Serum polychlorinated biphenyl levels and circulating miRNAs in non-obese women with and without polycystic ovary syndrome.

Introduction: Polychlorinated biphenyls (PCBs), organic lipophilic pollutants that accumulate through diet and increase with age, have been associated with polycystic ovary syndrome (PCOS) and shown to affect microRNA (miRNA) expression. This work aimed to determine if PCBs were associated with circulating miRNAs and whether there were any correlations with serum PCB/miRNA levels and hormonal changes. Methods: 29 non-obese PCOS and 29 healthy control women, with similar age and body mass index (BMI), had their serum miRNAs measured together with 7 indicator PCBs (PCB28, PCB52, PCB101, PCB118, PCB138, PCB153, PCB180) using high resolution gas chromatography coupled with high resolution mass spectrometry. Results: In the combined study cohort, four miRNAs (hsa-miR-139-5p, hsa-miR-424-5p, hsa-miR-195-5p, hsa-miR-335-5p) correlated with PCBs, but none correlated with metabolic parameters. hsa-miR-335-5p correlated with FSH. When stratified, 25 miRNAs correlated with PCBs in controls compared to only one (hsa-miR-193a-5p) in PCOS; none of these miRNAs correlated with the metabolic parameters of BMI, insulin resistance, or inflammation (C-reactive protein, CRP). However, of these 25 miRNAs in controls, hsa-miR-26a-5p, hsa-miR-193a-5p, hsa-miR-2110 and hsa-miR-195-5p positively correlated with luteinizing hormone (LH), hsa-miR-99b-5p and hsa-miR-146b-5p correlated with estradiol, hsa-miR-193a-5p correlated with progesterone, hsa-miR-195-5p correlated with follicle stimulating hormone (FSH), and hsa-miR-139-5p and hsa-miR-146b-5p negatively correlated with anti-müllerian hormone (AMH) (all p<0.05). hsa-miR-193a-5p in PCOS cases correlated with estradiol. Conclusion: In this cohort of women, with no difference in age and BMI, and with similar PCB levels, the miRNAs correlating to PCBs associated with menstrual cycle factors in healthy menstruating controls versus the anovulatory PCOS subjects. The PCB-associated miRNAs did not correlate with non-reproductive hormonal and metabolic parameters. This suggests that PCB effects on miRNAs may result in changes to the hypothalamo-ovarian axis that may thus affect fertility.

Exploration of the correlation of serum polychlorinated biphenyl levels with luteal phase hormonal parameters and infertility in women with or without polycystic ovary syndrome.

Introduction: Polychlorinated biphenyls (PCBs) are organic lipophilic pollutants that accumulate in the body. Previous research has linked PCBs with menstrual function; therefore, this study was undertaken to investigate the correlation of PCBs with luteal phase hormonal parameters of menstrual function at day 21 in a group of non-obese women prior to in vitro fertilization (IVF). Methods: Fifty-eight non-obese Caucasian women from a UK academic center, 29 with polycystic ovary syndrome (PCOS) and 29 without, were recruited. PCOS women all had anovulatory infertility. Non-PCOS women: five with unexplained infertility, the remainder with male factor infertility (n=14) or tubal problems (n=10). Blood was withdrawn at day 21 of the menstrual cycle for non-PCOS women, at the time of mock embryo transfer. PCBs were measured using high resolution gas chromatography. Results: Only PCB118, PCB153, PCB138 and PCB180 were detected in all samples, and levels did not differ between PCOS and non-PCOS subjects. In non-PCOS subjects, PCB153, PCB138 and PCB180 inversely correlated with estradiol (p<0.05); PCB118 and PCB138 inversely correlated with follicle stimulating hormone (FSH) (p<0.05); PCB118 (p<0.05), PCB153, PCB138 and PCB180 (all p<0.01) inversely correlated with luteinizing hormone (LH). Control women without PCOS with unexplained infertility showed higher levels of PCB118, PCB153, PCB138 and PCB180 (p<0.05) compared to those control women without PCOS with tubal or male factor infertility, though other hormonal parameters did not differ other than that FSH that was lower in the unexplained group (p=0.01). The only correlation observed in PCOS women with anovulatory infertility was that between PCB180 and progesterone (p<0.05). Conclusion: PCBs correlated with luteal phase menstrual cycle hormones in control women without PCOS and may contribute to the mechanism of unexplained infertility; in PCOS women, no correlations of the PCBs were seen for estradiol, LH or FSH.

Persistent Organic Contaminants in Dust from the International Space Station.

Polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCDD), "novel" brominated flame retardants (NBFRs), organophosphate esters (OPEs), polycyclic aromatic hydrocarbons (PAH), perfluoroalkyl substances (PFAS), and polychlorinated biphenyls (PCBs) were measured in a composite sample of dust from the International Space Station (ISS). Notwithstanding the unique environment from which the dust originated, while concentrations of all target compound classes frequently exceeded the median values in terrestrial indoor microenvironments in the US and western Europe, ISS dust concentrations were generally within the terrestrial range. The relative abundance of the three HBCDD diastereomers is dominated by γ-HBCDD (96.6% ΣHBCDD). This matches very closely with the commercial mixture added to materials and contrasts with the diastereomer distribution observed in most terrestrial indoor dust samples (in which γ-HBCDD is typically ∼60-70% ΣHBCDD). This suggests conditions inside the ISS do not favor the previously reported photolytically mediated formation in dust of α-HBCDD. Also of note, the concentration of perfluorooctanoic acid (PFOA) in ISS dust (3300 ng/g) exceeds the maximum reported (1960 ng/g) in a 2008 survey of dust from US child daycare centers and homes. This may reflect the widespread use of waterproofing treatments in the ISS to prevent microbial growth. Our findings can inform future material choices for manned spacecraft such as the ISS.

Association of flame retardants, polybrominated diethyl ethers (PBDEs), with vitamin D in female subjects.

INTRODUCTION: A class of flame retardants, polybrominated diethyl ethers (PBDEs), are known endocrine disrupters and may induce the hepatic enzymes CYP24 and CYP3A that promote 25-hydroxylation of vitamin D3. Therefore, this study examined the association of PBDEs with vitamin D3 (25(OH)D3) and the active 1,25-dihydrovitamin D3 (1,25(OH)2D3) in a cohort of non-obese women. METHODS: 58 female participants (age:31.9 ± 4.6 years; body mass index (BMI):25.7 ± 3.7 kg/m2) had seven indicator PBDEs [PBDE28; PBDE47; PBDE99; PBDE100; PBDE153; PBDE154; PBDE183] measured using high resolution gas chromatography, with Æ©PBDE level calculated. 25(OH)D3 and 1,25(OH)2D3 levels were determined by isotope-dilution liquid chromatography tandem mass spectrometry. Plasma level of calcium/calmodulin-dependent protein kinase type 1 (CaMK1) was measured by Somascan proteomics. RESULTS: In this cohort, vitamin D3 (25(OH)D3) and 1,25(OH)2D3 levels were 22.9 ± 11.2 ng/mL and 0.05 ± 0.02 ng/mL, respectively. Of those, 28 had vitamin D deficiency [25(OH)D3 level <20 ng/mL (<50 nmol/L)]. For the whole group, individual PBDEs (PBDE28; PBDE47; PBDE99; PBDE100; PBDE153; PBDE154; PBDE183) and Æ©PBDEs did not correlate with 25(OH)D3 or its active metabolite 1,25(OH)2D3 nor with BMI. For the subset who were 25(OH)D3 sufficient, negative correlations were found for 1,25(OH)2D3 with PBDE153 (ρ = -0.77; p = 0.02) and PBDE100 (ρ = -0.72; p = 0.005). In the subset of women who were 25(OH)D3 deficient, positive correlations were found for 1,25(OH)2D3 with PBDE153 (ρ = 0.68; p = 0.02) and Æ©PBDEs (ρ = 0.57; p = 0.03). Using sufficient and deficient subset categories, no correlations were seen with 25(OH)D3 nor any of the PBDEs, and PBDEs did not correlate to renal function (estimated glomerular filtration rate, eGFR). 1,25(OH)2D3 was negatively associated with CaMK1 (r = -0.36; p = 0.03) as was PBDE153 (r = -0.31; p = 0.02). CONCLUSION: PBDEs were not associated with 25(OH)D3, but PBDE100 and 153 correlated with its active 1,25(OH)2D3 metabolite and PBDE153 correlated to the calcium modulator CaMKI, suggesting that PBDE effects could either be mediated through vitamin D status or that functional inactivation or inhibition of 1,25(OH)2D3 may contribute to the impact of vitamin D deficiency.

Association of polychlorinated biphenyls with vitamin D in female subjects.

INTRODUCTION: Polychlorinated biphenyls (PCBs) are known endocrine disrupters. A potentially causal association of PCBs with vitamin D has been reported. Higher body mass index (BMI) is associated with lower PCB levels whilst the strongest association of PCBs with BMI is in non-obese individuals. Therefore, this study examined the association of PCBs with vitamin D3 (25(OH)D3) and the active 1,25-dihydrovitamin D3 (1,25(OH)2D3) in a cohort of non-obese women. METHODS: 58 female participants (age 31.9 ± 4.6 years; BMI 25.7 ± 3.7 kg/m2) had seven indicator PCBs [PCB28, PCB52, PCB101, PCB118, PCB138, PCB153 and PCB180] measured using high resolution gas chromatography, with total PCB level calculated. 25(OH)D3 and 1,25(OH)2D3 levels were determined by isotope-dilution liquid chromatography tandem mass spectrometry. RESULTS: In this cohort, vitamin D3 (25(OH)D3) and 1,25(OH)2D3 levels were 50.7 ± 25.3 nmol/L and 0.05 ± 0.02 ng/ml, respectively. Of those, 28 had vitamin D deficiency [25(OH)D3 level <20 ng/ml (<50nmol/)]. Total PCBs correlated positively with total group 25(OH)D3 (r = 0.22, p = 0.04) as did PCB118 (r = 0.25, p = 0.03). Total PCBs did not correlate with total group 1,25(OH)2D3; however, PCB180 did correlate positively with 1,25(OH)2D3 (r = 0.34, p = 0.03) as did PCB153 (r = 0.33, p < 0.03), with PCB 28 correlating negatively (r = -0.29, p < 0.04). In the vitamin D deficient subgroup, total PCBs, PCB153 and PCB180 positively correlated with 25(OH)D3 (p < 0.05). Multilinear regression analysis indicated all associations could be accounted for by BMI. CONCLUSION: Though certain PCBs associated with 25(OH)D3 and 1,25(OH)2D3, all associations could be accounted for by BMI. This study therefore indicates that the deleterious effects from PCB accumulation are not mediated by effects on 25(OH)D3 or 1,25(OH)2D3.

Association between Organochlorine Pesticides and Vitamin D in Female Subjects.

In human population studies, organochlorine pesticides (OCPs) have been linked to vitamin D deficiency. Therefore, this study examined the association between OCPs, vitamin D3 (cholecalciferol, 25(OH)D3), and the active metabolite 1,25-dihydrovitamin D3 (1,25(OH)2D3) in a cohort of non-obese women. The serum samples of 58 female participants (age-31.9 ± 4.6 years; body mass index (BMI)-25.7 ± 3.7 kg/m2) were screened for 10 indicator OCPs. 25(OH)D3 and 1,25(OH)2D3 levels were determined via isotope dilution liquid chromatography tandem mass spectrometry. In this cohort, the 25(OH)D3 and 1,25(OH)2D3 levels were 22.9 ± 11.2 ng/mL and 0.05 ± 0.02 ng/mL, respectively, with 28 participants classified as 25(OH)D3-deficient (<50 nmol/L). In the study cohort, no correlations were found between individual or total OCPs (Æ©OCPs) and 25(OH)D3. p,p'-dichlorodiphenyldichloroethylene (DDE) and Æ©OCPs correlated positively with 1,25(OH)2D3, with the latter being negatively correlated with estimated glomerular filtration rate (eGFR). In women with sufficient 25(OH)D3 levels, p,p'-dichlorodiphenyltrichloroethan (DDT) was positively correlated with 1,25(OH)2D3, whilst in the deficient group, hexachlorobenzene (HCB) and p,p'-(DDE) were positively correlated with 1,25(OH)2D3, ß-Hexachlorocyclohexane (HCH) was positively correlated with 25(OH)D3, and none of the OCPs were associated with measures of renal function. Overall, OCPs and Æ©OCPs were not associated with 25(OH)D3, suggesting that they are unrelated to vitamin D deficiency, but p,p'-DDE and Æ©OCPs correlated positively with active 1,25(OH)2D3, while Æ©OCPs correlated negatively with eGFR, suggesting a possible renal effect. Analysis of vitamin D deficiency revealed an association between ß-HCH and 25(OH)D3, and between HCB and p,p'-DDE and 1,25(OH)2D3, suggesting that OCP effects may be enhanced in cases of vitamin D deficiency.

Rapid Determination of Selected PFAS in Textiles Entering the Waste Stream.

Due to new European legislation, products entering the waste stream containing some perfluoro alkyl substances (PFAS) are subject to "low persistent organic pollutant concentration limits". Concentrations of restricted PFAS must be below this limit for them to be legally recycled or disposed of. A rapid extraction and clean-up method was developed for the determination of 21 PFAS in various polymers used in soft furnishings and upholstery. The optimised method used vortexing and ultrasonication in methanol (0.1% NH4OH), followed by a dilution and syringe filter clean-up step. PFAS were subsequently determined via UPLC-TripleTOF/MS. Good recoveries (80-120%) of target analytes were obtained with tall and narrow chromatogram peaks. The method was validated using control matrix samples spiked with target analytes. Repeated measurements of concentrations of target compounds showed good agreement with the spiked concentrations demonstrating good accuracy and precision. The resultant extracts provided low noise levels resulting in low limits of quantification ranging from 0.1 to 0.4 mg/kg. The developed method was applied successfully to real consumer products and it provided various advantages over traditional methods, including a substantially reduced analysis time, consumables and solvent consumption, and a high sample throughput which is critical to comply with implemented and proposed legislation.

Elevated concentrations of halogenated flame retardants in waste childcare articles from Ireland.

Concentrations of legacy and alternative halogenated flame retardants (HFRs) including chlorinated organophosphate esters (Cl-OPEs), were measured in waste childcare articles (n = 275 for Cl-OPEs, n = 187 for other HFRs) from the Republic of Ireland between 2019 and 2020. Articles studied comprised foams and fabrics from: child car seats, cot mattresses, changing mats, pushchairs, prams, and related items. Fifteen articles (7.7%) exceeded the European Union limit value of 1000 mg/kg for polybrominated diphenyl ethers (PBDEs) (all due to BDE-209), an additional 15 exceeded the limit for hexabromocyclododecane (HBCDD), with 7 articles exceeding the limit for both PBDEs and HBCDD. An even greater proportion of articles contained concentrations exceeding 1000 mg/kg for: tris(1-chloro-2-propyl) phosphate (TCIPP) (n = 73, 27%) and tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) (n = 58, 21%), with concentrations greater than 1000 mg/kg also observed for: tris(2-chloroethyl) phosphate (TCEP) (n = 14, 5.1% articles), 2-ethylhexyl tetrabromobenzoate (EH-TBB) (n = 7, 3.7%), decabromodiphenyl ethane (DBDPE), and bis(2-ethylhexyl)tetrabromophthalate (BEH-TEBP) (both n = 5, 2.7%). Overall, 120 samples contained at least one HFR at a concentration exceeding 1000 mg/kg. In addition to the waste management implications of our findings, our data raise concerns about child exposure to HFRs during the use phase of these everyday items.

Chlorinated organophosphate esters in Irish waste foams and fabrics: Concentrations, preliminary assessment of temporal trends and evaluation of the impact of a concentration limit value.

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.

POP-BFRs in consumer products: Evolution of the efficacy of XRF screening for legislative compliance over a 5-year interval and future trends.

In 2015-16, a study of approximately 500 waste plastic articles showed that portable X-ray fluorescence (XRF) was up to 95 % effective in screening for compliance with low persistent organic pollutant (POP) concentration limits (LPCLs) on brominated flame retardants (BFRs) in waste. The present study conducted in 2019-20 mirrors that conducted five years prior on a similar number and range of articles, testing the hypothesis that increased use of alternative BFRs as replacements for POP-BFRs will reduce the effectiveness of XRF as a tool for monitoring compliance with LPCLs. In comparing the results, the overall screening efficacy for LPCL compliance reduced from ~95 % to ~88 %, due in part to decreased prevalence of POP-BFRs and potentially increased presence of alternative flame retardants, particularly in goods with shorter lifecycles such as electronics. We additionally examined the impacts of a number of modifications to the XRF measurement protocol on its efficacy, including: using elemental Sb as a qualifier in detecting POP-BFRs in hard plastics; reduced XRF analysis time; and the elimination of background interference using a test stand. The rate at which hard plastics from electronic waste may be analysed by XRF can be substantially improved by reducing analysis time to 5 s, with minimal increase in false exceedances of the LPCL. Monitoring Sb does not appear an effective qualifier for the presence of POP-BFRs, as Sb seems to be used with a range of BFRs. Use of the test stand, while reducing interference, appeared to reduce accuracy when screening low density and thin samples. Despite a seeming increased use of alternative BFRs, screening of waste for compliance with LPCLs using rapid and low-cost screening methods such as portable XRF is still necessary as methods such as GC-MS cannot be scaled up to match the quantities of waste requiring screening.

A case-control study of polychlorinated biphenyl association with metabolic and hormonal outcomes in polycystic ovary syndrome.

Polychlorinated biphenyls (PCBs) are a class of environmental pollutants with a long half-life that sequester in fat. Women with polycystic ovarian syndrome (PCOS) may represent a sensitive subgroup to endogenous exposure to PCBs because of associated weight gain. Seven PCB congeners were compared in age, ethnicity, and BMI matched women with (n = 29) and without (n = 30) PCOS and related to metabolic outcomes, and steroid and thyroid hormone levels. PCB118, PCB138, PCB153, and PCB180 were detected in all serum samples but geometric mean did not differ between cases and controls. PCBs correlated with increasing concentrations of each other (p < .01), increasing age (p < .01) and decreasing lneGFR (p < .05). lnPCB118 correlated with increasing Free-T4 (p = .028). lnPCB158, lnPCB180, and ln∑PCB correlated with increasing lnSHBG (p = .044). In regression modeling, although not significant, PCB118 positively associated with lnSHBG in controls (p = .0504) but not in cases; estradiol inversely associated with PCB138 in controls (p = .055) and ∑PCB in cases (p = .051). No significant associations were observed between metabolic endpoints, and steroid and thyroid hormone levels. The results presented do not suggest the PCOS cases in this cohort are at adverse risk compared to age, ethnicity, and BMI matched controls.

Halogenated flame retardants in Irish waste polymers: Concentrations, legislative compliance, and preliminary assessment of temporal trends.

Halogenated flame retardants (HFRs) were measured in 470 waste plastic articles from Ireland between 2019 and 2020. We identified articles containing concentrations of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCDD), and tetrabromobisphenol-A (TBBP-A) exceeding European Union limits. Enforcement of existing limits of 1000 mg/kg will render an estimated 3.1% (2800 t) of articles in the waste categories studied unrecyclable, increasing to: 4.0, 4.9, and 5.6% if limits were reduced to 500, 200, and 100 mg/kg respectively. Meanwhile, enforcing limits of 1,000, 500, 200, and 100 mg/kg will respectively remove 78, 82, 84, and 85% of PBDEs, HBCDD, and TBBP-A present in such waste. Other FRs targeted were detected infrequently and predominantly at very low concentrations. However, 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine (TTBP-TAZ) was detected in 3 display/IT product samples at 14,000 to 32,000 mg/kg, indicating elevated concentrations of FRs used as alternatives to PBDEs and HBCDD, will likely increase in future. Comparison with data for Ireland in 2015-16, revealed concentrations and exceedances of limits for PBDEs, HBCDD, and TBBP-A were similar or have declined. For end-of-life vehicle fabrics and foams, HBCDD and ΣPBDE concentrations declined significantly (p < 0.05) since 2015-16. Moreover, ΣPBDE concentrations in waste small domestic appliances are significantly lower in 2019-20, with a similarly significant decline for TBBP-A in waste IT and telecommunications articles. In contrast, HBCDD concentrations in waste extruded polystyrene increased significantly between 2015-16 and 2019-20. For other waste categories studied, no statistically significant temporal trends are evident (p > 0.05). Fewer samples exceeded PBDE and HBCDD limits in 2019-20 (7.8%) than 2015-16 (8.7%), while exceedances for TBBP-A fell from 2.4% in 2015-16 to 0.57% in 2019-20. While comparison between the 2015-16 and 2019-20 datasets provide a preliminary indication of changes, further monitoring is required if the impact of legislation designed to eliminate HFRs from the waste stream is to be fully evaluated.

Exposure, risk and predictors of hexabromocyclododecane and Tetrabromobisphenol-A in house dust from urban, rural and E-waste dismantling sites in Thailand.

In this study, for the first time, we determined concentrations of hexabromocyclododecane (HBCDD) and tetrabromobisphenol-A (TBBPA) in house dust and estimated human exposure to these substances in houses located in an e-waste dismantling site and in urban and rural residential areas of Thailand. The median HBCDD concentration in urban residential houses (2.10 ng g-1) was similar to that in houses in an e-waste dismantling site (2.05 ng g-1, p > 0.05) and slightly higher than that in rural residential houses (1.11 ng g-1, p > 0.05). In contrast, significantly higher TBBPA concentrations were present in house dust from an e-waste dismantling site (median = 720 ng g-1; range = 44-2300 ng g-1) compared to those in urban (68.6 ng g-1; 3.5-300 ng g-1, p < 0.001) and rural residential areas (17 ng g-1; 2.0-201 ng g-1, p < 0.001). TBBPA concentrations increased with the increasing presence of electronic devices and a decreasing distance to the e-waste dismantling site. These results suggest that e-waste dismantling activities may contribute to TBBPA contamination of house dust. The median estimated daily intake (EDI) of HBCDD and TBBPA through dust ingestion for toddlers exceeded that for children and adults. However, EDI values for HBCDD and TBBPA from all age groups were below the oral reference dose guideline value suggested by the US National Research Council and National Toxicology Program (NTP).

Comparison of lipid-normalised concentrations of persistent organic pollutants (POPs) between serum and adipose tissue.

Human biomonitoring of persistent organic pollutants (POPs) is typically based on serum analysis and for comparison and modelling purposes, data are often normalised to the lipid content of the serum. Such approach assumes a steady state of the compound between the serum lipids and for example lipid-rich adipose tissue. Few published data are available to assess the validity of this assumption. The aim of this study was to measure concentrations of POPs in both serum and adipose tissue samples from 32 volunteers and compare the lipid-normalised concentrations between serum and adipose tissue. For p,p'-DDE, PCB-138, PCB-153 and PCB-180, lipid-normalised adipose tissue concentrations were positively correlated to the respective serum concentrations but generally were more highly concentrated in adipose tissue. These results suggest that the investigated legacy POPs that were consistently found in paired samples may often not be in a steady state between the lipid compartments of the human body. Consequently, the analysis of serum lipids as a surrogate for adipose tissue exposure may more often than not underestimate total body burden of POPs. Further research is warranted to confirm the findings of this study.

Interspecies comparisons of brominated flame retardants in relation to foraging ecology and behaviour of gulls frequenting a UK landfill.

This study quantifies and compares concentrations and profiles of legacy and alternative (alt-) brominated flame retardants (BFRs) in the eggs of three gull (Laridae) species of international/UK conservation concern - great black-backed gulls (Larus marinus; n = 7), European herring gulls (L. argentatus; n = 16) and lesser black-backed gulls (L. fuscus; n = 11) in relation to their foraging ecology and behaviour in order to investigate potential exposure pathways at a remote landfill in western Scotland, UK. Egg concentrations of sum (∑) polybrominated diphenyl ethers (∑8PBDEs) in all three species exceeded those for most reported avian species using landfill, except for those in North America. Despite relatively high detection frequencies of ∑hexabromocyclododecanes (∑3HBCDDs) (94-100%), concentrations of ∑8PBDEs exceeded ∑3HBCDDs and ∑5alt-BFRs, with ∑8PBDE levels similar in all three species. Egg carbon isotopic (δ13C) values highlighted a greater marine dietary input in great black-backed gulls that was consistent with their higher BDE-47 levels; otherwise, dietary tracers were minimally correlated with measured BFRs. ∑3HBCDD egg concentrations of herring gulls markedly exceeded those reported elsewhere in Europe. Decabromodiphenylethane (DBDPE) was the only alt-BFR detected (6-14% detection rate), in a single egg of each species. The great black-backed gull egg contained the highest concentration of DBDPE measured in biota to date globally and provides strong evidence for its emerging environmental presence as a BDE-209 replacement in UK wildlife. Correlations between δ13C (dietary source) and some measured BFRs in eggs suggest multiple routes of BFR exposure for gulls frequenting landfill through their diet, behaviour, preening, dermal exposure and likely inhalation. The frequent use of landfill by herring gulls and their increased egg BFR burdens suggest that this species may be an important bioindicator of BFR emissions from such sites.

Phasing-out of legacy brominated flame retardants: The UNEP Stockholm Convention and other legislative action worldwide.

Due to their toxicity and persistence, several families of brominated flame retardants (BFRs) have been listed as persistent organic pollutants (POPs) in the Stockholm Convention, a multilateral treaty overseen by the United Nations Environment Programme. This treaty mandates that parties who have signed must take administrative and legislative actions to prevent the environmental impacts that POPs pose, both within their jurisdictions and in the global environment. The specific BFRs listed in the Stockholm Convention are Polybrominated Diphenyl Ethers (PBDEs), Hexabromocyclododecane (HBCDD), and Hexabromobiphenyl (HBB), chemicals which must therefore be heavily restricted within the jurisdictions of the signatories. As an example, within the EU, hexabromobiphenyl (HBB), the PBDE commercial mixtures, and HBCDD are almost entirely prohibited in terms of both production and use in commercial goods. Waste articles containing excess concentrations of these BFRs are similarly restricted and must be disposed of in a manner that destroys or irreversible transforms the BFR in question. In some cases, specific exemptions for these limits are defined by the Convention for certain parties: for example, Penta- and Octa-BDE can be present in waste materials for recycling until 2030, while Deca-BDE can be applied to some aviation and automotive applications until 2036. However, in such cases, very specific criteria and guidelines apply for their use and/or production. Worldwide, China, Japan, India, and the United States of America have made significant advances in the regulation of POPs, in line with the provisions of the Stockholm Convention. China has established concentration limits for Penta- and Octa-BDEs in electronic goods. It is also currently availing of an exemption to allow for the use of HBCDD and has not yet ratified the Convention with regards to Deca-BDE. Japan meanwhile has classified HBB and Penta-/Octa-BDE compounds as Class I Specified Chemical Substances which virtually prohibits the manufacture, import, and use of these chemicals in all applications. India has banned the manufacture, trade, import, and use of HBB, HBCDD and some PBDEs, and has established concentration limits for all PBDEs in certain electrical goods. Finally, the United States has no federal mandate for the restriction of POPs and has not ratified the annexes to the Convention requiring them to do so. However, thirteen states have implemented their own state-wide concentration limits on a variety of flame retarding chemicals in various commercial applications. Though these limits worldwide are a very positive step for the removal of POP-BFRs from the environment, the increased use of replacement flame retardants renders such legislation only partially effective. The lack of effective screening mechanisms in waste management facilities means that BFR-treated plastics can be inadvertently recycled and remain in circulation. The rise in the use of novel BFRs (NBFRs) can furthermore hinder screening methods currently being developed and the additives themselves may pose similar issues to their predecessors owing to their similar chemical properties. Thus, restrictions on current BFRs will result in the use of new flame retardants, which may in turn be banned and replaced once again. Further research into and development of methods to screen for hazardous chemicals in end of life materials is therefore of the utmost importance. This must be coupled with pro-active legislation that eliminates the need for using such persistent and potentially harmful chemicals in the future.

Children's exposure to hazardous brominated flame retardants in plastic toys.

We report concentrations of brominated flame retardants (BFRs) in 23 plastic samples from 20 new and second-hand children's toys sourced from the UK that had been previously shown to be Br-positive by XRF. The results reinforce existing evidence that the recycling of BFR-treated electronic plastics has led to the unintentional BFR contamination of articles not required to be flame-retarded. The principal BFRs detected were PBDEs (and in particular BDE-209), HBCDD and TBBP-A. PBDEs were detected in all samples with a maximum concentration of BDE-209 of 2500 mg/kg, and while TBBP-A was detected in 11 samples with a maximum concentration of 3100 mg/kg. HBCDD was detected in 14 cases and was present in four toys at concentrations (139-840 mg/kg) that would currently prevent their sale on the EU market. While estimated exposures to PBDEs via accidental ingestion of toy plastic fell well below USEPA reference doses, a child weighing 8.67 kg and ingesting 8 mg/day of a toy (the default assumption of the European Commission's Toy Safety Directive for scraped-off toy material) contaminated at our arithmetic mean concentration would be exposed to 0.2 ng/kg bw/day BDE-99. This compares closely to a health-based limit value (HBLV) proposed in The Netherlands of 0.23-0.30 ng/kg bw/day BDE-99. Of greater concern, the same child playing with a toy contaminated at the maximum concentration in this study would be exposed to 1.4 ng/kg bw/day BDE-99, thereby exceeding the HBLV. This paper is the first to consider BFR exposure via incidental ingestion of plastic from both contemporary and historical toys, revealing it to be considerable and for some children their most significant pathway of exposure.

Perfluoroalkyl substances and brominated flame retardants in landfill-related air, soil, and groundwater from Ireland.

Between November 2018 and January 2019, samples of air and soil were collected from locations downwind and upwind of 10 landfills across the Republic of Ireland. Samples of groundwater (n = 10) were also collected from locations with links traceable to the studied landfills. Concentrations of perfluoroalkyl substances (PFASs), polybrominated diphenyl ethers (PBDEs), hexabromocyclodecane (HBCDD), and decabromodiphenyl ethane (DBDPE) determined in air and soil samples were not significantly different (p > 0.05) between downwind and upwind locations. The arithmetic mean concentration of PFOA in groundwater sourced from landfills (n = 4) that were not fully lined (69 ng/L) exceeded that in groundwater samples sourced from lined landfills (n = 6; 4.1 ng/L), with the difference, however being not statistically significant (p > 0.1). A positive correlation (p = 0.014) was observed between concentrations of PFOA in groundwater in our study and those reported previously in leachate from the same landfills. However, this correlation was driven substantially by one landfill which displayed the highest concentrations in both groundwater and leachate and no significant correlation (p > 0.1) was observed between log-transformed concentrations of PFOA in groundwater and leachate. DBDPE was detected in groundwater for the first time anywhere, in all samples at concentrations (median = 9.4 ng/L; arithmetic mean = 78 ng/L) that exceeded those of any other BFRs or PFASs targeted in this study. This likely reflects its recent use as a "drop-in" replacement for the recently restricted Decabromodiphenyl ether product. Overall, our data suggest that the 10 landfills studied do not exert a discernible influence on local air and soil concentrations of BFRs and PFASs. In contrast, while not of immediate concern, our data suggest that further more detailed study of the impact of landfill emissions on concentrations of DBDPE and PFOA is advisable.

Concentrations of perfluoroalkyl substances in human milk from Ireland: Implications for adult and nursing infant exposure.

Concentrations of 10 perfluoroalkyl substances (PFASs) were measured in 16 pools of human milk from Ireland. Only four PFASs were detected (PFOA, PFNA, PFHxS and PFOS), with concentrations dominated by PFOA which was detected in all samples at a median of 0.10 ng/mL. Concentrations and the relative abundance of PFASs in human milk from Ireland are within the range reported for other countries. Estimated exposures for nursing infants to perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) do not suggest a health concern. A one compartment pharmacokinetic model was used to predict the intakes of PFOS and PFOA required to support the observed concentrations in human milk. This suggests current adult exposure in Ireland to PFOS is below the provisional tolerable weekly intake (TWI) proposed by EFSA. In contrast, the model predicts that the maximum concentration detected in human milk in this study, implies a level of adult exposure that would exceed EFSA's provisional TWI for PFOA. As exposure of the Irish population to PFASs via drinking water, indoor air and dust is well-characterised, current understanding suggests that the major contributor to overall exposure of the Irish population is via the diet and/or less well-studied pathways like dermal uptake from PFAS-containing fabrics and cosmetics.