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.     

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.     

Can car air filters be useful as a sampling medium for air pollution monitoring purposes?

Urban air quality and real human exposure to chemical environmental stressors is an issue of high scientific and political interest. In an effort to find innovative and inexpensive means for air quality monitoring, the ability of car engine air filters (CAFs) to act as efficient samplers collecting street level air, to which people are exposed to, was tested. In particular, in the case of taxis, air filters are replaced after regular distances, the itineraries are almost exclusively urban, cruising mode is similar and, thus, knowledge of the air flow can provide with an integrated city air sample. The present pilot study focused on polycyclic aromatic hydrocarbons (PAHs), the most important category of organic pollutants associated with traffic emissions. Concentrations of ΣPAHs in CAFs ranged between 650 and 2900 μg CAF^− 1, with benzo[b]fluoranthene, benzo[k]fluoranthene and indeno[123-cd]pyrene being the most abundant PAHs. Benzo[a]pyrene (BaP) ranged between 110 and 250 μg CAF^− 1, accounting regularly for 5–15% of the total carcinogenic PAHs. The CAF PAH loads were used to derive road-level atmospheric PAH concentrations from a standard formula relating to the CAF air flow. Important parameters/assumptions for these estimates are the cruising speed and the exposure duration of each CAF. Based on information obtained from the garage experts, an average ‘sampled air volume’ of 48,750 m³ per CAF was estimated, with uncertainty in this calculation estimated to be about a factor of 4 between the two extreme scenarios. Based on this air volume, ΣPAHs ranged between 13 and 56 ng m^− 3 and BaP between 2.1 and 5.0 ng m^− 3, suggesting that in-traffic BaP concentrations can be many times higher than the limit values set by the UK (0.25 ng m^− 3) and the European Union (1.0 ng m^− 3), or from active sampling stations normally cited on building roof tops or far from city centres.Notwithstanding the limitations of this approach, the very low cost, the continuous availability of very high amounts of “sample”, and the “retroactivity” render it very useful and complementary to existing passive sampling techniques. This approach yields estimated air concentrations that reflect the pollutant concentrations to which taxi drivers, pedestrians, cyclists and road-related professionals are exposed.     

Seasonal variation in outdoor,indoor, and personal air pollution exposures of women using wood stoves in the Tibetan Plateau: Baseline assessment for an energy intervention study

Cooking and heating with coal and biomass is the main source of household air pollution in China and a leading contributor to disease burden. As part of a baseline assessment for a household energy intervention program, we enrolled 205 adult women cooking with biomass fuels in Sichuan, China and measured their 48-h personal exposure to fine particulate matter (PM_2.5) and carbon monoxide (CO) in winter and summer. We also measured the indoor 48-h PM_2.5 concentrations in their homes and conducted outdoor PM_2.5 measurements during 101 (74) days in summer (winter). Indoor concentrations of CO and nitrogen oxides (NO, NO₂) were measured over 48-h in a subset of ~ 80 homes. Women's geometric mean 48-h exposure to PM_2.5 was 80 μg/m³ (95% CI: 74, 87) in summer and twice as high in winter (169 μg/m³ (95% CI: 150, 190), with similar seasonal trends for indoor PM_2.5 concentrations (winter: 252 μg/m³; 95% CI: 215, 295; summer: 101 μg/m³; 95% CI: 91, 112). We found a moderately strong relationship between indoor PM_2.5 and CO (r = 0.60, 95% CI: 0.46, 0.72), and a weak correlation between personal PM_2.5 and CO (r = 0.41, 95% CI: − 0.02, 0.71). NO₂/NO ratios were higher in summer (range: 0.01 to 0.68) than in winter (range: 0 to 0.11), suggesting outdoor formation of NO₂ via reaction of NO with ozone is a more important source of NO₂ than biomass combustion indoors. The predictors of women's personal exposure to PM_2.5 differed by season. In winter, our results show that primary heating with a low-polluting fuel (i.e., electric stove or wood-charcoal) and more frequent kitchen ventilation could reduce personal PM_2.5 exposures. In summer, primary use of a gaseous fuel or electricity for cooking and reducing exposure to outdoor PM_2.5 would likely have the greatest impacts on personal PM_2.5 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.     

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.     

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 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.     

Aggregate consumer exposure to UV filter ethylhexyl methoxycinnamate via personal care products

Ultraviolet (UV) filters are substances designed to protect our skin from UV-induced damage and can be found in many categories of personal care products (PCPs). The potential endocrine-disrupting effects attributed to UV filter ethylhexyl methoxycinnamate (EHMC) are being debated. We evaluated the aggregate exposure of the Swiss–German population (N = 1196; ages ≤ 1–97 years) to EHMC via the use of PCPs; thus we provide the first comprehensive information about the current EHMC exposure sources and aggregate exposure levels. In our probabilistic modeling method performed at an individual level, PCP use data obtained by a postal questionnaire were linked to concentration data on EHMC gained from chemical analyses of PCPs used by the questionnaire respondents. The modeled median and 99.9th percentile of the internal aggregate exposure for the general population were 0.012 and 0.873 mg day^− 1 kg^− 1 and 0.008 and 0.122 mg day^− 1 kg^− 1 for the summer/autumn and winter/spring period, respectively. The major contributors to internal aggregate exposure were sunscreen products in summer/autumn (females: 64%; males: 85%; children aged ≤ 12 years 93%). In winter/spring, lip care dominated for females (30%) and sunscreen for males (38%) and children aged ≤ 12 years (50%). Overall, the internal aggregate exposure estimates for the studied population are shown to be below the Derived No Effect Level (DNEL) for EHMC i.e., the level of exposure above which humans should not be exposed; however, when an intense short-term exposure via sunscreen is accounted for during a sunbathing day, at the high-end percentiles (99.9th) the predicted aggregate exposure exceeds the DNEL for thyroid-disrupting effects such as for children aged ≤ 4 years, who might be particularly susceptible to endocrine disrupting events. It is nevertheless critical to acknowledge that quantitative data on transdermal penetration of EHMC from PCPs are currently insufficient. Since long-term effects of endocrine disruptors are not known, future studies are warranted to provide accurate quantitative data on transdermal penetration of EHMC and to determine its metabolic fate in humans.     

Association between maternal exposure to perfluorooctanoic acid (PFOA) from electronic waste recycling and neonatal health outcomes

ObjectivePerfluorooctanoic acid (PFOA) has applications in numerous industrial and consumer products. The widespread prevalence of PFOA in humans demonstrated in recent studies has drawn considerable interest from the public. We aimed to evaluate the exposure of mothers to PFOA and the potential hazards to neonates in a primitive electronic waste recycling area, Guiyu, China, and a control area, Chaonan, China.MethodsOur investigation included analyses of maternal serum samples, health effect examinations, and other relevant factors. Questionnaires were administered and maternal serum samples were collected for 167 pregnant women. Solid phase extraction method was used for all analytical sample preparation, and analyses were completed using high performance liquid chromatography tandem mass spectrometry method.ResultsThe PFOA concentration was higher in maternal serum samples from Guiyu than in samples from Chaonan (median 16.95, range 5.5–58.5 ng mL^− 1; vs. 8.7, range 4.4–30.0 ng mL^− 1; P < 0.001). Residence in Guiyu, involvement in e-waste recycling, husband's involvement in e-waste and use of the family residence as workshop were significant factors contributing to PFOA exposure. Maternal PFOA concentrations were significantly different between normal births and adverse birth outcomes including premature delivery, term low birth weight, and stillbirths. After adjusting for potential confounders, PFOA was negatively associated with gestational age [per lg-unit: β = − 15.99 days, 95% confidence interval (CI), − 27.72 to − 4.25], birth weight (per lg-unit: β = − 267.3 g, 95% CI, − 573.27 to − 37.18), birth length (per lg-unit: β = − 1.91 cm, 95% CI, − 3.31 to − 0.52), and Apgar scores (per lg-unit: β = − 1.37, 95% CI, − 2.42 to − 0.32), but not associated with ponderal index.ConclusionsMothers from Guiyu were exposed to higher levels of PFOA than those from control areas. Prenatal exposure to PFOA was associated with decreased neonatal physical development and adverse birth outcomes.     

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.     

Radionuclide concentrations in soil and lifetime cancer risk due to gamma radioactivity in Kirklareli,Turkey

The objective of this study is to evaluate and map soil radionuclides' activity concentrations and environmental outdoor gamma dose rates (terrestrial and cosmic) in Kirklareli, Turkey. The excess lifetime cancer risks are also calculated. Outdoor gamma dose rates were determined in 230 sampling stations and soil samples were taken from 177 locations. The coordinates of the readings were determined by the Global Positioning System (GPS). The outdoor gamma dose rates were determined by Eberline smart portable device (ESP-2) and measurements were taken in air for two minutes at 1 m from the ground. The average outdoor gamma dose rate was 118 ± 34 nGy h^?1. Annual effective gamma dose of Kirklareli was 144 μSv and the excess lifetime cancer risk of 5.0 × 10^?4. Soil samples were analyzed by gamma spectroscopy. The average ²²⁶Ra, ²³⁸U, ²³²Th, ¹³⁷Cs, and ⁴⁰K activities were 37 ± 18 Bq kg^?1, 28 ± 13 Bq kg^?1, 40 ± 18 Bq kg^?1, 8 ± 5 Bq kg^?1 and 667 ± 281 Bq kg^?1, respectively. The average soil radionuclides' concentrations of Kirklareli were within the worldwide range although some extreme values had been determined. Annual effective gamma doses and the excess lifetime risks of cancer were higher than the world's average.     

Associations between PBDEs in office air,dust, and surface wipes

Increased use of flame-retardants in office furniture may increase exposure to PBDEs in the office environment. However, partitioning of PBDEs within the office environment is not well understood. Our objectives were to examine relationships between concurrent measures of PBDEs in office air, floor dust, and surface wipes.We collected air, dust, and surface wipe samples from 31 offices in Boston, MA. Correlation and linear regression were used to evaluate associations between variables. Geometric mean (GM) concentrations of individual BDE congeners in air and congener specific octanol–air partition coefficients (K_oa) were used to predict GM concentrations in dust and surface wipes and compared to the measured concentrations.GM concentrations of PentaBDEs in office air, dust, and surface wipes were 472 pg/m³, 2411 ng/g, and 77 pg/cm², respectively. BDE209 was detected in 100% of dust samples (GM = 4202 ng/g), 93% of surface wipes (GM = 125 pg/cm²), and 39% of air samples. PentaBDEs in dust and air were moderately correlated with each other (r = 0.60, p = 0.0003), as well as with PentaBDEs in surface wipes (r = 0.51, p = 0.003 for both dust and air). BDE209 in dust was correlated with BDE209 in surface wipes (r = 0.69, p = 0.007). Building (three categories) and PentaBDEs in dust were independent predictors of PentaBDEs in both air and surface wipes, together explaining 50% (p = 0.0009) and 48% (p = 0.001) of the variation respectively. Predicted and measured concentrations of individual BDE congeners were highly correlated in dust (r = 0.98, p < 0.0001) and surface wipes (r = 0.94, p = 002). BDE209 provided an interesting test of this equilibrium partitioning model as it is a low volatility compound.Associations between PentaBDEs in multiple sampling media suggest that collecting dust or surface wipes may be a convenient method of characterizing exposure in the indoor environment. The volatility of individual congeners, as well as physical characteristics of the indoor environment, influence relationships between PBDEs in air, dust, and surface wipes.     

Perfluoroalkyl substances and extractable organic fluorine in surface sediments and cores from Lake Ontario

Fourteen perfluoroalkyl substances (PFASs) including short-chain perfluorocarboxylates (PFCAs, C4–C6) and perfluoroalkane sulfonates (PFSAs, C4 and C6) were measured in surface sediment samples from 26 stations collected in 2008 and sediment core samples from three stations (Niagara, Mississauga, and Rochester basins) collected in 2006 in Lake Ontario. Perfluorooctanesulfonate (PFOS), perfluorooctanoate (PFOA), perfluorononanoate (PFNA), perfluorodecanoate (PFDA), and perfluoroundecanoate (PFUnDA) were detected in all 26 surface sediment samples, whereas perfluorohexane sulfonate (PFHxS), perfluorooctane sulfonamide (FOSA), perfluorododecanoate (PFDoDA) and perfluorobutanoate (PFBA) were detected in over 70% of the surface sediment samples. PFOS was detected in all of the sediment core samples (range: 0.492–30.1 ng g^− 1 d.w.) over the period 1952–2005. The C8 to C11 PFCAs, FOSA, and PFBA increased in early 1970s. An overall increasing trend in sediment PFAS concentrations/fluxes from older to more recently deposited sediments was evident in the three sediment cores. The known PFCAs and PFSAs accounted for 2–44% of the anionic fraction of the extractable organic fluorine in surface sediment, suggesting that a large proportion of fluorine in this fraction remained unknown. Sediment core samples collected from Niagara basin showed an increase in unidentified organic fluorine in recent years (1995–2006). These results suggest that the use and manufacture of fluorinated organic compounds other than known PFCAs and PFSAs has diversified and increased.     

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.     

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.     

Can polychlorinated biphenyl (PCB) signatures and enantiomer fractions be used for source identification and to age date occupational exposure?

Detailed polychlorinated biphenyl (PCB) signatures and chiral Enantiomer Fractions (EFs) of CB-95, CB-136 and CB-149 were measured for 30 workers at a transformer dismantling plant. This was undertaken to identify sources of exposure and investigate changes to the PCB signature and EFs over different exposure periods. Approximately 1.5 g of serum was extracted and PCB signatures were created through analysis by comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry (GC × GC–TOFMS) and EFs calculated following analysis by gas chromatography with high resolution mass spectrometry (GC–HRMS). A total of 84 PCBs were identified in the serum samples with concentrations of the 7 indicator PCBs ranging from 11–350 ng g^− 1 of serum (1.2–39 μg g^− 1 lipid). The PCB signatures were interpreted using principal component analysis (PCA) which was able to distinguish workers with background or recent minimal exposure from those with prolonged occupational exposure. Occupationally exposed individuals had a similar PCB profile to Aroclor A1260. However, individuals with prolonged exposure had depleted proportions of several PCB congeners that are susceptible to metabolism (CB-95, CB-101 and CB-151) and elevated proportions of PCBs that are resistant to metabolism (CB-74, CB-153, CB-138 and CB-180). The results also identified a third group of workers with elevated proportions of CB-28, CB-60, CB-66, CB-74, CB-105 and CB-118 who appeared to have been exposed to an additional source of PCBs. The results show near complete removal of the CB-95 E2 enantiomer in some samples, indicating that bioselective metabolism or preferential excretion of one enantiomer occurs in humans. By considering PCB concentrations along with detailed congener specific signatures it was possible to identify different exposure sources, and gain an insight into both the magnitude and duration of exposure.     

Sorption of trihalomethanes in foods

Trihalomethanes (THMs, namely, CHCl₃, CHCl₂Br, CHClBr₂ and CHBr₃) are disinfection by-products that are present in drinking water. These toxic chemicals are also present in meat, dairy products, vegetables, baked goods, beverages and other foods, although information regarding their concentrations and origin is very limited. This study investigates sorption of THMs occurring during rinsing and cooking of foods and the significance of food as an exposure source.Initial estimates of THM uptake were measured in experiments representing rinsing with tap water at 25 C using nine types of food, and for cooking in tap water at 90 C for fourteen other foods. A subset of foods was then selected for further study over a range of THM concentrations (23.7–118.7 μg/l), temperatures (25 C and 90 C), food concentrations (0.2–1.4, food weight: water weight), and contact times (5–240 min). Data were analyzed using regression and exponential models, and diffusion models were used to help explain the trends of THM uptake.Among vegetables, sorbed THM concentrations at 25 C were 213 to 774 ng/g for CHCl₃, 53 to 609 ng/g for CHCl₂Br, and 150–845 ng/g for CHClBr₂. Meats at 90 C tended to have higher concentrations, e.g., 870–2634 ng/g for CHCl₃. Sorbed concentrations increased with contact time and THM concentration, and decreased with food concentration in rinsing tests (using spinach, iceberg-head lettuce and cauliflower) and cooking tests (using tomato, potato, beef and miso–tofu soup). For most foods, THM uptake was diffusion limited and several hours were needed to approach steady-state levels. Swelling, hydrolysis and other physical and chemical changes in the food can significantly affect sorption. Screening level estimates for CHCl₃ exposures, based on experimental results and typical food consumption patterns, show that uptake via foods can dominate that due to direct tap water consumption, suggesting the importance of sorption and the need for further evaluation of THM intake due to foods.     

Recreational swimmers' exposure to Vibrio vulnificus and Vibrio parahaemolyticus in the Chesapeake Bay,Maryland, USA

Vibrio vulnificus and Vibrio parahaemolyticus are ubiquitous in the marine–estuarine environment, but the magnitude of human non-ingestion exposure to these waterborne pathogens is largely unknown. We evaluated the magnitude of dermal exposure to V. vulnificus and V. parahaemolyticus among swimmers recreating in Vibrio-populated waters by conducting swim studies at four swimming locations in the Chesapeake Bay in 2009 and 2011. Volunteers (n = 31) swam for set time periods, and surface water (n = 25) and handwash (n = 250) samples were collected. Samples were analyzed for Vibrio concentrations using quantitative PCR. Linear and logistic regressions were used to evaluate factors associated with recreational exposures. Mean surface water V. vulnificus and V. parahaemolyticus concentrations were 1128 CFU mL^− 1 (95% confidence interval (CI): 665.6, 1591.4) and 18 CFU mL^− 1 (95% CI: 9.8, 26.1), respectively, across all sampling locations. Mean Vibrio concentrations in handwash samples (V. vulnificus, 180 CFU cm^− 2 (95% CI: 136.6, 222.5); V. parahaemolyticus, 3 CFU cm^− 2 (95% CI: 2.4, 3.7)) were significantly associated with Vibrio concentrations in surface water (V. vulnificus, p < 0.01; V. parahaemolyticus, p < 0.01), but not with salinity or temperature (V. vulnificus, p = 0.52, p = 0.17; V. parahaemolyticus, p = 0.82, p = 0.06). Handwashing reduced V. vulnificus and V. parahaemolyticus on subjects' hands by approximately one log (93.9%, 89.4%, respectively). It can be concluded that when Chesapeake Bay surface waters are characterized by elevated concentrations of Vibrio, swimmers and individuals working in those waters could experience significant dermal exposures to V. vulnificus and V. parahaemolyticus, increasing their risk of infection.     

Priority and emerging flame retardants in rivers: Occurrence in water and sediment,Daphnia magna toxicity and risk assessment

The occurrence, partitioning and risk of eight polybrominated diphenyl ethers (PBDEs), nine new brominated (NBFRs) and ten organophosphorus flame retardants (OPFRs) were evaluated in three Spanish rivers suffering different anthropogenic pressures (Nalón, Arga and Besòs). OPFRs were ubiquitous contaminants in water (ΣOPFRs ranging from 0.0076 to 7.2 μg L^− 1) and sediments (ΣOPFRs ranging 3.8 to 824 μg kg^− 1). Brominated flame retardants were not detected in waters, whereas ΣPBDEs ranged from 88 to 812 μg kg^− 1 and decabromodiphenyl ethane (DBDPE) reached 435 μg kg^− 1 in sediments from the River Besòs, the most impacted river. The occurrence of flame retardants in river water and sediment was clearly associated with human activities, since the highest levels occurred near urban and industrial zones and after wastewater treatment plants discharge. Daphnia magna toxicity was carried out for OPFRs, the most ubiquitous flame retardants, considering individual compounds and mixtures. Toxicity of nine tested OPFRs differed largely among compounds, with EC₅₀ values ranging over three magnitude orders (0.31–381 mg L^− 1). Results evidenced that these compounds act by non-polar narcosis, since their toxicity was proportional to their lipophilicity (K_ow). Furthermore, their joint toxicity was additive, which means that single and joint toxicity can be predicted knowing their concentration levels in water using quantitative structure activity relationships (QSARs) and predictive mixture models. Based on these results, a risk assessment considering joint effect was performed calculating and summing risk quotients (RQs) for the water and sediment samples. No significant risk to D. magna (ΣRQs < 1) was observed for any of the monitored rivers.