Brominated and chlorinated flame retardants in San Francisco Bay sediments and wildlife

Restrictions on the use of polybrominated diphenyl ethers (PBDEs) have resulted in the use of alternative flame retardants in consumer products to comply with flammability standards. In contrast to PBDEs, information on the occurrence and fate of these alternative compounds in the environment is limited, particularly in the United States. In this study, a survey of flame retardants in San Francisco Bay was conducted to evaluate whether PBDE replacement chemicals and other current use flame retardants were accumulating in the Bay food web. In addition to PBDEs, brominated and chlorinated flame retardants (hexabromocyclododecane (HBCD) and Dechlorane Plus (DP)) were detected in Bay sediments and wildlife. Median concentrations of PBDEs, HBCD, and DP, respectively, were 4.3, 0.3, and 0.2 ng g^− 1 dry weight (dw) in sediments; 1670, < 6.0, and 0.5 ng g^− 1 lipid weight (lw) in white croaker (Genyonemus lineatus); 1860, 6.5, and 1.3 ng g^− 1 lw in shiner surfperch (Cymatogaster aggregata); 5500, 37.4, and 0.9 ng g^− 1 lw in eggs of double-crested cormorant (Phalacrocorax auritus); 770, 7.1, and 0.9 ng g^− 1 lw in harbor seal (Phoca vitulina) adults; and 330, 3.5, and < 0.1 ng g^− 1 lw in harbor seal (P. vitulina) pups. Two additional flame retardants, pentabromoethylbenzene (PBEB) and 1,2-bis(2,4,6 tribromophenoxy)ethane (BTBPE) were detected in sediments but with less frequency and at lower concentrations (median concentrations of 0.01 and 0.02 ng g^− 1 dw, respectively) compared to the other flame retardants. PBEB was also detected in each of the adult harbor seals and in 83% of the pups (median concentrations 0.2 and 0.07 ng g^− 1 lw, respectively). The flame retardants hexabromobenzene (HBB), decabromodiphenyl ethane (DBDPE), bis(2-ethylhexyl) tetrabromophthalate (TBPH), and 2-ethylhexyl 2,3,4,5-tetrabromobenzoate (TBB), were not detected in sediments and BTBPE, HBB and TBB were not detected in wildlife samples. Elevated concentrations of some flame retardants were likely associated with urbanization and Bay hydrodynamics. Compared to other locations, concentrations of PBDEs in Bay wildlife were comparable or higher, while concentrations of the alternatives were generally lower. This study is the first to determine concentrations of PBDE replacement products and other flame retardants in San Francisco Bay, providing some of the first data on the food web occurrence of these flame retardants in a North American urbanized estuary.     

Flame retardants and organochlorines in indoor dust from several e-waste recycling sites in South China: Composition variations and implications for human exposure

Several classes of flame retardants, such as polybrominated diphenyl ethers (PBDEs), novel brominated flame retardants (NBFRs), dechlorane plus (DPs), and organophosphate flame retardants (PFRs), together with polychlorinated biphenyls (PCBs) were measured in indoor dust from five villages located in three e-waste recycling regions in Guangdong Province, South China. The medians of PBDEs, NBFRs, and PFRs in dust in five sites ranged from 685–67,500, 1460–50,010, and 2180–29,000 ng/g, respectively. These concentrations were much higher than the medians of PCBs (52–2900 ng/g). BDE 209 and decabromodiphenyl ethane (DBDPE) were the two major halogen flame retardants in dust, while tris-(1-chloro-2-propyl) phosphate (TCIPP) and triphenyl phosphate (TPHP) were the major PFRs. Principle component analysis revealed the different pollutant patterns among different sites. The estimated median human exposures of PBDEs, NBFRs, PFRs, and PCBs via dust ingestion were 1.1–24.1, 0.73–20.3, 1.36–23.5, and 0.04–0.93 ng/kg bw/day for adults, and 16.2–352, 10.7–296, 19.9–343, 0.05–0.61, 0.65–13.6 ng/kg bw/day for toddlers, respectively. Residents from Site 5 had the highest exposure (95 percentile levels and high dust ingestion for toddlers) of PBDEs (3920 ng/kg bw/day), NBFRs (3200 ng/kg bw/day), and PFRs (5280 ng/kg bw/day). More attention should be paid to the contamination with NBFRs and PFRs, instead of PCBs, in these e-waste recycling regions, and local public health threat from PBDE alternatives should remain of concern. To the best of our knowledge, this is the first study on human exposure assessment of PFRs at e-waste sites.     

From the shop to the drain — Volatile methylsiloxanes in cosmetics and personal care products

Organosiloxanes are widely used in the formulation of a broad range of cosmetic and personal care products (PCPs), including creams and lotions, bath soaps, shampoo and hair care products to soften, smooth, and moisten. In fact, the intensive and widespread use of organosiloxanes combined with their lipophilic nature, makes them interesting targets for future research, particularly in the toxicology area.This study focused on determining the concentration levels of these compounds in the bestselling brands of PCPs in the Oporto region (Portugal), allowing the estimation of dermal and inhalation exposure to siloxanes and the evaluation of the quantities released to the environment “down-the-drain” and to air. To accomplish this task, a QuEChERS technique (“Quick, Easy, Cheap, Effective, Rugged, and Safe”) was employed to extract the siloxanes from the target PCPs, which has never been tested before. The resulting extract was analysed by gas chromatography–mass spectrometry (GC–MS). The limits of detection varied between 0.17 (L2) and 3.75 ng g^− 1 (L5), being much lower than any values reported in the literature for this kind of products. In general, satisfactory precision (< 10%) and accuracy values (average recovery of 84%) were obtained.123 PCPs were analysed (moisturizers, deodorants, body and hair washes, toilet soaps, toothpastes and shaving products) and volatile methylsiloxanes were detected in 96% of the samples, in concentrations between 0.003 μg g^− 1 and 1203 μg g^− 1. Shampoo exhibited the highest concentration for cyclic and aftershaves for linear siloxanes. Combining these results with the daily usage amounts, an average daily dermal exposure of 25.04 μg kg_bw^− 1 day^− 1 for adults and 0.35 μg kg_bw^− 1 day^− 1 for baby/children was estimated. The main contributors for adult dermal exposure were body moisturizers, followed by facial creams and aftershaves, while for babies/children were body moisturizers, followed by shower gel and shampoo. Similarly, the average daily inhalation exposure was also estimated. Values of 1.56 μg kg_bw^− 1 day^− 1 for adults and 0.03 μg kg_bw^− 1 day^− 1 for babies/children were calculated. An estimate of the siloxanes amount released “down-the-drain” into the sewage systems through the use of toiletries was also performed. An emission per capita between 49.25 and 9574 μg day^− 1 (mean: 1817 μg day^− 1) is expected and shampoo and shower gel presented the higher mean total values (1008 μg day^− 1 and 473.3 μg day^− 1, respectively). In the worst-case scenario, D5 and D3 were the predominant siloxanes in the effluents with 3336 μg day^− 1 and 3789 μg day^− 1, respectively. Regarding the air emissions per capita, values between 8.33 and 6109 μg day^− 1 (mean: 1607 μg day^− 1) are expected and D5 and D6 were the predominant siloxanes.     

Sources and human exposure implications of concentrations of organophosphate flame retardants in dust from UK cars,classrooms, living rooms,and offices

Concentrations of a number of organophosphate flame retardants (PFRs) were measured in floor dust collected from UK living rooms (n = 32), cars (n = 21), school and child daycare centre classrooms (n = 28), and offices (n = 61). While concentrations were overall broadly within the range of those reported previously for North America, Japan, and other European countries, median concentrations of TCIPP in all UK microenvironments exceeded those reported elsewhere in the world. Moreover, concentrations of TCIPP and TDCIPP in 2 UK car dust samples were – at 370 μg g^− 1 and 740 μg g^− 1 respectively – amongst the highest reported globally in indoor dust to date. Consistent with this, concentrations of TDCIPP in dust from UK cars exceed significantly those detected in the other microenvironments studied. Concentrations of EHDPP were shown for the first time to be significantly higher in classroom dust than in samples from other microenvironments. When compared to concentrations of PBDEs determined previously in the classroom dust samples; concentrations of all target PFRs exceeded substantially those of those PBDEs that are the principal constituents of the Penta- and Octa-BDE formulations. Moreover, while mass-based concentrations of BDE-209 exceeded those of most of our target PFRs, they still fell below those of TCIPP and EHDPP. In line with a previous observation in Sweden that indoor air contamination with TNBP was significantly lower in newer buildings; concentrations of TNBP in classroom dust were significantly higher in older compared to more recently-constructed schools. Consistent with the reported extensive use of TCIPP and TDCIPP in polyurethane foam, the highest concentrations of both TCIPP and TDCIPP in the classrooms studied, were observed in rooms containing the highest numbers of foam chairs (n = 31 and 18 respectively). Exposure to PFRs of both adults and young children via ingestion of indoor dust was estimated. While even our high-end exposure estimate for young children was ~ 100 times lower than one previously reported health-based limit (HBLV) value for TCIPP; the margin of safety was only 5-fold when compared to another HBLV for this contaminant.     

Body burden of metals and persistent organic pollutants among Inuit in the Canadian Arctic

Inuit living in the Arctic are exposed to elevated levels of environmental contaminants primarily due to long-range atmospheric transport. Blood sampling and contaminant biomonitoring was conducted as part of the International Polar Year Inuit Health Survey in 2007-2008. The body burden of metals (e.g. Cd, Pb) and persistent organic pollutants (e.g. PCBs, DDT & DDE, toxaphene, chlordane, PBDEs) were measured for Inuit participants (n = 2172) from 36 communities in Nunavut, Nunatsiavut, and the Inuvialuit Settlement Region, in Canada. The geometric mean of blood concentrations for Cd, Pb, PCBs, DDE & DDT, toxaphene, and chlordane were higher than those in the Canadian general population. A total of 9% of study participants exceeded the intervention guideline of 100 μg L^− 1 for Pb, 11% of participants exceeded the trigger guideline of 5 μg L^− 1 for Cd, and 1% exceeded the intervention guideline of 100 μg L^− 1 for PCBs. Also, 3% of women of child-bearing age exceeded blood Pb of 100 μg L^− 1 while 28% of women of child-bearing age exceeded 5 μg L^− 1 of PCBs. This work showed that most Inuit Health Survey participants were below blood contaminant guidelines set by Health Canada but that metal and POP body burdens commonly exceed exposures observed in the general population of Canada.     

Country specific comparison for profile of chlorinated,brominated and phosphate organic contaminants in indoor dust. Case study for Eastern Romania, 2010

We have evaluated the levels and specific profiles of several organohalogenated contaminants, including organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and flame retardants (FRs), such as polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs), novel brominated FRs (NBFRs), and organophosphate FRs (OPFRs), in 47 indoor dust samples collected in 2010 from urban locations from Iasi, Eastern Romania. The dominant contaminants found in the samples were OPFRs (median sum OPFRs 7890 ng/g). Surprisingly, OCPs were also measured at high levels (median 1300 ng/g). Except for BDE 209 (median 275 ng/g), PBDEs were present in dust samples at relatively low levels (median sum PBDEs 8 ng/g). PCBs were also measured at low levels (median sum PCBs 35 ng/g), while NBFRs were only occasionally detected, showing a low usage in goods present on the Romanian market. The results of the present study evidence the existence of a multitude of chemical formulations in indoor dust. FRs are usually associated to human exposure via ingestion of dust, but other chemicals, such as OCPs, are not commonly reported in such matrix. Although OCPs were found at comparable levels with OPFRs in Romanian dust, OCPs possess a higher risk to human health due to their considerably lower reference dose (RfD) values. Indeed, the OCP exposure calculated for various intake scenarios was only 2-fold lower than the corresponding RfD. Therefore, the inclusion of OCPs as target chemicals in the indoor environment becomes important for countries where elevated levels in other environmental compartments have been previously shown.     

Monocyclic and bicyclic monoterpenes in air of German daycare centers and human biomonitoring in visiting children,the LUPE 3 study

To investigate the assumed association between indoor air pollution with monoterpenes (MTps) and the internal MTp exposure of occupants, a comparative study was performed in daycare centers in two federal states of Germany. Three well-known monoterpenoid air pollutants, viz. α-pinene (αPN), Δ³-carene (CRN), and R-limonene (LMN), were measured in indoor air in 45 daycare centers. Additionally, urine samples of 222 children visiting these facilities were collected in the evening after a full-day stay. Altogether 11 MTp metabolites were analyzed in the urine samples using a novel highly sensitive and selective gas chromatographic–tandem-mass spectrometric procedure. The medians (95th percentiles) of the MTp levels in indoor air were 9.1 μg m^− 3 (94 μg m^− 3) for LMN, 2.6 μg m^− 3 (13 μg m^− 3) for αPN, and < 1.0 μg m^− 3 (3.2 μg m^− 3) for CRN. None of the day care centers exceeded the German health precaution or hazard guide value. In spite of the low MTp air exposure, the urine analyses revealed an exposure to the three monoterpenes in almost all children. The median levels of MTp metabolites in urine were 0.11 mg L^− 1 for LMN-8,9-OH, 0.10 mg L^− 1 for LMN-1,2-OH, 49 μg L^− 1 for PA, 2.9 μg L^− 1 for POH, 5.2 μg L^− 1 for tCAR, and 4.1 μg L^− 1 for cCAR (LMN metabolites), 7.2 μg L^− 1 for MYR, 19 μg L^− 1 for tVER, and 19 μg L^− 1 for cVER (αPN metabolites), as well as 8.2 μg L^− 1 for CRN-10-COOH (CRN metabolite). Statistically significant and strong correlations among the urinary metabolites of each MTp were found. Moreover, statistical associations between LMN metabolites and the LMN indoor air levels were revealed. However, the weakness of the associations indicates a considerable impact of other MTp sources, e.g. diet and consumer products, on the internal exposure.     

Polybrominated diphenyl ethers (PBDEs) in human samples of mother–newborn pairs in South China and their placental transfer characteristics

There are limited data concerning the placenta transfer characteristics and accumulation of polybrominated diphenyl ethers (PBDEs) in infants. However, PBDEs received increasing health concerns due to their endocrine disrupt and neurodevelopment toxicity effects. The present study assessed the accumulation of PBDEs in 30 paired placenta, breast milk, fetal cord blood, and neonatal urine samples collected from five major cities of the South China. The age of mothers ranged from 21 to 39 (mean 27.6 ± 4.56). The ∑ PBDE concentrations were 15.8 ± 9.88 ng g^− 1 lipid in placenta, 13.2 ± 7.64 ng g^− 1 lipid in breast milk, 16.5 ± 19.5 ng g^− 1 lipid in fetal cord blood, and 1.80 ± 1.99 ng ml^− 1 in neonatal urine. BDE-47 was the predominant congener in all types of human sample. Octa-BDEs such as BDE-196/-197 were detected highly in placenta and cord blood while moderately in breast milk and neonatal urine. Significant (p < 0.01) correlations were observed for both total and most individual PBDEs in cord blood–maternal placenta and breast milk–urine paired individual samples. The extent of placental transfer of higher brominated BDEs such as BDE-196/-197 was greater than that of BDE-47. The estimated daily intake (EDI) analysis for breast-fed infants revealed that newborns in these areas were exposed to relatively high levels of PBDEs via breast milk. Our study not only provided systematic fundamental data for PBDE distribution but also revealed the placenta transfer characteristics of PBDE congeners in South China.     

Determination of heavy metals in indoor dust from Istanbul,Turkey: Estimation of the health risk

Levels of eight potentially toxic heavy metals in indoor dust from homes and offices in Istanbul were investigated. The concentrations of heavy metals in indoor dust from homes + office ranged from 62 to 1800 μg g^− 1 for Cu, 3–200 μg g^− 1 for Pb, 0.4–20 μg g^− 1 for Cd, 210–2800 μg g^− 1 for Zn, 2.8–460 μg g^− 1 for Cr, 8–1300 μg g^− 1 for Mn, 2.4–25 μg g^− 1 for Co, 120–2600 μg g^− 1 for Ni. Results of the study were comparable to other studies conducted on indoor dust and street dust from a variety of cities globally. Considering only ingestion + inhalation, the carcinogenic risk level of Cr for adults and children (3.7 × 10^− 5 and 2.7 × 10^− 5) in Istanbul was in the range of EPA's safe limits (1 × 10^− 6 and 1 × 10^− 4), indicating that cancer risk of Cr due to exposure to indoor dust in Istanbul can be acceptable. According to calculated Hazard Quotient (HQ), for non-cancer effects, the ingestion of indoor dust appears to be the major route of exposure to the indoor dust that results in a higher risk for heavy metals, followed by dermal contact and inhalation pathways. However, compared to ingestion and dermal contact exposure, exposure through inhalation is almost negligible. Hazard Index (HI) values for all studied elements were lower than safe limit of 1 and this result suggested that none of the population groups would likely to experience potential health risk due to exposure to heavy metals from indoor dust in the study area.     

Risks associated with the transfer of toxic organo-metallic mercury from soils into the terrestrial feed chain

Although the transfer of organo-metallic mercury (OrgHg) in aquatic food webs has long been studied, it has only been recently recognized that there is also accumulation in terrestrial systems. There is still however little information about the exposure of grazing animals to OrgHg from soils and feed as well as on risks of exposure to animal and humans.In this study we collected 78 soil samples and 40 plant samples (Lolium perenne and Brassica juncea) from agricultural fields near a contaminated industrial area and evaluated the soil-to-plant transfer of Hg as well as subsequent trophic transfer. Inorganic Hg (IHg) concentrations ranged from 0.080 to 210 mg kg^− 1 d.w. in soils, from 0.010 to 84 mg kg^− 1 d.w. in roots and from 0.020 to 6.9 mg kg^− 1 d.w. in shoots. OrgHg concentrations in soils varied between 0.20 and 130 μg kg^− 1 d.w. representing on average 0.13% of the total Hg (THg). In root and shoot samples OrgHg comprised on average 0.58% (roots) and 0.66% (shoots) of THg. Average bioaccumulation factors (BAFs) for OrgHg in relation to soil concentrations were 3.3 (for roots) and 1.5 (for shoots).The daily intake (DI) of THg in 33 sampling sites exceeded the acceptable daily intake (ADI) of THg of both cows (ADI = 1.4 mg d^− 1) and sheep (ADI = 0.28 mg d^− 1), in view of food safety associated with THg in animal kidneys. Estimated DI of OrgHg for grazing animals were up to 220 μg d^− 1 (for cows) and up to 33 μg d^− 1 (for sheep).This study suggested that solely monitoring the levels of THg in soils and feed may not allow to adequately taking into account accumulation of OrgHg in feed crops and properly address risks associated with OrgHg exposure for animals and humans. Hence, the inclusion of limits for OrgHg in feed quality and food safety legislation is advised.     

Rice consumption contributes to low level methylmercury exposure in southern China

Fish consumption is considered as the primary pathway of human methylmercury (MeHg) exposure. However, recent studies highlighted that, rice, rather than fish, is the main route of human MeHg exposure in Guizhou, inland China. China is considered as the largest anthropogenic source of mercury (Hg) emission in the world, which has led to serious environmental Hg pollution. But there are no comprehensive studies regarding this environmental health problem to evaluate human Hg exposure and associated health effects. This study aimed to estimate daily MeHg intake and health risk in 7 provinces in southern China, and to assess the relative contribution from rice and fish consumption. The average levels of total mercury (THg) and MeHg in rice samples were generally low at 10.1 ng·g^− 1 and 2.47 ng·g^− 1, respectively. But a total of 36 rice samples (12.7%) had THg concentration exceeding the national limit (20 ng·g^− 1). Generally, rural population had significantly higher Probable Daily Intakes (PDIs) of MeHg than urban population from rice consumption and its relative contribution to MeHg exposure increased significantly from coastal to inland area. The averages of PDIs of MeHg were 0.020 μg·kg^− 1·d^− 1 and 0.028 μg·kg^− 1·d^− 1 for urban and rural population in southern China, respectively. Despite the serious environmental Hg pollutions in China, the general population in southern China had low risk of MeHg exposure. But rice is an important route of human MeHg exposure in southern China, especially for the rural population in inland area. The findings indicate that rice consumption should be considered when evaluating MeHg exposure in rice eating population in southern China.     

A geographical comparison of mercury in seabirds in the eastern Canadian Arctic

Mercury (Hg) is a potentially toxic metal ubiquitous in arctic biota. Livers of adult thick-billed murres (Uria lomvia) and northern fulmars (Fulmarus glacialis) sampled from several locations in the eastern Canadian Arctic during 2007–2008 were analyzed for total Hg in order to assess geographical patterns. Thick-billed murres were collected from five colonies (Coats Island, Digges Island, Akpatok Island, Prince Leopold Island, Minarets) and northern fulmars from two colonies (Prince Leopold Island, Minarets). Murres at the two high Arctic colonies of Prince Leopold Island and the Minarets had significantly higher (two-fold) Hg concentrations (4.13 ± 019 μg g^− 1 dw and 4.41 ± 0.33 μg g^− 1 dw, respectively) than at the three low Arctic colonies (colony means of 1.62, 1.99 and 2.15 μg g^− 1 dw). The differences in Hg concentrations observed between high and low Arctic murre colonies may reflect a combination of different source regions for Hg, as well as a recent dietary shift among low Arctic murres. Fulmars from Prince Leopold Island had significantly higher Hg levels (6.99 ± 1.13 μg g^− 1 dw) than those from the Minarets (3.42 ± 0.53 μg g^− 1 dw) which may reflect different Hg deposition and methylation patterns on both summer and winter feeding areas. Although there is no evidence linking Hg to adverse population effects in either murres or fulmars at the colonies sampled, levels in some Canadian Arctic marine birds have increased over recent decades and, therefore, continued monitoring, particularly of the high Arctic colonies, is warranted.     

Assessment of cadmium bioaccessibility to predict its bioavailability in contaminated soils

In vitro assays have been developed to determine metal bioaccessibility in contaminated soils; however, their application to Cd is limited. To assess their suitability to determine Cd relative bioavailability (RBA), Cd-RBA in 12 contaminated soils containing 3.00–296 mg kg^− 1 Cd were determined using a mouse model and compared with Cd bioaccessibility data based on four assays including the UBM, SBRC, IVG, and PBET. After being administered feed amended with soil or CdCl₂ for 10-day, the Cd concentrations in the mouse liver and/or kidneys were used as biomarkers to estimate Cd-RBA. Cd-RBA was comparable at 34–90% and 40–78% based on mouse liver and kidneys with RSD of 7.10–8.99%, and 37–84% based on mouse liver plus kidneys with lower RSD of 5.8%. Cadmium bioaccessibility in soils varied with assays, with 61–99, 59–103, 54–107, and 35–97% in the gastric phase and 20–56, 38–77, 42–88, and 19–64% in the intestinal phase of the UBM, SBRC, IVG and PBET assays. Based on the combined biomarker of liver plus kidneys, better correlation was observed for PBET (r² = 0.61–0.70) than those for IVG, UBM and SBRC assays (0.12–0.52). The monthly Cd intake in children was 0.24–23.9 μg kg^− 1 using total Cd concentration in soils, which was reduced by 43% to 0.18–12.3 μg kg^− 1 using bioavailable Cd. Our data suggest it is important to consider Cd-RBA to assess risk associated with contaminated soils and the PBET may have potential to predict Cd-RBA in contaminated soils.     

Measurement and health risk assessment of PM2.5, flame retardants,carbonyls and black carbon in indoor and outdoor air in kindergartens in Hong Kong

Indoor air pollution is closely related to children's health. Polybrominated diphenyl ethers (PBDEs) and dechlorane plus (DP) transmitted through indoor PM_2.5 and dust, along with carbonyl compounds and black carbon (BC) aerosol were analysed in five Hong Kong kindergartens. The results showed that 60% of the median PM_2.5 levels (1.3 × 10¹ to 2.9 × 10¹ μg/m³ for indoor; 9.5 to 8.8 × 10¹ μg/m³ for outdoor) in the five kindergartens were higher than the guidelines set by the World Health Organization (2.5 × 10¹ μg/m³). Indoor PM_2.5 mass concentrations were correlated with outdoor PM_2.5 in four of the kindergartens. The PBDEs (0.10–0.64 ng/m³ in PM_2.5; 0.30–2.0 × 10² ng/g in dust) and DP (0.05–0.10 ng/m³ in PM_2.5; 1.3–8.7 ng/g in dust) were detected in 100% of the PM_2.5 and dust samples. Fire retardant levels in the air were not correlated with the levels of dust in this study. The median BC concentrations varied by > 7-fold from 8.8 × 10² ng/m^− 3 to 6.7 × 10³ ng/m^− 3 and cooking events might have caused BC concentrations to rise both indoors and outdoors. The total concentrations of 16 carbonyls ranged from 4.7 × 10¹ μg/m³ to 9.3 × 10¹ μg/m³ indoors and from 1.9 × 10¹ μg/m³ to 4.3 × 10¹ μg/m³ outdoors, whilst formaldehyde was the most abundant air carbonyl. Indoor carbonyl concentrations were correlated with outdoor carbonyls in three kindergartens. The health risk assessment showed that hazard indexes (HIs) HIs of non-cancer risks from PBDEs and DPs were all lower than 0.08, whilst non-cancer HIs of carbonyl compounds ranged from 0.77 to 1.85 indoors and from 0.50 to 0.97 outdoors. The human intake of PBDEs and DP through inhalation of PM_2.5 accounted for 78% to 92% of the total intake. The cancer hazard quotients (HQs) of formaldehyde ranged from 4.5E − 05 to 2.1E − 04 indoors and from 1.9E − 05 to 6.2E − 05 outdoors. In general, the indoor air pollution in the five Hong Kong kindergartens might present adverse effects to children, although different schools showed distinct pollution levels, so indoor air quality might be improved through artificial measures. The data will be useful to developing a feasible management protocol for indoor environments.     

Hydroxylated and methoxylated polybrominated diphenyl ethers in blood plasma of humans in Hong Kong

Hydroxylated (OH-) and methoxylated (MeO-) polybrominated diphenyl ethers (PBDE) are suspected endocrine disruptors. Little is known about the accumulation or sources of these chemicals in tissues of humans, particularly those residing in Hong Kong, which is one of the most densely populated cities in the world. Seven MeO-BDEs, fifteen OH-BDEs and three bromophenols (BRPs) were analyzed in blood plasma of 116 humans that had been collected by the Hong Kong Red Cross. Total concentrations of MeO-BDEs, OH-BDEs and BRPs ranged from 3.8 × 10² to 52 × 10³ pg g^− 1 lipid (median 4.5 × 10³ pg g^− 1), 5.3 to 4.9 × 10² pg g^− 1 lipid (81 pg g^− 1) and ND to 1.1 × 10² pg g^− 1 lipid (3.7 pg g^− 1), respectively. 3-MeO-BDE-47, 6-OH-BDE-47 and 2, 4, 5-TBP were the predominant MeO-BDEs, OH-BDEs and BRPs, respectively. These results are consistent with accumulation of MeO-BDEs, OH-BDEs and BRPs in human plasma being primarily from natural products and inter-conversion of natural products. Coefficients of determination for some pairs of congeners such as 3-OH-BDE-100 and 6-OH-BDE-47, 6-OH-BDE-85 and 5′-OH-BDE-99, and 2, 4-DBP and 6-OH-BDE-85, were near 1.0, which is consistent with them having common sources. Patterns of relative concentrations of the target analytes were similar in the diet, particularly fish, as in blood plasma of humans, which suggests that the diet and particularly seafood might be a source of these compounds and PBDEs. Furthermore, biotransformation of natural chemicals such as OH-BDEs to BRPs might be the primary route of their elimination from humans.     

Polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs) in breast milk from Zhejiang,China

Breast milk samples (n = 74) from the general maternal population of Zhejiang province were analyzed for polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs). Samples were divided into urban and rural groups. Mean ∑PCDD/F, ∑PCB and ∑PBDE concentrations were 71.4 ± 40.8, 42774 ± 27841 and 2679 ± 944 pg g^− 1 lipid in the urban group and 38.6 ± 38.1, 26546 ± 11375 and 2731 ± 1093 pg g^− 1 lipid in the rural group, respectively. WHO-TEQ concentrations for dioxin-like PCBs and PCDD/Fs were 2.66 ± 1.43 and 3.90 ± 2.60 pg g^− 1 lipid in the urban group and 1.83 ± 0.93 and 2.27 ± 1.55 pg g^− 1 lipid in the rural group, respectively. Congener profiles for these pollutants were compared between human samples (adipose tissue and breast milk) and foodstuffs (seafood, hen eggs, and freshwater fish). Similar PCB and PCDD/F congener patterns were observed, suggesting that dietary intake is a significant source for human exposure to PCBs and PCDD/Fs. However, much lower PBDE congener levels were detected in breast milk than in foodstuffs, which implies that pathways other than dietary intake may also account for human exposure to PBDEs.     

First report of pyrethroid bioaccumulation in wild river fish: A case study in Iberian river basins (Spain)

For the first time, this work described pyrethroid bioaccumulation in edible river fish samples. We analyzed 42 whole fish samples collected in 4 different Iberian rivers. All samples were positive to these insecticides. Levels of concentration ranged from 12 to 4938 ng g^− 1 lipid weight (lw). Moreover, isomeric characterization was carried out. Our results remarked a general preference of cis isomers in bioaccumulation. Finally, the enantiomeric evaluation showed that there was an enantioselective bioaccumulation of some pyrethroids, depending on the studied species. Pyrethroid concentrations were compared with levels obtained for other common pollutants, such as flame retardants, personal care products, hormones and pharmaceuticals. The highest values corresponded to pyrethroid insecticides, even though, pyrethroid levels are safe for human consumption taken into account the current regulations.     

Within-room and within-building temporal and spatial variations in concentrations of polybrominated diphenyl ethers (PBDEs) in indoor dust

Within-house and within-room spatial temporal variability in PBDE contamination of indoor dust may influence substantially the reliability of human exposure assessments based on single point samples, but have hitherto been little studied. This paper reports concentrations of PBDEs 17, 28, 47, 49, 66, 85, 99, 100, 153, and 154 in indoor dust samples (n = 112) from two houses in Birmingham, UK. To evaluate within-house spatial variability, four separate rooms were sampled in house 1 and two separate rooms sampled in house 2. Up to four different 1 m² areas in the same room were sampled to evaluate within-room spatial variability, and for all studied areas, samples were taken for eight consecutive months to evaluate temporal and seasonal variability. Concentrations of ΣPBDEs in individual samples from house 1 varied between 21 and 280 ng g^− 1; while the range of concentrations in house 2 was 20–1000 ng g^− 1. This indicates that where and when a sample is taken in a house can influence substantially the contamination detected. In one room, concentrations of PBDEs in an area located close to putative PBDE sources exceeded substantially those in an area 2 m away, with marked differences also observed between two areas in another room. Substantial within-room spatial differences in PBDE concentrations were not discernible in the other rooms studied. Concentrations of PBDEs in the majority of rooms within the same houses were not markedly different between rooms. Nevertheless, large differences were observed between PBDE concentrations detected in two rooms in the same house in both houses studied. In one instance, this is hypothesised to be attributable to the presence of a carpet in one room and bare wooden floor in another, but firm conclusions cannot be drawn. Within-room temporal (month-to-month) variability was substantial (relative standard deviations for ΣPBDEs = 15–200%). In some rooms, the introduction and removal of putative sources like a TV and a bed, appeared to exert a discernible influence on PBDE concentrations. PBDE concentrations in spring and summer were not markedly different from those observed in autumn and winter. Possible dilution of PBDE concentrations in dust at higher dust loadings (g dust per m² floor surface) was investigated in a small number of rooms, but no firm evidence of such dilution was evident.     

Mechanistic polychlorinated biphenyl exposure modeling of mothers in the Canadian Arctic: the challenge of reliably establishing dietary composition

BackgroundTraditional food (TF) consumption represents the main route of persistent organic pollutant (POP) exposure for indigenous Arctic Canadians. Ongoing dietary transitions away from TFs and toward imported foods (IFs) may contribute to decreasing POP exposures observed in these groups.MethodsTo explore this issue, we combined the global fate and transport model GloboPOP and the human food chain bioaccumulation model ACC-Human Arctic to simulate polychlorinated biphenyl (PCB) exposure in two indigenous Arctic Canadian communities from the Inuvik region, Northwest Territories and Baffin region, Nunavut. Using dietary survey information from initial (1996–98) and follow-up (2005–07) biomonitoring campaigns in Inuvik and Baffin, we simulated PCB exposures (PCB-118, -138, -153, and -180) for each individual study participant and also whole study populations.ResultsTF intake rates, particularly of marine mammals (MMs), were the most important predictors of modeled PCB exposure, while TF consumption did not associate consistently with measured PCB exposures. Further, reported mean TF intake increased from baseline to follow-up in both Inuvik (from 8 to 183 g d^− 1) and Baffin (from 60 to 134 g d^− 1), opposing both the expected dietary transition direction and the observed decrease in human PCB exposures in these communities (ΣPCB Inuvik: from 43 to 29 ng g lipid^− 1, ΣPCB Baffin: from 213 to 82 ng g lipid^− 1). However dietary questionnaire data are frequently subject to numerous biases (e.g., recall, recency, confirmation), and thus casts doubt on the usefulness of these data.ConclusionsUltimately, our model's capability to reproduce historic PCB exposure data in these two groups was highly sensitive to TF intake, further underscoring the importance of accurate TF consumption reporting, and clarification of the role of dietary transitions in future POP biomonitoring of indigenous Arctic populations.     

Measurement of flame retardants and triclosan in municipal sewage sludge and biosolids

As polybrominated diphenyl ethers (PBDEs) face increasing restrictions worldwide, several alternate flame retardants are expected to see increased use as replacement compounds in consumer products. Chemical analysis of biosolids collected from wastewater treatment plants (WWTPs) can help determine whether these flame retardants are migrating from the indoor environment to the outdoor environment, where little is known about their ultimate fate and effects. The objective of this study was to measure concentrations of a suite of flame retardants, and the antimicrobial compound triclosan, in opportunistic samples of municipal biosolids and the domestic sludge Standard Reference Material (SRM) 2781. Grab samples of biosolids were collected from two WWTPs in North Carolina and two in California. Biosolids samples were also obtained during three subsequent collection events at one of the North Carolina WWTPs to evaluate fluctuations in contaminant levels within a given facility over a period of three years. The biosolids and SRM 2781 were analyzed for PBDEs, hexabromobenzene (HBB), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), 2-ethylhexyl 2,3,4,5-tetrabromobenzoate (TBB), di(2-ethylhexyl)-2,3,4,5-tetrabromophthalate (TBPH), the chlorinated flame retardant Dechlorane Plus (syn- and anti-isomers), and the antimicrobial agent 5-chloro-2-(2,4-dichlorophenoxy)phenol (triclosan). PBDEs were detected in every sample analyzed, and ΣPBDE concentrations ranged from 1750 to 6358 ng/g dry weight. Additionally, the PBDE replacement chemicals TBB and TBPH were detected at concentrations ranging from 120 to 3749 ng/g dry weight and from 206 to 1631 ng/g dry weight, respectively. Triclosan concentrations ranged from 490 to 13,866 ng/g dry weight. The detection of these contaminants of emerging concern in biosolids suggests that these chemicals have the potential to migrate out of consumer products and enter the outdoor environment.