be useful for the assessment of the influence of the studied compounds to child health and development. Graphical abstract Flow diagram of the method and levels of the developmental neurotoxicants in Dutch human milk samples., Funding Agencies:"Employment of Best Young Scientists for International Cooperation Empowerment" - European Social Fund CZ.1.07/2.3.00/30.0037Sate budget of the Czech RepublicCzech Ministry of Education, Youth and Sports LO1214 LM 2015051