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.

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.

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.

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.

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.

Polycyclic aromatic hydrocarbons, polychlorinated biphenyls and legacy and current pesticides in indoor environment in Australia - occurrence, sources and exposure risks.

Paired indoor air and floor dust samples were collected from residential houses and offices (n = 28) in two Australian cities in 2015. For the air samples, a modified passive air sampler (PAS) was used to collect semi-volatile organic compounds (SVOCs) in gaseous phase and airborne particles simultaneously. Sampling rates (R) of the PAS for gaseous SVOCs ranged from 0.69 to 3.4 m3 sampler-1 day-1. Out of the 33 analytes, 22, 14 and 17 compounds were detected (above the method detection limit) in over 50% of air, airborne particles and floor dust samples respectively. The highest median level in air, airborne particles and floor dust was observed for phenanthrene (2.0 ng m-3), permethrin (8800 ng g-1) and permethrin (5100 ng g-1) respectively. Among polychlorinated biphenyl (PCB) congeners, with few exceptions, the largest contribution was from 3,3'-dichlorobiphenyl (PCB11) for both indoor air and floor dust samples. In these houses and offices, the indoor level of polycyclic aromatic hydrocarbons (PAHs) was mainly influenced by ambient (outdoor) air. Primary sources of PCBs were from within indoor environments and generally older houses have higher concentrations in air. Among pesticides, hexachlorobenzene in indoor environments appeared to be due to transfer from outdoor sources whereas chlordanes and pyrethroids were associated with past and current household application respectively. Compared to data from other countries/regions, concentrations of chlordanes, chlorpyrifos and pyrethroids in indoor air and dust samples from Australia were among the highest whereas PCB and PAH levels were among the lowest. The sum of estimated daily intakes (EDIs) via inhalation and dust contact and ingestion were calculated. The highest median value of EDI was observed for permethrin at 2.8 (for adults) and 74 ng kg-1 day-1 (for toddlers), which are <0.15% of the U.S. EPA reference dose.

Brominated flame retardants and perfluoroalkyl substances in landfill leachate from Ireland.

Between June and November 2017, leachate samples were collected from 40 landfills across the Republic of Ireland. Concentrations of perfluoroalkyl substances (PFASs), polybrominated diphenyl ethers (PBDEs), and hexabromocyclododecane (HBCDD) determined in these samples were within the range previously reported in other countries. Average concentrations of PFASs exceeded those of PBDEs and HBCDD; likely due to the higher water solubility of PFASs. Log-transformed concentrations of BDEs-47, 100, 153, and 183, as well as perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA) and perfluorobutane sulfonate (PFBS) were significantly (p < 0.05) higher in leachate from newer, lined landfills than in samples from unlined landfills. These higher concentrations in lined landfills are likely related to the fact that lined landfills are found to retain organic matter leading to a higher organic content of leachate from such landfills. This is evidenced by the significant (p < 0.05) correlation between log-transformed concentrations in leachate of most of the same contaminants and those of chemical oxygen demand (COD). Concentrations of the less water-soluble, higher molecular weight BDE-209 were not correlated with leachate COD, nor landfill age or the presence of a landfill liner. This suggests that the presence of BDE-209 in landfill leachate is driven more by physical abrasion of particles and fibres from waste articles, than dissolution into the aqueous phase. The higher concentrations of some PFASs and PBDEs in leachate from lined landfills present a challenge with respect to leachate disposal, when leachate is sent to wastewater treatment plants that do not necessarily have mechanisms in place to remove or destroy these chemicals prior to discharge into the environment. Moreover, the presence of these persistent organic chemicals in leachate from unlined landfills raises concerns about releases to the environment including groundwater over the lifetime of such landfills and beyond.

Serum measures of hexabromocyclododecane (HBCDD) and polybrominated diphenyl ethers (PBDEs) in reproductive-aged women in the United Kingdom.

We investigated the serum concentrations of two brominated flame retardants (BFRs) - polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCDD) -in 59 women aged between 23 and 42 from the United Kingdom. We also collected demographic data, including age, bodyweight and height in order to test for associations with BFR levels. Temporal and global differences were also assessed using previously published data. HBCDD was detected in 68% of samples with a mean concentration of 2.2 ng/g lipid (range = <0.3-13 ng/g lipid). The dominant stereoisomer was α-HBCDD with an average contribution of 82% (0-100%) towards ΣHBCDD, was followed by γ-HBCDD (average contribution = 17%). PBDEs were detected in 95% of samples with a mean ∑PBDE (sum of BDEs -28, -47, -99, -100, -153, -154 and -183) concentration of 2.4 ng/g lipid (range = <0.4-15 ng/g lipid). BDEs -153 and -47 were the dominant congeners, contributing an average of 40% and 37% respectively, to the average ΣPBDE congener profile. Data from this study suggests that HBCDD levels decrease with age, it also suggests a positive association between bodyweight and HBCDD levels, which likewise requires a large-scale study to confirm this. The data also show that 10 years after their European ban, PBDE body burden has begun to decrease in the UK. Whilst it is too early to draw any firm conclusions for HBCDDs, they appear to be following a similar pattern to PBDEs, with levels decreasing by a factor of >2.5 since 2010. Whilst the human body burden appear to be decreasing, both PBDEs and HBCDD are still consistently detected in human serum, despite legislative action limiting their production and use. This highlights the need to continuously assess human exposure and the effectiveness of policy aimed at reducing exposure.

Human biomonitoring in Australian children: Brominated flame retardants decrease from 2006 to 2015.

Polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCDD) were used intensively as flame retardants, worldwide. They have been detected in human serum samples and PBDEs have been found to be elevated in young children. Commercial Penta- and Octa-PBDE mixtures were banned in Australia in 2005, while HBCDD was banned worldwide in 2013. We investigated PBDE and HBCDD concentrations in serum collected from young children. We also investigated temporal trends in PBDE concentration 10 years after their Australian ban. Surplus human blood serum samples were collected through a pathology clinic (n = 800), in 2014/15, stratified by age (0-6, 6-12, 12-18, 18-24, 24-30, 30-36, 36-42, 42-48, 48-54 and 54-60 months) and sex and pooled for analysis of PBDEs (BDEs -28, -47, -99, -100, -153, -154, -183) and HBCDD. In 2014/15, the geometric mean concentration of the sum of all PBDEs measured (ΣPBDEs) was 4.5 ng/g lipid (median: 4.6 ng/g lipid, range: 0.88-26 ng/g lipid). A positive association between BDE-47 concentration and age was observed (R = 0.41, p = 0.008), however there were no trends between other PBDE congeners or HBCDD and age. There were no significant differences between genders for PBDEs (t-test, p = 0.802) or HBCDD (t-test, p = 0.740).The highest concentrations observed were in pools from the females 30-36 month (26 ng/g lipid) and Males 6-12 month (21 ng/g lipid) categories. BDEs -47 and -99 were the predominant congeners with a combined average contribution of 75% of ΣPBDEs. PBDEs showed a significant reduction in children aged 0-4 years over an eight year period. In 2014/15, the mean (range) concentration of BDE-47 is 2.8 (0.23 to 11) ng/g lipid compared to pools in 2006/07 at 19 (3-55) ng/g lipid (p < 0.0001) and for BDE-153 is 0.73 (<0.1 = -2.9) ng/g lipid compared to pools in 2006/07 at 4.7 (2-10) ng/g lipid (p < 0.0001). HBCDD concentrations were lower than PBDEs with a mean concentration of 0.45 ng/g lipid. There were no temporal trends observed for HBCDD when compared to samples collected in 2012. The dominant stereoisomer was α-HBCDD (mean = 0.38 ng/g lipid) with an average contribution of 65% towards ΣHBCDD. Levels of PBDEs in young Australian children have significantly decreased since the bans of commercial Penta- and Octa-BDE in 2005. There has been no observed decrease in HBCDD levels in Australian children since its ban in 2012.

Brominated flame retardants in Irish waste polymers: Concentrations, legislative compliance, and treatment options.

A comprehensive survey was performed to construct an inventory of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCDD) associated with waste polymers in Ireland. Based on our data, ~2200 t/yr of waste generated in Ireland exceeds "Low POP Concentration Limits" (LPCLs) set by the European Commission, of 1000 mg/kg of PBDEs (BDE-209 excluded) and HBCDD - collectively referred to as POP-BFRs. Waste articles containing concentrations exceeding the LPCL values require special treatment to remove POP-BFRs before they can be recycled. Waste articles exceeding LPCLs in our study consist primarily of expanded polystyrene used as building insulation (44%), waste furniture foams and fabrics (41%), with waste electrical and electronic equipment (WEEE) accounting for 13% and end of life vehicle waste contributing 1.7%. The recent listing of Deca-BDE under the Stockholm Convention means that a similar LPCL for its principal congener (BDE-209) is likely. Our data show that enforcement of an LPCL of 1000 mg/kg for BDE-209 would result in a further 1650 t/year of waste articles requiring special treatment. Our data show there to be 17,125 kg of POP-BFRs associated with waste polymers generated annually in Ireland. Enforcement of current LPCL values would prevent approximately 98% of these POP-BFRs from entering recycled goods. Introduction and enforcement of a similar LPCL for BDE-209 would prevent 93% of the 15,518 kg/yr of BDE-209 associated with Irish waste polymers from entering the recycling stream.

Portable X-ray fluorescence for the detection of POP-BFRs in waste plastics.

The purpose of this study was to establish the efficacy of portable X-ray fluorescence (XRF) instrumentation as a screening tool for a variety of end of life plastics which may contain excess amounts of brominated flame retardants (BFRs), in compliance with European Union (EU) and United Nations Environment Programme (UNEP) legislative limits (low POP concentration limits - LPCLs). 555 samples of waste plastics were collected from eight waste and recycling sites in Ireland, including waste electrical and electronic equipment (WEEE), textiles, polyurethane foams (PUFs), and expanded polystyrene foams. Samples were screened for bromine content, in situ using a Niton™ XL3T GOLDD XRF analyser, the results of which were statistically compared to mass spectrometry (MS)-based measurements of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCDD) and tetrabromobisphenol-A (TBBP-A) concentrations in the same samples. Regression between XRF and MS for WEEE samples shows that, despite an overall favourable trend, large deviations occur for a cluster of samples indicative of other bromine-based compounds in some samples; even compensating for false-positives due to background interference from electronic components, XRF tends to over-estimate MS-determined BFR concentrations in the 100 to 10,000 mg kg-1 range. Substantial deviations were additionally found between results for PUFs, textiles and polystyrene samples, with the XRF over-estimating BFR concentrations by a factor of up to 1.9; this is likely due to matrix effects influencing XRF measurements. However, expanded (EPS) and extruded polystyrene (XPS) yielded much more reliable estimations of BFR-content due to a dominance of HBCDD in these materials. XRF proved much more reliable as a "pass/fail" screening tool for LPCL compliance (including a prospective LPCL on Deca-BDE based on REACH). Using a conservative threshold of BFR content exceeding legislative limits (710 mg kg-1 bromine attributed to Penta-BDE), XRF mistakenly identifies only 6 % of samples (34/555) as exceeding legislative limits.

A rapid method for the determination of brominated flame retardant concentrations in plastics and textiles entering the waste stream.

Due to new European legislation, products going to waste are subject to 'low persistent organic pollutant concentration limits'. Concentrations of restricted brominated flame retardants in waste products must be determined. A rapid extraction and clean-up method was developed for determination of brominated flame retardants in various plastics and textiles. The optimised method used vortexing and ultrasonication in dichloromethane followed by sulfuric acid clean-up to determine target compounds. Poly-brominated diphenyl ethers were determined by gas chromatography with mass spectrometry and hexabromocyclododecane by liquid chromatography with tandem mass spectrometry. Good recoveries of target analytes were obtained after three extraction cycles. The method was validated using poly-propylene and poly-ethylene certified reference materials as well as previously characterised textiles, expanded and extruded poly-styrene samples. Measured concentrations of target compounds showed good agreement with the certified values indicating good accuracy and precision. Clean extracts provided low noise levels resulting in low limits of quantification (0.8-1.5 ng/g for poly-brominated diphenyl ethers and 0.3 ng/g for α-, ß- and γ-hexabromocyclododecane). The developed method was applied successfully to real consumer products entering the waste stream and it provided various advantages over traditional methods, including reduced analysis time, solvent consumption, minimal sample contamination and high sample throughput, which is crucial to comply with the implemented legislation.

Distribution of PBDEs, HBCDs and PCBs in the Brisbane River estuary sediment.

To date, very little or no data exist in literature for some brominated flame retardants (BFRs) and polychlorinated biphenyls in Queensland sediments. These pollutants were measured in the sediments along the Brisbane River estuary. The target compounds were regularly detected in measurable concentrations: PBDEs=33.3-97.8% (n=45), PCBs=94.1-100% (n=51) and HBCDs=79-98% (n=48). Consistently, >90% of the observed ∑8PBDE concentration was attributed to BDE-209. Mean PBDE levels (ng/g dry wt.) were: 4.4±3.2 (∑8PBDE) and 4.4±3.0 (BDE-209) across 22 sampling sites. The mean ∑7PCB and ∑HBCD were 5.4±4.5 and 1.0±1.5ng/g dry wt. respectively. The 25% (α-HBCD), 8% (ß-HBCD) and 67% (γ-HBCD) diastereoisomer contributions observed were consistent with values reported in the literature. Contaminant levels are fairly distributed along the River and were generally low compared to similar studies around the world.

Demographic and temporal trends of hexabromocyclododecanes (HBCDD) in an Australian population.

Hexabromocyclododecanes (HBCDD) were measured in 67 pooled serum samples collected between 2002 and 2015 in South East Queensland, Australia. These data are the first report of HBCDD in Australian human serum. Temporal and demographic (age and gender) trends were investigated. HBCDD were detected in measurable concentrations in 69% of samples. The average ∑HBCDD concentration was 3.1ng/g lipid, whilst the range was <0.5 to 36ng/g lipid. α-HBCDD was the dominant stereoisomer making up an average of 60% of ∑HBCDD. The remainder was made up by γ-HBCDD. In contrast to another group of brominated flame retardants (BFRs, (polybrominated diphenyl ethers (PBDEs)), HBCDD were found in the lowest concentrations in pools from children aged 0-4 years. This could be attributed to differences in exposure, usage, and/ or the much lower half-life of HBCDD in the human body compared to PBDEs. HBCDD concentrations appear to be significantly higher in females than in males, however the reasons for this are unclear.

Concentrations of legacy and emerging flame retardants in air and soil on a transect in the UK West Midlands.

Passive air samples were collected monthly for 6 months from 8 sites along a transect of Birmingham, United Kingdom between June 2012 and January 2013. Soil samples were collected once at each site. Average concentrations of BDE-209, ΣPBDEs17:183 and ΣPBDEs in ambient air were 150, 49, and 180 pg m(-3), respectively. Atmospheric concentrations of PBDEs were negatively correlated with distance from the city centre, exhibiting an "urban pulse". The average ΣHBCDD air concentration was 100 pg m(-3), however concentrations were not correlated with distance from the city centre. Several emerging flame retardants (EFRs) were identified in air and/or soil samples: 2,3,4,5-tetrabromo-bis(2-ethylhexyl) phthalate (BEH-TEBP), 1,2-dibromo-4-(1,2 dibromoethyl)cyclohexane (TBECH or DBE-DBCH), allyl 2,4,6-tribromophenyl ether (ATE), 2-bromoallyl 2,4,6-tribromophenyl ether (BATE), decabromodiphenyl ethane (DBDPE), and dechlorane plus (DP or DDC-CO). Average concentrations of BDE-209, ΣPBDEs17:183 and ΣPBDEs in soil were 11, 3.6, and 15 ng g(-1) soil organic matter. PBDE concentrations in soil were higher at sites closest to the city centre, however correlations with distance from the city centre were not significant. BDEs-47 and -99 contributed more to ΣPBDEs in soil samples than air samples, but in both, the predominant congener was BDE-209. BATE was more abundant in air than soil but ATE was abundant in soil but not air.