Nitrifying Microorganisms Linked to Biotransformation of Perfluoroalkyl Sulfonamido Precursors from Legacy Aqueous Film-Forming Foams.

Drinking water supplies across the United States have been contaminated by firefighting and fire-training activities that use aqueous film-forming foams (AFFF) containing per- and polyfluoroalkyl substances (PFAS). Much of the AFFF is manufactured using electrochemical fluorination by 3M. Precursors with six perfluorinated carbons (C6) and non-fluorinated amine substituents make up approximately one-third of the PFAS in 3M AFFF. C6 precursors can be transformed through nitrification (microbial oxidation) of amine moieties into perfluorohexane sulfonate (PFHxS), a compound of regulatory concern. Here, we report biotransformation of the most abundant C6 sulfonamido precursors in 3M AFFF with available commercial standards (FHxSA, PFHxSAm, and PFHxSAmS) in microcosms representative of the groundwater/surface water boundary. Results show rapid (<1 day) biosorption to living cells by precursors but slow biotransformation into PFHxS (1-100 pM day-1). The transformation pathway includes one or two nitrification steps and is supported by the detection of key intermediates using high-resolution mass spectrometry. Increasing nitrate concentrations and total abundance of nitrifying taxa occur in parallel with precursor biotransformation. Together, these data provide multiple lines of evidence supporting microbially limited biotransformation of C6 sulfonamido precursors involving ammonia-oxidizing archaea (Nitrososphaeria) and nitrite-oxidizing bacteria (Nitrospina). Further elucidation of interrelationships between precursor biotransformation and nitrogen cycling in ecosystems would help inform site remediation efforts.

PFAS and Precursor Bioaccumulation in Freshwater Recreational Fish: Implications for Fish Advisories.

Per- and polyfluoroalkyl substances (PFAS) are a diverse class of fluorinated anthropogenic chemicals that include perfluoroalkyl acids (PFAA), which are widely used in modern commerce. Many products and environmental samples contain abundant precursors that can degrade into terminal PFAA associated with adverse health effects. Fish consumption is an important dietary exposure source for PFAS that bioaccumulate in food webs. However, little is known about bioaccumulation of PFAA precursors. Here, we identify and quantify PFAS in recreational fish species collected from surface waters across New Hampshire, US, using a toolbox of analytical methods. Targeted analysis of paired water and tissue samples suggests that many precursors below detection in water have a higher bioaccumulation potential than their terminal PFAA. Perfluorobutane sulfonamide (FBSA), a short-chain precursor produced by electrochemical fluorination, was detected in all fish samples analyzed for this compound. The total oxidizable precursor assay interpreted using Bayesian inference revealed fish muscle tissue contained additional, short-chain precursors in high concentration samples. Suspect screening analysis indicated these were perfluoroalkyl sulfonamide precursors with three and five perfluorinated carbons. Fish consumption advisories are primarily being developed for perfluorooctane sulfonate (PFOS), but this work reinforces the need for risk evaluations to consider additional bioaccumulative PFAS, including perfluoroalkyl sulfonamide precursors.

Passive Sampling of Persistent Organic Pollutants in Four Coastal Aquatic Systems of Puerto Rico: A Pilot Study.

Little is known about the presence and effects of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in Puerto Rico's waters. Four coastal aquatic systems were investigated using low-density polyethylene passive sampling for PCBs and OCPs in water and its overlying air. The highest total freely dissolved and gaseous concentrations of PCBs were found in Guánica Bay, with 4000 pg/L and 270 pg/m3, respectively. Five OCPs were detected, mainly in water, with greatest concentrations (pg/L) in Guánica Bay: α-HCH (7400), p,p'-DDE (390), aldrin (2000), dieldrin (420), and endrin (77). The compound α-HCH was also measured at elevated water concentrations in Condado Lagoon (5700 pg/L) and Laguna Grande (2900 pg/L). Jobos Bay did not show values of concern for these persistence organic pollutants. Levels of PCBs and OCPs in water, particularly in Guánica Bay, exceeded USEPA ambient water quality criteria values representing a human health risk regarding consumption of aquatic organisms.

Challenges in the Analysis of Novel Flame Retardants in Indoor Dust: Results of the INTERFLAB 2 Interlaboratory Evaluation.

The Interlaboratory Study of Novel Flame Retardants (INTERFLAB 2) was conducted by 20 laboratories in 12 countries to test the precision and accuracy of the analysis of 24 "novel" flame retardants (NFRs). Laboratories analyzed NFRs in injection-ready test mixtures, in extracts of residential dust, and in residential dust to evaluate the influence of dust handling and extraction. For test mixtures, mean reported concentrations of PBT, PBEB, EH-TBB, TBBPA, TBDP-TAZTO, TBOEP, α-TBCO, ß-DBE-DBCH, and total HBCDD differed by >25% relative to reference values. Coefficients of variation were higher in dusts/dust extracts than in test mixtures. Concentrations among laboratories ranged over 3-4 orders of magnitude for HBB, TBP-DBPE, TBP-AE, and TDCIPP in dust extracts and dusts. Most laboratories produced repeatable dust concentrations, but differences reported in the literature among laboratories of <70% could be due to analytical variability, and the attribution of such differences to other causes should be made with caution. Most variations in accuracy and precision were introduced by matrix effects and/or sample processing, rather than instrumental analysis. We recommend recovery correction to improve accuracy. There is a need to improve analytical methods and to validate methods on complex matrices such as standard reference materials for dust or spiked matrices.

Changes in Flame Retardant and Legacy Contaminant Concentrations in Indoor Air during Building Construction, Furnishing, and Use.

A newly constructed university building was selected for targeted assessment of changes in the levels of flame retardants and legacy contaminants during the installation of building equipment, furniture, electronics, and first year of building use. Indoor air samples were collected during several periods of intensive equipment installation to determine a relationship between newly introduced equipment and changes in the concentrations and profiles of contaminants in indoor air. Samples were analyzed for polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDDs), and new types of flame retardants: brominated (BFRs) and organophosphate esters (OPEs). Additionally, typical outdoor contaminants such as polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were also analyzed for comparison. From the set of 90 compounds analyzed here, hexabromobenzene (HBB) and tris(2-chloroisopropyl)phosphate (TCIPP) showed a significant concentration increase in indoor air concentrations during computer installation and operation, suggesting emission by operating computers, while an order of magnitude concentration increase in tris(1,3-dichloro-2-propyl)phosphate (TDCIPP) and tri-m-cresyl phosphate (TMTP) was observed after the furniture and carpet was introduced to the computer room, suggesting furniture or carpet as a source. However, the majority of compounds had no systematic change in concentrations during equipment installation, indicating that no sources of target compounds were introduced or, that source introduction was not reflected in indoor air concentrations. Generally, low levels of legacy flame retardants compared to their novel alternatives were observed.

An effective clean-up technique for GC/EI-HRMS determination of developmental neurotoxicants in human breast milk.

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.

Particle size distribution of halogenated flame retardants and implications for atmospheric deposition and transport.

This study investigates the distribution of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD) and a group of novel flame retardants (NFRs) on atmospheric aerosols. Two high volume cascade impactors were used to collect particulate fractions of ambient air over a one year period at urban and rural sites. The majority of FRs were found on the finest aerosols (<0.95 µm). Concentrations of HBCD were higher than those of ΣPBDEs. Moreover, we noted seasonality and spatial differences in particle size distributions, yet a large portion of the observed differences were due to differences in particulate matter (PM) itself. When normalized by PM, the size distributions of the FRs exhibited much greater heterogeneity. Differences existed between the FR distributions by molecular weight, with the higher molecular weight FRs (e.g., BDE-209, Dechlorane Plus) distributed more uniformly across all particulate size fractions. The seasonal, spatial, and compound-specific differences are of crucial importance when estimating dry and wet deposition of FRs as smaller aerosols have longer atmospheric residence times. Estimated wet and dry deposition of four representative FRs (BDE-47, BDE-209, HBCD, and Dechlorane Plus) using size-segregated aerosol data resulted in lower deposition estimates than when bulk aerosol data were used. This has implications for estimates of long-range atmospheric transport and atmospheric residence times, as it suggests that without size-specific distributions, these parameters could be underestimated for FRs.

Passive Sampler Derived Profiles and Mass Flows of Perfluorinated Alkyl Substances (PFASs) across the Fram Strait in the North Atlantic.

Per- and polyfluorinated alkyl substances (PFAS) are a family of pollutants of high concern due to their ubiquity and negative human health impacts. The long-range marine transport of PFAS was observed during year-long deployments of passive tube samplers in the Fram Strait across three depth transects. Time weighted average concentrations ranged from 2.4-360 pg L-1, and 10 different PFAS were regularly observed. PFAS profiles and concentrations were generally similar to those previously characterized for polycyclic aromatic hydrocarbons (PAHs) at these sites. The detection of several anionic PFAS in "old" water demonstrated that they are not perfect water mass tracers, but are also transported to depth via settling particles. Mass flows of PFAS through the Fram Strait in and out of the Arctic Ocean were basically similar (112 ±82 Mg year-1 northward flow, 100 ±54 Mg year-1 southward flow). For FOSA, export from the Arctic Ocean via the Fram Strait exceeded import by Atlantic Water, likely due to preferential transport and deposition in the Arctic Ocean. These observations suggest PFAS in the Arctic are governed by the feedback loop previously described for PAHs in the region - with additional atmospheric transport delivering volatile PFAS to the Arctic, which then get exported further.

Unregulated Active and Closed Textile Mills Represent a Significant Vector of PFAS Contamination into Coastal Rivers.

Despite concerns over the ubiquity of per- and polyfluoroalkyl substances (PFAS), little is known about the diversity of input sources to surface waters and their seasonal dynamics. Frequent use of PFAS in textiles means both active and closed textile mills require evaluation as PFAS sources. We deployed passive samplers at seven sites in an urban river and estuary adjacent to textile mills in Southern Rhode Island (USA) over 12 months. We estimated monthly mass flows (g month-1) of perfluorohexanoic acid (PFHxA: 45±56), and perfluorooctanoic acid (PFOA: 30±45) from the upstream river influenced by an active mill. Average mass flows were 73-155% higher downstream, where historical textile waste lagoons contributed long chain perfluoroalkyl acids (PFAA). Mass flows of PFNA increased from 7.5 to 21 g month-1 between the upstream and downstream portions of the rivers. Distinct grouping of the two main PFAS sources, active textile mills and historical waste lagoons, were identified using principal components analysis. Neither suspect screening nor extractable organofluorine analysis revealed measurable PFAS were missing beyond the targeted compounds. This research demonstrates that both closed and active textile mills are important ongoing PFAS sources to freshwater and marine regions and should be further evaluated as a source category.

Bioconcentration of per- and polyfluoroalkyl substances and precursors in fathead minnow tissues environmentally exposed to aqueous film-forming foam-contaminated waters.

Exposure to per- and polyfluoroalkyl substances (PFAS) has been associated with toxicity in wildlife and negative health effects in humans. Decades of fire training activity at Joint Base Cape Cod (MA, USA) incorporated the use of aqueous film-forming foam (AFFF), which resulted in long-term PFAS contamination of sediments, groundwater, and hydrologically connected surface waters. To explore the bioconcentration potential of PFAS in complex environmental mixtures, a mobile laboratory was established to evaluate the bioconcentration of PFAS from AFFF-impacted groundwater by flow-through design. Fathead minnows (n = 24) were exposed to PFAS in groundwater over a 21-day period and tissue-specific PFAS burdens in liver, kidney, and gonad were derived at three different time points. The ∑PFAS concentrations in groundwater increased from approximately 10,000 ng/L at day 1 to 36,000 ng/L at day 21. The relative abundance of PFAS in liver, kidney, and gonad shifted temporally from majority perfluoroalkyl sulfonamides (FASAs) to perfluoroalkyl sulfonates (PFSAs). By day 21, mean ∑PFAS concentrations in tissues displayed a predominance in the order of liver > kidney > gonad. Generally, bioconcentration factors (BCFs) for FASAs, perfluoroalkyl carboxylates (PFCAs), and fluorotelomer sulfonates (FTS) increased with degree of fluorinated carbon chain length, but this was not evident for PFSAs. Perfluorooctane sulfonamide (FOSA) displayed the highest mean BCF (8700 L/kg) in day 21 kidney. Suspect screening results revealed the presence of several perfluoroalkyl sulfinate and FASA compounds present in groundwater and in liver for which pseudo-bioconcentration factors are also reported. The bioconcentration observed for precursor compounds and PFSA derivatives detected suggests alternative pathways for terminal PFAS exposure in aquatic wildlife and humans. Environ Toxicol Chem 2024;00:1-12. © 2024 The Author(s). Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Avoiding artifacts in the determination of per- and polyfluoroalkyl substance sorbent-water distribution.

Characterizing sorbent affinity for a target compound (described by sorbent-water distribution coefficient, Ksw) is a necessary step in the sorbent selection and performance-testing process in the process of capturing aquatic contaminants. However, no standardized procedure exists to measure Ksw, and studies display significant variations in set-up and performance. For per- and polyfluoroalkyl substances (PFAS), most Ksw determinations employ batch experiments with small-scale water-sorbent mixtures, methanol-based spike of target compound(s), and analysis after assumed equilibrium, but methodological details of the above procedure differ and might cause artifacts in the determination of Ksw. We conducted several batch experiments systematically varying a general procedure to characterize effects of sub-optimal experimental design. Using a selection of PFAS (6-carbon fluorinated chain length with differing functional groups) and two sorbents, we tested variations of solution:sorbent ratio, methanol content, and PFAS initial concentration, and compared derived Ksw values. Each methodological component affected log(Ksw), usually by suppressing the value (by 0-48%) when compared with a "best design" procedure. Thus, we suggest (1) a reference procedure for PFAS and sorbents used here, and (2) general guidelines for batch experiment design with different compounds and sorbents. Additionally, we report well-constrained Ksw values for 23 PFAS and two sorbents.

Gaseous polycyclic aromatic hydrocarbons over the South China Sea: Implications for atmospheric transport under monsoon influences.

The seasonal monsoon variations have significant impact on the atmospheric transport of semi-volatile organic pollutants over the South China Sea (SCS). We analyzed polycyclic aromatic hydrocarbons (PAHs) over the basin and island areas (Yongxing Island and Yongshu Island) in 2017. Gaseous PAHs (0.17-1.4 ng m-3) showed spatio-temporal distinctions in their composition and sources among the basin and island areas. Mixed combustion sources of PAHs were identified over the SCS, including a petroleum source near the island areas. The transport routes of PAHs were inferred by the air mass back trajectories and potential source contribution factor analysis, identifying strong biomass burning signals from the Indochina Peninsula and other Southeast Asian countries. Emissions from approximately 90 % of the combustion sources were transported to basin areas by monsoons, whereas the island areas were dominated by local emissions. This study emphasizes the main potential terrestrial source of PAHs over the SCS under monsoon influences.

Poly- and Perfluorinated Alkyl Substances in Air and Water from Dhaka, Bangladesh.

Bangladesh hosts extensive textile manufacturing, for some of which per- and polyfluorinated alkyl substances (PFAS) have been used to impart water and dirt repellency, among other things. Textile waste emissions to the atmosphere and discharge into rivers and other bodies of water could present a significant concern for human and ecosystem health, but there is little information on PFAS in Bangladesh. To assess the presence of ionic PFAS and their precursors in air and water from Dhaka, Bangladesh, polyethylene sheets were deployed for 28 days as passive samplers for neutral PFAS in outdoor air and water, while ionic PFAS were measured from discrete water grabs. Fluorotelomer alcohols (FTOHs) were detected at almost all sites in air and water; the most frequently detected compound was 6:2 FTOH, ranging from below instrumental detection limits (

Spatial distribution and air-water exchange of organophosphate esters in the lower Great Lakes.

Organophosphate esters (OPEs) have been detected at elevated concentrations in the Great Lakes region, dwarfing other flame retardants, such as polybrominated diphenylethers (PBDEs), as chemicals of emerging concern (CECs). This prompted us to deploy polyethylene (PE) passive samplers in air and water column of the lower Great Lake region (Lake Erie and Lake Ontario) to detect gaseous and dissolved OPEs, evaluate their occurrence and spatial distribution, and estimate their air-water gas exchange fluxes. The median concentration of the total dissolved and gaseous phase OPEs detected (Σ9OPEs) were 95 ng L-1 and 404 pg m-3, respectively, during April-November 2014. Gaseous and dissolved concentrations were dominated by chlorinated compounds, in particular (tris(2-chloroethyl) phosphate (TCEP) and tris(2-chloroisopropyl) phosphate (TCPP), while tri-n-butyl phosphate (TnBP) was the dominant non-chlorinated OPEs in both media. Decreasing concentration gradients from shoreline/nearshore to offshore sites for both gaseous and aqueous OPEs reflect anthropogenic influence from the adjacent rural and urban regions. The partial dependence of gaseous OPEs on temperature indicate the importance of volatilization from local sources, fresh emissions as well as advection from distant sources to air. Almost all OPEs underwent net gas-phase deposition to the lakes, dominated by TCEP and TCPPs with median fluxes of -3980 ng/m2/day and -1320 ng/m2/day; the exception was TnBP, which underwent volatilization with the median fluxes of 1980 ng/m2/day. For all air-water pairs, the gaseous diffusive fluxes were 2-4 orders of magnitude greater than the estimated particle dry deposition fluxes.

The Air that we Breathe: Neutral and volatile PFAS in Indoor Air.

Sources of exposure to per- and polyfluorinated alkyl substances (PFAS) include food, water, and given that humans spend typically 90% of our time indoors, air and dust. Quantifying PFAS prevalent indoors, such as neutral, volatile PFAS, and estimating their exposure risk to humans is thus important. To accurately measure these compounds indoors, polyethylene (PE) sheets were employed and validated as passive detection tools, and analyzed by gas chromatography-mass spectrometry. Air concentrations were compared to dust and carpet concentrations reported elsewhere. Partitioning between PE sheets of different thicknesses suggested that interactions of the PEs with the compounds are occurring by absorption. Volatile PFAS, specifically fluorotelomer alcohols (FTOHs), were ubiquitous in indoor environments. For example, in carpeted Californian kindergarten classrooms, 6:2 FTOH dominated with concentrations ranging from 9-600 ng m-3, followed by 8:2 FTOH. Concentrations of volatile PFAS from air, carpet and dust were closely related to each other, indicating that carpets and dust are major sources of FTOHs in air. Nonetheless, air posed the largest exposure risk of FTOHs and biotransformed perfluorinated alkyl acids (PFAA) in young children. This research highlights inhalation of indoor air as an important exposure pathway and the need for further reduction of precursors to PFAA.

Linking past uses of legacy SVOCs with today's indoor levels and human exposure.

Semivolatile organic compounds (SVOCs) emitted from consumer products, building materials, and indoor and outdoor activities can be highly persistent in indoor environments. Human exposure to and environmental contamination with polychlorinated biphenyls (PCBs) was previously reported in a region near a former PCB production facility in Slovakia. However, we found that the indoor residential PCB levels did not correlate with the distance from the facility. Rather, indoor levels in this region and those reported in the literature were related to the historic PCB use on a national scale and the inferred presence of primary sources of PCBs in the homes. Other SVOCs had levels linked with either the activities in the home, e.g., polycyclic aromatic hydrocarbons (PAHs) with wood heating; or outdoor activities, e.g., organochlorine pesticides (OCPs) with agricultural land use and building age. We propose a classification framework to prioritize SVOCs for monitoring in indoor environments and to evaluate risks from indoor SVOC exposures. Application of this framework to 88 measured SVOCs identified several PCB congeners (CB-11, -28, -52), hexachlorobenzene (HCB), benzo(a)pyrene, and γ-HCH as priority compounds based on high exposure and toxicity assessed by means of toxicity reference values (TRVs). Application of the framework to many emerging compounds such as novel flame retardants was not possible because of either no or outdated TRVs. Concurrent identification of seven SVOC groups in indoor environments provided information on their comparative levels and distributions, their sources, and informed our assessment of associated risks.

Small-scale spatial variability of flame retardants in indoor dust and implications for dust sampling.

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.

PCBs and organochlorine pesticides in indoor environments - A comparison of indoor contamination in Canada and Czech Republic.

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.

Screening for halogenated flame retardants in European consumer products, building materials and wastes.

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.

Legacy and alternative halogenated flame retardants in human milk in Europe: Implications for children's health.

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.