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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)., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

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

2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EH-TBB) and a mixture of EH-TBB, Bis(2-ethylhexyl)tetrabromphthalate (BEH-TEBP) and Triphenyl phosphate (TPhP), prepared in a ratio similar to the Firemaster-550™ (FM550) flame retardant formulation, were exposed to human skin subcellular fractions (S9) to evaluate their dermal in vitro metabolism for the first time. After 60 min of incubation, tetrabromobenzoic acid (TBBA) and diphenyl phosphate (DPhP) were identified as the major metabolites of EH-TBB and TPhP, respectively using UPLC-Q-Exactive Orbitrap™-MS analysis. Dermal biotransformation of EH-TBB and TPhP was catalyzed by skin carboxylesterases rather than CYP450 enzymes, while no stable metabolites could be identified for BEH-TEBP. Metabolite formation rates of EH-TBB as individual compound and as a component of FM550 fitted the Michaelis-Menten model, while no steady state could be reached for TPhP under experimental conditions. Estimated maximum metabolic rate (V max ) for TBBA formation upon exposure to FM550 was lower than V max for EH-TBB (1.08 and 15.2 pmol min -1 mg protein -1 , respectively). This indicates dermal metabolism would contribute less to the clearance of EH-TBB body burden than hepatic metabolism (V max  = 644 pmol min -1 mg protein -1 ). Implications for human exposure include EH-TBB accumulation in skin tissue and human exposure to dermal metabolic products, which may have different toxicokinetic and toxicodynamic parameters than parent flame retardants., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Concentrations of 7 indicator polychlorinated biphenyls (PCBs) were measured in dust and soil samples from 12 power stations collected over the two major seasons of the Nigerian climate. Median ƩPCB 7 concentrations in soil ranged from 2 ng/g for power station A to 220 ng/g for power station I; while those in dust ranged from 21 ng/g for power station L to 2200 ng/g for power station I. For individual congeners, median PCB concentrations ranged from 3.8 ng/g for PCB 101 to 52 ng/g for PCB 180 in dust, and <0.07 ng/g for PCB 28 to 5.9 ng/g for PCB 153 in soil. The type of power station activity exerted a significant influence on concentrations of ΣPCB 7 in dust and soil (generation > transmission > distribution). Congener patterns in dust and soil samples were compared using principal component analysis (PCA) with those in transformer oil samples from 3 of the power stations studied and with common PCB mixtures (Aroclors). This revealed congener patterns in soil were more closely related to that in the transformer oil than dust. Congener patterns in most samples were similar to Aroclor 1260. Concentrations of PCBs in soil samples close to the transformers significantly exceeded those in soil sampled further away., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

While there are no regulatory fire safety obligations for polystyrene (PS) when used as packaging material, concerns exist that such packaging material may contain the flame retardant hexabromocyclododecane (HBCDD) as a result of uncontrolled recycling activities. To evaluate these concerns, we collected 50 samples of PS packaging materials from the UK and 20 from Ireland. HBCDD was detected in 63 (90%) of samples, with concentrations in 4 samples from Ireland exceeding the EU's low POP concentration limit (LPCL) of 0.1% above which articles may not be recycled. Moreover, 2 further samples contained HBCDD >0.01%. While our samples were obtained in the 12 month period prior to the March 2016 introduction of the EU's 0.01% concentration limit above which articles may not be placed on the market, our data suggest that continued monitoring is required to assess compliance with this limit value. Ratios of α vs. γ-HBCDD in our EPS packaging samples (average = 0.63) exceeded significantly (p = 0.025) those in EPS building insulation material samples (average = 0.24) reported previously for Ireland. This shift towards α-HBCDD in packaging EPS is consistent with the additional thermal processing experienced by recycled PS and suggests the source of HBCDD in PS packaging is recycled PS insulation foam. This is of concern owing to the higher bioavailability and lower metabolic clearance of α-HBCDD compared to the β- and γ-isomers., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) were measured in dust from 16 cars, 12 homes, and 18 offices in Lagos, Nigeria. These represent the first and second reports respectively of contamination of Nigerian indoor dust with these contaminants, and the second report on PCBs in car dust worldwide. Concentrations of BDE-47 and BDE-99 in two car dust samples (9300 and 3700 ng g(-1) for BDE-47 and 4200 and 19,000 ng g(-1) for BDE-99), are amongst the highest ever reported in car dust. ANOVA comparison with Canada, New Zealand, the UK, and the USA; reveals concentrations of BDEs-28, 49, 47, 66, 100, 99, 154, and 153 in Nigerian house dust, to be significantly lower than in Canada and the USA, with those of BDE-49 and 154 significantly lower than in New Zealand and the UK. Concentrations of BDE-209 in Nigeria were significantly lower than concentrations in the UK and the USA; while concentrations of PCB-180 were significantly greater than those in New Zealand, the UK, and the USA. Median concentrations of PCBs in cars were substantially higher than in the only previous study (in Kuwait and Pakistan). While median concentrations of PBDEs in cars generally exceeded those in homes, this was significant only for BDEs-49, 154, and 197, with concentrations in cars significantly greater than those in offices for BDEs-49 and 154. Contrastingly, concentrations of all target PCBs in offices exceeded significantly those in cars. This study underlines the truly global distribution of indoor contamination with PBDEs and PCBs., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Humans are routinely exposed to mixtures of flame retardants (FRs) from multiple sources including indoor dust. As a model to explore the potential effects of FR exposure from indoor dust on human health, the molecular responses of human hepatoma cells (HepG2/C3A cells) to a defined mixture of FRs and to a dust extract were investigated using multiple non-targeted omics approaches. A solvent extract of an indoor dust standard reference material SRM2585 was used as the surrogate dust sample, while a mixture of four FRs (TCEP, TCIPP, TDCIPP and HBCD) was used to mimic the FR mixture in the indoor dust. Cytotoxicity tests indicated there were no significant changes to cell viability or cell integrity after a 24- or 72-h exposure of HepG2/C3A cells to the FR mixture or to the dust extract. However, transcriptomics revealed changes in gene expression associated with the metabolism of xenobiotics (e.g. CYP1A1, CYP1A2, CYP2B6) in the dust extract group but not in the FR mixture group after a 72-h exposure. Few metabolic or lipidomic changes were detected in response to either the FR mixture or to the dust extract group. Given that the dust extract contained components that elicited a biological response, in contrast to the lack of response induced by the FR mixture, our findings suggest that the most likely causes of the molecular responses to indoor dust exposure lie in components other than the four FRs investigated, e.g. caused by PAHs or PCBs., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Concentrations of tri-to-hexa-BDEs were determined in water samples taken from 9 English lakes on 13 occasions between April 2008 and February 2012. Across all sites, concentrations of ΣBDEs in individual samples ranged from 9.2 to 171.5pgL(-)(1), with an average of 61.9pgL(-)(1). Notwithstanding the far greater use of the Penta-BDE commercial formulation in the USA, concentrations in this study are comparable to the limited data available for the Great Lakes. PBDE concentrations showed no evidence of a decline at any monitored location over the study period. This may be because this study commenced 4years after the introduction of restrictions on the Penta- and Octa-BDE formulations. While concentrations normalised to water volume at the different locations were statistically indistinguishable; significant spatial variation was apparent when the data were normalised to total suspended solids (TSS) content. However, this spatial variation was not correlated with factors such as population density and lake catchment area, suggesting that concentrations of PBDEs in lake water in this study are a complex integral of numerous factors. BDE-47:99 ratios and concentrations of ΣBDEs respectively decreased and increased significantly with increasing TSS content. As TSS content was elevated in colder compared with warmer periods, such seasonal variation in TSS content appears a major contributor to the observed elevation of ΣBDE concentrations in colder periods, and higher BDE-47:99 ratios in warmer periods., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs), and tetrabromobiphenol-A (TBBP-A) were measured in a preliminary study of dust from passenger cabins and trunks of 14 UK cars. Concentrations in cabin dust of HBCDs, TBBP-A, and BDEs 47, 85, 99, 100, 153, 154, 183, 196, 197, 202, 203, 206, 207, 208, and 209 exceeded significantly (p<0.05) those in trunk dust. Sampling cabin dust thus appears to provide a more accurate indicator of human exposure via car dust ingestion than trunk dust. Elevated cabin concentrations are consistent with greater in-cabin use of BFRs. In five cars, while no significant differences (p>0.05) in concentrations of HBCDs and most PBDEs were detected in dust sampled from four different seating areas; concentrations of TBBP-A and of PBDEs 154, 206, 207, 208, and 209 were significantly higher (p<0.05) in dust sampled in the front seats. Possible photodebromination of BDE-209 was indicated by significantly higher (p<0.05) concentrations of BDE-202 in cabin dust. In-vehicle exposure via dust ingestion to PBDEs, HBCDs and TBBP-A exceeded that via inhalation. Comparison with overall exposure via diet, dust ingestion, and inhalation shows while in-vehicle exposure is a minor contributor to overall exposure to BDE-99, ΣHBCDs, and TBBP-A, it is a significant pathway for BDE-209., (Copyright © 2010 Elsevier Ltd. All rights reserved.)

Using synthetic functionalized analogues of pyochelin, a siderophore common to several pathogenic Pseudomonas and Burkholderia species, four fluoroquinolone-pyochelin conjugates were efficiently synthesized and evaluated for their biological activities.

A novel and straightforward total synthesis of cepabactin and its iron (III) complex is described. The latter compound was compared and identified to that obtained from the cultures of Burkholderia cepacia. On treatment of the growth medium of two different strains of B. cepacia with ferric chloride, we have isolated and characterized an unexpected mixed complex of iron (III), cepabactin and pyochelin.

The synthesis and biological activities of four pyochelin analogues substituted in different parts of the molecule are reported: 5-NHBoc-pyochelin, 3"N-Boc-pyochelin, 3"-nor-NH-pyochelin and neopyochelin II, the enantiomer of natural pyochelin. All these compounds complex iron(III) and transport it at different rates into the cells of Pseudomonas aeruginosa.