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Every day we are exposed to a cocktail of anthropogenic compounds many of which are biologically active and capable of inducing negative effects. The simplest way to monitor contaminants in a population is via human biomonitoring (HBM), however conventional targeted approaches require foreknowledge of chemicals of concern, often have compound specific extractions and provide information only for those compounds. This study developed an extraction process for human biomarkers of interest (BoE) in urine that is less compound specific. Combining this with an ultra-high resolution mass spectrometer capable of operating in full scan, and a suspect and non-targeted analysis (SS/NTA) approach, this method provides a more holistic characterization of human exposure. Sample preparation development was based on enzymatically hydrolysed urine spiked with 34 native standards and extracted by solid-phase extraction (SPE). HRMS data was processed by MzMine2 and 80% of standards were identified in the final data matrix using typical NTA data processing procedures., (Copyright © 2022 The Authors. Published by Elsevier Ltd.. All rights reserved.)

The personal care product (PCP) industry is a worldwide multi-billion-dollar industry. Several synthetic compounds like parabens and antimicrobial agents triclosan (TCS) and triclocarban (TCC) are ingredients in many PCPs. Due to growing public awareness of potential risks associated with parabens and other synthetic compounds, more PCPs are being marketed as "green," "alternative," or "natural." We analyzed 19 green and 34 conventional PCP products obtained from a European store for seven parabens, TCC, and TCS. We found no statistically significant difference in the concentrations between green and conventional products. Only four products mentioned parabens in the list of ingredients; however, parabens were detected in 43 products, and at μg/g levels in seven PCPs. Methylparaben was typically present at the highest concentration, and one mascara exceeded the European legal concentration limit of methylparaben. Low concentrations of isopropyl-, isobutyl-, and benzylparabens, which are banned in the EU, were detected in 70% of PCPs. The cumulative estimated daily intake of parabens is an order of magnitude higher for people using only conventional products than those using green products exclusively. We propose that legislation be developed with more explicit rules on when a product can be advertised as "green" to aid consumers' choices., (Copyright © 2022 The Authors. Published by Elsevier Ltd.. All rights reserved.)

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/m 3 ) and chlorpyrifos (median 0.70 ng/m 3 ) 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., (Copyright © 2021 The Authors. Published by Elsevier Ltd.. All rights reserved.)

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., (Copyright © 2021 The Authors. Published by Elsevier Ltd.. All rights reserved.)

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 Σ 17 NPAHs, from 32 to 2600 pg m -3 for Σ 10 OPAHs and from 5.1 to 4300 pg m -3 for Σ 2 O-heterocycles. The average particulate mass fraction (θ) ranged from 0.01 ± 0.02 (2-nitronaphthalene) to 0.83 ± 0.22 (1-nitropyrene) for individual NPAHs and from <0.01 ± 0.01 (dibenzofuran) to 0.96 ± 0.08 (6H-benzo (c,d)pyren-6-one) for individual OPAHs and O-heterocycles. The multiyear variations showed downward trends for a number of targeted compounds. This suggests that on-going emission reductions of PAHs are effective also for co-emitted NPAHs and OPAHs., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Persistent halogenated compounds (PHC) are of concern for human and environmental health. Persistent Organic Pollutants (POPs) are regulated by international treaties, but alternative compounds such as novel brominated flame retardants (NBFRs) and Dechlorane Plus (DP) are not-yet they are increasingly used. There are no data on PHCs in coral reef biota from tropical islands in the western Indian Ocean (WIO). For this assessment, three hard coral genera, two soft coral genera, and ember parrotfish (Scarus rubroviolaceus) were collected from the remote Rodrigues, Agalega, and St. Brandon's Atoll (Republic of Mauritius) in the Mascarene Basin of the WIO. Five compounds - Pentabromotoluene (PBT), γ-HCH, p,p'-DDE, HCB, and BDE-47- were quantifiable in all samples. Hard coral consistently contained the lowest concentrations of PHCs, except for NBFRs. The presence of BDE-47 suggests long-range aerial transport. We quantified DP, currently a candidate POP, in coral reef biota. PBT was measured in all samples also suggests long-range transport. Because the hard coral, soft coral, and fish had differing concentrations and patterns of PHCs, future surveys should stratify sampling accordingly. Agalega and St. Brandon's Atoll can be considered as locations to monitor changes in background concentrations of pollutants due to their remoteness., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Increasing use of current-use pesticides (CUPs) in Africa raises environmental and public health concerns. But there is a large uncertainty about their occurrence and the composition of pesticide mixtures on this continent. This paper investigates the presence of 27 CUPs in air across 20 sampling sites in Africa. 166 passive air samples, consisting of polyurethane foam (PUF), were collected in 12 African countries between 2010 and 2018. Samples were extracted with methanol and analyzed via high-performance liquid chromatography coupled with tandem mass spectrometry. The detection frequencies of CUPs per site were compared to land use patterns and sampling years, while their similarities were assessed using hierarchical cluster analysis. Overall, 24 CUPs were detected at least once. In 93% of all samples, at least one CUP was detected, while 78% of the samples had mixtures of two or more CUPs (median 3, interquartile range 5). Atrazine and chlorpyrifos were detected in 19 out of 20 sampling sites. Carbaryl, metazachlor, simazine, tebuconazole and terbuthylazine had the highest detection frequencies at sampling sites dominated by croplands. Across all the sampling years, 16 CUPs were present. Seven CUPs were newly detected from 2016 onwards (azinfos-methyl, dimetachlor, chlorsulfuron, chlortoluron, isoproturon, prochloraz and pyrazon), while metamitron was only present before 2012. Sites within a radius of about 200 km showed similarities in detected CUP mixtures across all samples. Our results show the presence of CUP mixtures across multiple agricultural and urban locations in Africa which requires further investigation of related environmental and human health risks., Competing Interests: Declaration of competing interest The authors declare that they have no conflict of interest., (Copyright © 2020 The Authors. Published by Elsevier Ltd.. All rights reserved.)

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 WHO 2005 -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., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Indoor dust is often used to evaluate levels of organic compounds indoors, particularly for compounds with indoor sources, such as flame retardants (FRs). Yet there are uncertainties about the type of information that can be obtained from indoor dust. This study reports detailed dust sampling to assess spatial variability in indoor dust concentrations, the relationship between FR sources and dust, and the implications when interpreting dust concentrations. Multiple dust samples were collected from a range of surface types in three large rooms: a residential flat, a university seminar room, and a university computer room. Samples were analysed for polybrominated diphenyl ethers (PBDEs), novel halogenated flame retardants (NFRs) and organophosphate esters (OPEs). FR levels in dust varied significantly between and within rooms. Levels typically ranged over one order of magnitude within a room, and up to four orders of magnitude for a few OPEs. The spatial distribution of FRs related (in some cases) to proximity to sources, surface properties, and dust surface loadings. Differences also existed between surface and floor dusts, e.g., the contribution of TBOEP to ∑OPEs was higher in floor than surface dust, which has implications for human exposure assessment; adults typically have more contact with elevated surfaces, while young children have greater contact with floor surfaces. Overall, significant spatial heterogeneity exists in indoor dust, even in seemingly homogeneous indoor spaces, thus hampering comparability between studies and locations when single samples are collected. Composite samples are strongly recommended to limit the influence of spatial heterogeneity., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Coniferous needles can be used as a passive air sampler of semivolatile organic compounds (SVOC) and an indicator of atmospheric pollution patterns and trends. There is limited information on whether different parts of the plant (e.g., foliage leaves, dwarf shoots, twig, etc.) contain different levels of SVOC. Only few studies have compared levels of SVOC surface layer of wax and to their total content in all needle tissues and what affects an uptake and distribution of SVOC. It is important to have better understanding of the extent to which sampling and sample preparation procedures affect measured levels of SVOC in pine needles and reduce comparability of data from samples processed in different ways. In the present study, we assessed an impact of various sampling and sample preparation techniques on the levels of SVOC in Pinus sylvestris needles. While the impact of various storing, washing and drying methods was not significant, presence of dwarf shoots in the sample or structural damage of needles affected the results significantly. Results show that levels of SVOC in dwarf shoots are 2-8 times higher than those in foliage leaves. Therefore, dwarf shoots must be carefully removed before foliage leaves extraction to improve comparability of results. There were different patterns in SVOC on the surface of the foliage leaves compared to the whole leaves. An uptake of these substances by the surface wax as well as their occurrence in the internal structure was of function of the physico-chemical properties of the substances (log K ow , molar weight)., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

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 Σ 4 HBCDDs of 300 mg kg -1 in polystyrenes. The highest median concentration of Σ 10 PBDEs was found in recycled plastic materials, reaching 4 mg kg -1 . The lowest concentrations were observed for NFRs, where the median of Σ 12 NFRs 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., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Polyurethane foam (PUF) disk passive air samplers were deployed concurrently at five sites across Kolkata megacity and the rural mangrove wetland of Sundarban (UNESCO World Heritage Site) between January-March in 2014. Samples were analyzed for hexachlorocyclohexanes (HCHs), dichlorodiphenyltricholoroethanes (DDTs), polychlorinated biphenyls (PCBs) and, polybrominated diphenyl ethers (PBDEs) using gas chromatography and mass spectrometry (GC-MS). Derived air concentrations (pg/m 3 ) for Kolkata ranged: for ∑α- and γ-HCH between 70 and 207 (114 ± 62), ∑ 6 DDTs: 127-216 (161 ± 36), ∑ 7 PCBs: 53-213 (141 ± 64), and ∑ 10 PBDEs: 0.30-23 (11 ± 9). Low values for all the studied POPs were recorded in the remote area of the Sundarban site (with the exception of DDTs: o,p'-DDT and p,p'-DDT), where ∑ 4 DDTs was 161 ± 36. In particular, the site of Ballygunge, located in the southern part of Kolkata, showed the highest level of all the metabolites/congeners of POPs, suggesting a potential hot spot of usage and emissions. From HCHs, α-/γ-HCH isomers ratio was low (0.67-1.96) indicating a possible sporadic source of lindane. γ-HCH dominated the HCH signal (at 3 sites) reflecting wide spread use of lindane both in Kolkata and the Sundarban region; however, isomeric composition in Kolkata also suggests potential technical HCHs use. Among DDT metabolites, both o,p'-DDT and p,p'-DDT shared the dominant percentages accounting for ∼26-46% of total DDTs followed by p,p'-DDE (∼12-19%). The PCB congener profile was dominated by tri- and tetra-Cl at the southern and eastern part of Kolkata. These results are one of the few contributions that reports air concentrations of POPs, concurrently, at urban and remote villages in India. These data are useful to assess atmospheric pollution levels and to motivate local and regional authorities to better understand the potential human exposure risk associated to urban areas in India., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Perfluoroalkyl and polyfluoroalkyl substances (PFASs) are a large group of important chemical compounds with unique and useful physico-chemical properties, widely produced and used in many applications. However, due to the toxicity, bioaccumulation and long-range transport potential of certain PFASs, they are of significant concern to scientists and policy makers. To assess human exposure to PFASs, it is necessary to understand the concentrations of these emerging contaminants in our environment, and particularly environments where urban population spend most of their time, i.e. buildings and vehicles. A total of 126 samples of building materials, consumer products, car interior materials and wastes were therefore analyzed for their content of key PFASs - 15 perfluoroalkyl acids (PFAAs). At least one of the target PFAAs was detected in 88% of all samples. The highest concentration of Σ 15 PFAAs was found in textile materials (77.61 μg kg -1 ), as expected, since specific PFAAs are known to be used for textile treatment during processing. Surprisingly, PFAAs were also detected in all analyzed composite wood building materials, which were dominated by perfluoroalkyl carboxylic acids with 5-8 carbons in the chain (Σ 4 PFCAs up to 32.9 μg kg -1 ). These materials are currently widely used for building refurbishment, and this is the first study to find evidence of the presence of specific PFASs in composite wood materials. Thus, in addition to consumer products treated with PFASs, materials used in the construction of houses, schools and office buildings may also play an important role in human exposure to PFASs., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Pine needles were sampled to determine levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and metals in Scots pine (Pinus sylvestris) needles at industrial, urban and background sites in Sweden (SW), Czech Republic (CZ) and Slovakia (SK). Spatial and temporal patterns of PCDD/Fs in pine needles were investigated and principal component analysis (PCA) used to determine spatial patterns, potential sources and transport of PCDD/Fs. Levels of PCDD/Fs in pine needles were generally greatest near to industrial sites (Ʃ2,3,7,8-PCDD/Fs (lower bound (LB)): 6 ng kg(-1) - 190 ng kg(-1)) compared to urban and background sites (Ʃ2,3,7,8-PCDD/Fs (LB): 0.90 ng kg(-1) - 20 ng kg(-1)). Using metal contamination in pine needles helped to detect spatial patterns and separate local thermal sources of PCDD/Fs., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

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., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Two groups of perfluorined compounds (PFCs), i.e. perfluoroalkyl sulfonates (PFASs) and perfluoroalkyl carboxylates (PFCAs) were analysed during a period of 1 year in monthly collected riverbed sediment samples from five sampling sites in an industrial region in Morava River catchment in Czech Republic. Levels of PFCs determined in sediment samples were up to 6.8 μg kg(-1) of dry weight. Among PFCs analysed, mainly short-chain PFASs (C6 to C8) including PFOS were found in sediment samples and their levels were similar to those found in comparable river basins in other parts of Europe. Concentrations of PFCs were correlated with organic carbon content and their variations were mainly correlated by high flow events on Morava River and its tributaries. The changes in PFC concentrations were induced by displacing of PFCs containing particles to the river sediment during these elevated flow events., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Riverine sediments, collected on a monthly basis during a period of one year, from five sites in a mixed land use region of the Czech Republic were analysed for chlorinated and brominated persistent organic pollutants (POPs). The region is located in the upper catchment of the Danube River. The POPs concentrations were as follows: 11-930 pg g(-1) polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/Fs), 170-980 pg g(-1) dioxin-like polychlorinated biphenyls (dl-PCBs), 34-13,700 pg g(-1) polychlorinated naphthalenes (PCNs), 5.7-29,200 pg g(-1) polybrominated diphenylethers (PBDEs) and 0.21-351 ng g(-1) hexabromocyclododecanes (HBCDs). Concentrations expressed as toxic equivalents (TEQs), for PCDD/F+dl-PCB+PCN (TEQPCDD/F+dl-PCB+PCN) ranged from 0.37 to 19 pg g(-1). The results revealed a clear spatial separation between sites based on concentration and congener profile. There were also some obvious temporal patterns of selected POPs, which were related to river flow (seasonality) and organic carbon (TOC) of the sediment. Potential sources of POPs include local municipalities (flame retardants), some diffuse sources (PCNs and PCDDs/Fs) and potential point sources (PBDEs). Risk assessment based on risk quotients (RQ) revealed limited to medium ecological risk from PBDEs. TEQPCDD/F+dl-PCB+PCN were low relative to other European rivers, hence the risk to aquatic organisms was considered to be low. PCNs contributed significantly to overall TEQ in several cases., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

The photochemistry of selected organic compounds, including common pollutants, on the paraffin (as a model matrix) and spruce wax surfaces was studied under laboratory conditions. Two model transformations were evaluated: (1) intramolecular rearrangements of valerophenone and 2-nitrobenzaldehyde, and (2) hydrogen abstraction between an excited benzophenone and the hydrocarbon paraffin/wax chains. The steric or polar influence of the solid matrix on conformational and translational motion, its optical properties, hydrogen abstraction probabilities, and consequences of the guest-molecule segregation are discussed in this work. Furthermore, the photochemical reactivity of some common anthropogenic pollutants, such as chlorinated biphenyls (4-chlorobiphenyl, 2,4-dichlorobiphenyl, and 4,4'-dichlorobiphenyl), 4-chlorophenol, and DDT, was evaluated. The surface of spruce wax is presented as probable reaction medium for photochemical transformations. Although the matrix presents certain restrictions for bimolecular reactions, common photodegradations should be generally feasible in nature. In addition, paraffin was found to be a suitable model matrix for the studies of possible photochemical transformations that can occur on natural plant surfaces.