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A baseline assessment of legacy and emerging flame retardant chemicals was performed in inland and transitional sediments as well as biosolids emanating from a selection of wastewater treatment plants (WWTPs) in Ireland. A selection of 24 polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and chlorinated organophosphate esters (Cl-OPEs) were quantified in: 81 inland and transitional sediment samples collected during 2023; 39 transitional sediments collected between 2018 and 2022; and 21 biosolid samples collected from 7 WWTPs over 4-month intervals in January, May, and September 2023. Highest concentrations of BDE-209 and several Cl-OPEs were detected in both sediment and biosolid samples, while most PCBs and penta-/octa-BDEs were comparatively low. Moderate levels of PBDEs and Cl-OPEs were detected in Irish sediments compared to similar studies conducted internationally. In biosolid samples, levels of BDE-209 were on the higher end of figured reported worldwide while levels of Σ 8 Cl-OPEs were the highest relative to comparable international studies. PCBs meanwhile are on the lower end of international levels for both biosolids and sediments. Based on available predicted no-effect concentrations (PNECs), the majority of compounds assessed were found to be of low-risk based on their levels in sediments with the exception of TCIPP (Risk Quotient - RQ = 1.354 = high risk) as well as EHDPP, TEHP, PCB-118, and PCB-52 (RQ = 0.948, 0.576, 0.446, and 0.257 respectively = moderate risk). Similar risk assessment could not be performed on contaminants in biosolids, though levels of BDE-209 were on the higher end of figured reported worldwide (avg = 3155 ng/g) while levels of Σ 8 Cl-OPEs were the highest relative to comparable international studies (avg 8  = 3290 ng/g). As the legacy PBDEs and PCBs have been listed as persistent organic pollutants (POPs) and replacement flame retardants such as Cl-OPEs have been flagged by programmes such as human biomonitoring for EU (HBM4EU) and the NORMAN Network as chemicals of emerging concern, continued monitoring of these moderate and high-risk contaminants in sediments, as well as an investigation of potential contamination of the food chain through land-spreading of biosolids on agricultural lands, would be warranted., Competing Interests: Declaration of competing interest The authors wish to declare that they have no competing interests that could influence the work reported in this manuscript., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Increasing attention on the estimation of bioavailability of organophosphate esters (OPEs) in soil or sediment has urged the development of techniques to measure soil-/sediment-associated porewater concentrations of OPEs. In this study, we investigated the sorption dynamics of 8 OPEs to polyoxymethylene (POM) spanning one order of magnitude of aqueous OPE concentrations and proposed POM-water partitioning coefficients (K pom/w ) for OPEs. The results showed that the K pom/w values were mainly affected by the hydrophobicity of OPEs. OPEs with high solubility preferentially partitioned into the aqueous phase indicated by the low log K pom/w values; while lipophilic OPEs were observed to be taken up by POM. The concentration of lipophilic OPEs in the aqueous phase had a strong impact on their sorption dynamics on POM, with higher aqueous concentrations accelerating the sorption dynamics and shortening the time for equilibration. We proposed that the required time to reach equilibration for targeted OPEs should be 42 d. The proposed equilibration time and K pom/w values were further validated by applying POM to soil artificially contaminated with OPEs to measure OPEs soil-water partitioning coefficients (K s ). The variations of K s among soil types implied the need to elucidate the effects of soil properties and chemical properties of OPEs on their distribution between soil and water in the future., Competing Interests: Declaration of competing interest Authors have declared that they have no potential conflict of interest., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Global restrictions on use of legacy brominated flame retardants (BFRs) such as polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCDD) have generated demand for novel BFRs (NBFRs) as substitutes. Our research group has previously reported decreased concentrations of PBDEs and HBCDD and increased concentrations of NBFRs in UK indoor environments, suggesting that restrictions on PBDEs and HBCDD are exerting an impact. In this study, we analysed UK foodstuffs collected in 2020-21 and compared the BFR concentrations found with those found in similar samples collected in 2015 to investigate whether similar trends in BFR concentrations would be observed. Concentrations of PBDEs and HBCDD isomers detected in our samples had declined by 78-92 % and 59-97 % since the 2015 study, respectively. Moreover, concentrations of NBFRs (dominated by 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE or TBE), and bis(2-ethyl hexyl) tetrabromophthalate (BEH-TEBP or TBPH)) in UK foodstuffs increased significantly (28-1400 %) between 2015 and 2020-21. Combined, these findings suggest that restrictions on use of PBDEs and HBCDD have had a discernible impact on concentrations of these legacy BFRs and their NBFR replacements in UK foodstuffs. Interestingly, given recent reports of a significant increase in concentrations of decabromodiphenyl ethane (DBDPE) in UK house dust between 2014 and 2019, a significant decline (70-84 %) in concentrations of DBDPE was observed in UK foodstuffs., 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 © 2022 The Authors. Published by Elsevier B.V. All rights reserved.)

Concentrations of the chlorinated organophosphate esters (Cl-OPEs): tris(2-chloroethyl) phosphate (TCEP), tris(1-chloro-2-propyl) phosphate (TCIPP), and tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) were measured in 273 waste synthetic foam and fabric articles collected in Ireland between 2019 and 2020. Articles examined comprised: polystyrene building insulation foam, as well as foam fillings and fabric coverings from furniture, mattresses, end-of-life vehicles, curtains, and carpets. Cl-OPEs were also measured in 156 samples from the same categories (except for building insulation foam) collected in 2015-16. Concentrations of TCIPP and TDCIPP in most samples exceeded those of TCEP; with those of TCIPP and TDCIPP generally and for some waste categories significantly (p < 0.05) higher in samples collected in 2019-20. Given potential future restrictions on use of these Cl-OPEs, we identified articles containing concentrations that exceeded 1000 mg/kg, in line with a similar limit that at the time of sample collection existed for some brominated flame retardants within the European Union. In 2019-20, 82 articles contained at least one Cl-OPE above 1000 mg/kg, with at least one article exceeding this concentration in each waste category examined. By comparison, only 28 samples collected in 2015-16, contained at least one Cl-OPE >1000 mg/kg, and articles exceeding this concentration were restricted to furniture and mattress foam, along with foams and fabrics from end-of-life vehicles. In the event of the introduction of such a limit on Cl-OPE concentrations in waste, it will result in 7200 t/year of such waste (24 % of the total) being rendered unrecyclable, while removing 98 % of the estimated ∼147,000 kg/year of Cl-OPEs from the recycling stream., 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 © 2022 The Authors. Published by Elsevier B.V. All rights reserved.)

Polychlorinated biphenyls (PCBs), brominated flame retardants (BFRs) like polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCDD), and novel flame retardants (NFRs) like decabromodiphenyl ethane (DBDPE) are ubiquitous environmental pollutants. Despite this, little is known about their concentrations in outdoor air in the African continent. To address this knowledge gap, concentrations of BFRs, NFRs, and PCBs were measured in outdoor air at 8 sites located within the metropolitan area of Lagos, Nigeria. Concentrations of ∑ 8 BDEs, ∑HBCDD, ∑ 7 NFRs and ∑ 8 PCBs were: 21-750 (median = 100) pg/m 3 , <12-180 (median = < 12) pg/m 3 , 34-900 (median = 300) pg/m 3 and 85-460 (median = 300) pg/m 3 , respectively. Decabromodiphenyl ether (BDE-209, range: <16-620 pg/m 3 , median = 71 pg/m 3 ) and DBDPE (range: <37-890 pg/m 3 , median = 280 pg/m 3 ) were the dominant BFRs detected, while the non-Arochlor PCB 11 (range: 49-220 pg/m 3 , median = 100 pg/m 3 ) was the dominant PCB. To the authors' knowledge, these are the first data on the non-Arochlor PCB 11 in outdoor air in Africa. In general, concentrations of all target contaminants in this study were within the range reported elsewhere in Africa and worldwide. Likely due to the tropical climate of Lagos, no seasonal variation in concentrations was discernible for any of the target contaminants. While concentrations of PBDEs and some NFRs were correlated with population density, concentrations of PCBs appear more impacted by leaks from electrical transformers and for PCB 11 to proximity to activities like textile factories that produce and use dyes., (Copyright © 2021 Elsevier Inc. All rights reserved.)

Extensive use of halogenated flame retardants (HFRs) and organophosphate esters (OPEs) has generated great concern about their adverse effects on environmental and ecological safety and human health. As well as emissions during use of products containing such chemicals, there are mounting concerns over emissions when such products reach the waste stream. Here, we review the available data on contamination with HFRs and OPEs arising from formal waste treatment facilities (including but not limited to e-waste recycling, landfill, and incinerators). Evidence of the transfer of HFRs and OPEs from products to the environment shows that it occurs via mechanisms such as: volatilisation, abrasion, and leaching. Higher contaminant vapour pressure, increased temperature, and elevated concentrations of HFRs and OPEs in products contribute greatly to their emissions to air, with highest emission rates usually observed in the early stages of test chamber experiments. Abrasion of particles and fibres from products is ubiquitous and likely to contribute to elevated FR concentrations in soil. Leaching to aqueous media of brominated FRs (BFRs) is likely to be a second-order process, with elevated dissolved humic matter and temperature of leaching fluids likely to facilitate such emissions. However, leaching characteristics of OPEs are less well-understood and require further investigation. Data on the occurrence of HFRs and OPEs in outdoor air and soil in the vicinity of formal e-waste treatment facilities suggests such facilities exert a considerable impact. Waste dumpsites and landfills constitute a potential source of HFRs and OPEs to soil, and improper management of waste disposal might also contribute to HFR contamination in ambient air. Current evidence suggests minimal impact of waste incineration plants on BFR contamination in outdoor air and soil, but further investigation is required to confirm this., 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 © 2021 Elsevier B.V. All rights reserved.)

Identifying the presence of brominated flame retardants (BFRs) within individual polymer types prior to extrusion has given us a unique perspective on which polymers may be problematic in meeting European Union (EU) low persistent organic pollutant (POP) content limits (LPCLs) and the potential for mixed engineering plastics (MEP) to be used as a viable recycled product. Our findings suggest that careful management of the polymer types within the feed chips prior to extrusion could deliver extruded polymer pellets that meet the EU LPCL values for POP-BFRs (i.e. <1000 mg/kg). Within this study, three fractions of extruded polymer pellets ("light", "medium", and "heavy" MEP) were created using density separation. Each fraction was characterised for 28 legacy and novel BFRs with brominated diphenyl ether-209 (BDE-209) (68-37,000 mg/kg) and tetrabromobisphenol-A (TBBP-A) (17-120,000 mg/kg) both predominant and ubiquitous. Portable X-ray fluorescence (XRF) was utilised to measure Br in 120 individual MEP chips of various polymer types. Those chips that XRF flagged as having high Br concentrations (>2500 mg/kg) were subjected to further evaluation for BFR content via mass spectrometry analysis and the results compared with the XRF Br data. This revealed that in 22% of the 120 chips studied, XRF incorrectly identified the LPCL to be exceeded. Our data also identifies the presence of the novel BFRs decabromodiphenyl ethane (DBDPE) and 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE) in plastics derived from waste electronic and electrical equipment (WEEE). While the "light-MEP" samples contained POP-BFR concentrations below LPCLs, the "medium-MEP" and "heavy-MEP" fractions exceeded such limits. Management of the polymer chips by colour sorting resulted in significant reductions in concentrations of all BFRs in the clear polymers such that LPCL limits were not exceeded; however, concentration reductions in white polymers were insufficient to meet LPCLs., 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 © 2021 Elsevier B.V. All rights reserved.)

Here we report on the concentrations of 79 flame retardants (FRs) and plasticizers, including 34 polybrominated diphenyl ethers or PBDE congeners, 17 "novel" brominated FRs (NBFRs), 15 dechloranes, and 13 organophosphate esters (OPEs) in air (n = 9) and dust (n = 24) samples from an active waste electrical and electronic equipment (WEEE) dismantling facility in Ontario, Canada, collected in February-March 2017. This is the first study of its kind in North America. The facility processes a range of WEEE including monitors, computers, printers, phones, and toys. Of the 79 target compounds, at least 60 were detected at a frequency of at least 50% in both air and dust. Dust and air concentrations were dominated by three compounds: BDE-209 (median 110,000 ng/g and 100 ng/m 3 , respectively), DBDPE (median 41,000 ng/g and 41 ng/m 3 ), and TPhP (median 42,000 ng/g and 27 ng/m 3 ). Levels of PBDEs, NBFRs, and dechloranes were close to two orders-of-magnitude higher in dust from the dismantling facility than in residential homes, while OPEs were one order-of-magnitude higher. Congener profiles of PBDEs indicated debromination of BDE-209. We calculated that a total mass of 44 ± 1 mg day -1 of 79 target analytes were released to air from WEEE processed in the dismantling hall and a further 270 ± 91 mg day -1 were released to dust. It is clear that WEEE dismantling facilities are a serious concern as a source of emissions for a wide range of FRs at relatively high concentrations to both workers and the immediate environment., (Copyright © 2019 Elsevier B.V. All rights reserved.)

For the first time, we present an analytical method to simultaneously extract, fractionate, and quantify four groups of semi-volatile organic compounds (SVOCs) in silicone wristbands, including 35 polybrominated diphenyl ethers (PBDEs), 10 novel flame retardants (NFRs), 19 organophosphate esters (OPEs), and 13 polycyclic aromatic hydrocarbons (PAHs). Wristbands were extracted using ultrasonication, and cleaned and fractionated on two multi-layer columns: one consisting of neutral alumina, neutral silica and Florisil, and the other consisting of neutral alumina, neutral silica, and acidic silica. Method accuracy and precision were validated using spiked wristband samples (n = 8) and procedural blanks (n = 7). Average matrix spike percent recoveries for all target analytes were within 57-107% with relative standard errors < 20%, with a few exceptions. This method was applied to analyze thirteen wristbands worn by ten participants for seven days; three participants wore two wristbands to evaluate duplicate samples. Percent recoveries of surrogate standards for all four groups of analytes in these wristbands were all within the 80-120% range with a few exceptions: recoveries for 13 C 12 BDE-209 and for 13 C 12 -triphenyl phosphate ranged from 35 to 62% and 69-176%, respectively. The majority of target analytes were detected in at least half of worn wristbands. The levels of total PBDEs, NFRs, OPEs and PAHs in deployed wristbands ranged from 28.4 to 412 ng, 40.7 to 625 ng, 2440 to 9580 ng, and 76.2 to 1240 ng, respectively., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Samples of waste cathode ray tube (CRT) plastic housings were exposed to Milli-Q® water containing dissolved humic matter at concentrations of 0, 100 and 1000mgL(-1) as leaching fluid under laboratory conditions, and polybrominated diphenyl ethers (PBDEs) determined in the resulting leachate. Despite the relatively hydrophobic physicochemical properties of PBDEs, concentrations of ƩPBDEs in the leachate from the leaching experiments in this study ranged from 14,000 to 200,000ngL(-1). PBDE leaching appears to be a second order process, whereby a period of initially intense dissolution of more labile PBDEs is followed by a slower stage corresponding to external diffusion of the soluble residue in the material. The bulk of transfer of PBDEs to the leaching fluid occurs within the first 6h of contact, during which time we suggest that the most labile PBDEs are "washed" off the surface of the CRT plastics. The predominant congeners in the chips were BDE-209 (2600mgkg(-1)) and BDE 183 (220mgkg(-1)). The impacts on PBDE leaching of leachate pH and temperature were also examined. Increasing the temperature of leaching fluids from 20 to 80°C, enhances the leachability of BDE-209 and BDE-99 from plastics. In all cases, the alkaline pH8.5 examined, resulted in the greatest PBDE concentrations in leachate. Agitation of the waste/leachate mixture enhances PBDE leaching from CRT plastics. Potential evidence for debromination of heavy congeners to the lower brominated and more bioavailable BDEs was observed. Specifically, BDEs-47, -85 and -100 were detected in the leachates, but were absent from the CRT plastics themselves., (Copyright © 2016. Published by Elsevier B.V.)