Estrogen-, androgen- and aryl hydrocarbon receptor mediated activities in passive and composite samples from municipal waste and surface waters

Passive and composite sampling in combination with in vitro bioassays and identification and quantification of individual chemicals were applied to characterize pollution by compounds with several specific modes of action in urban area in the basin of two rivers, with 400,000 inhabitants and a variety of industrial activities. Two types of passive samplers, semipermeable membrane devices (SPMD) for hydrophobic contaminants and polar organic chemical integrative samplers (POCIS) for polar compounds such as pesticides and pharmaceuticals, were used to sample wastewater treatment plant (WWTP) influent and effluent as well as rivers upstream and downstream of the urban complex and the WWTP. Compounds with endocrine disruptive potency were detected in river water and WWTP influent and effluent. Year-round, monthly assessment of waste waters by bioassays documented estrogenic, androgenic and dioxin-like potency as well as cytotoxicity in influent waters of the WWTP and allowed characterization of seasonal variability of these biological potentials in waste waters. The WWTP effectively removed cytotoxic compounds, xenoestrogens and xenoandrogens. There was significant variability in treatment efficiency of dioxin-like potency. The study indicates that the WWTP, despite its up-to-date technology, can contribute endocrine disrupting compounds to the river. Riverine samples exhibited dioxin-like, antiestrogenic and antiandrogenic potencies. The study design enabled characterization of effects of the urban complex and the WWTP on the river. Concentrations of PAHs and contaminants and specific biological potencies sampled by POCIS decreased as a function of distance from the city.     

Human dietary intake of organohalogen contaminants at e-waste recycling sites in Eastern China

This study reports concentrations and human dietary intake of hexabromocyclododecanes (HBCDs), polychlorinated biphenyls (PCBs) as well as selected “novel” brominated flame retardants (NBFRs) and organochlorine pesticides, in ten staple food categories. Samples were sourced from areas in Taizhou City, eastern China, where rudimentary recycling and disposal of e-waste is commonplace, as well as from nearby non-e-waste impacted control areas. In most instances, concentrations in foods from e-waste recycling areas exceeded those from control locations. Concentrations of 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EH-TBB) and bis-(2-ethylhexyl)-3,4,5,6-tetrabromophthalate (BEH-TBP) in samples from e-waste sites were 3.09–62.2 ng/g and 0.81–16.3 ng/g lipid weight (lw), respectively; exceeding consistently those in foods acquired from control sites by an order of magnitude in many cases. In contrast, while concentrations of HBCD in some foods from e-waste impacted areas exceed those from control locations; concentrations in pork, shrimp, and duck liver are higher in control samples. This highlights the potential significance of non-e-waste sources of HBCD (e.g. building insulation foam) in our study areas. While concentrations of DDT in all foods examined except pork were higher in e-waste impacted samples than controls; our exposure estimates were well below the provisional tolerable daily intake of 0.01 mg/kg bw/day derived by the Joint FAO/WHO Meeting on Pesticide Residues. Concentrations of ΣPCBs resulted in exposures (650 and 2340 ng/kg bw/day for adults and children respectively) that exceed substantially the Minimal Risk Levels (MRLs) for ΣPCBs of 20 ng/kg bw/day derived by the Agency for Toxic Substances & Disease Registry. Moreover, when expressed in terms of dioxin-like toxicity equivalency based on the four dioxin-like PCBs monitored in this study (DL-PCBs) (PCB-105, 118, 156, and 167); concentrations in e-waste impacted foods exceed limits set by the European Union in 6 of the 8 food groups studied and result in dietary exposures for children (10.2 pg TEQ/kg bw/day) that exceed the WHO tolerable daily intake of 1–4 pg TEQ/kg bw/day.     

Dietary intake of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) from fish and meat by residents of Nanjing,China

Concentrations of 14 polybrominated diphenyl ether (PBDEs) and 28 polychlorinated biphenyl (PCBs) congers were measured in 137 samples of fish and meat from Nanjing, a city in the Yangtze River Delta, China. Total concentrations of PBDEs were less in fish (mean of 180 pg/g ww; range 8.0–1100 pg/g ww), but more in non fish foods (mean of 180 pg/g ww; range 15–950 pg/g ww) than those reported from other countries. The total dietary intake of PBDEs and PCBs by humans were 9.9 ng PBDE/d and 870 ng PCB/d, respectively. The daily intake by a 60 kg adult of 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEQ_WHO) from PCBs was estimated to be 49 pg ^PCBTEQ_WHO/d (0.82 pg ^PCBTEQ_WHO/kg bw), which is less than the tolerable daily intake suggested by the World Health Organization (WHO). The daily intake of meat and fish accounted for 57.2% and 42.8% of the total intake of ^PCBTEQ_WHO.     

Human exposure pathways to organophosphate triesters — A biomonitoring study of mother–child pairs

The worldwide ban of several formulations of brominated flame retardants has caused an increase in the production of organophosphorus flame retardants (PFRs) to meet the existing fire regulations for a wide range of household products. This biomonitoring study surveys the occurrence of the metabolites from PFRs and related plasticizers (dialkyl and diaryl phosphates; DAPs) in urine from a Norwegian mother–child cohort (48 mothers and 54 children). Concentrations of DAPs were higher in the children than in their mothers (Wilcoxon signed-rank test p = 0.001). Median urinary concentrations of diphenyl phosphate (DPHP) were 1.1 and 0.51 ng/mL in children and mothers, respectively, followed by bis(1,3-dichloro-2-propyl) phosphate (BDCIPP) with medians of 0.23 and 0.12 ng/mL, respectively. Detection frequencies for bis(2-butoxyethyl) phosphate (BBOEP) in urine from children and mothers were 32 and 1%, respectively (median < 0.18 ng/mL), and for di-n-butyl phosphate (DNBP) 15 and 8%, respectively (median < 0.12 ng/mL). The concentrations of DPHP and BDCIPP in urine from children were significantly correlated with those found for their parent compounds in air and dust from the households (Spearman's rank correlations 0.30 < R_s < 0.36; p < 0.05). For mothers, only the urinary concentration of BDCIPP was correlated to its precursor in dust from the households (R_s = 0.40; p < 0.01), which might indicate higher impact of the household environment on children than mothers. A diurnal variability study of the mothers' urinary concentrations of DPHP and BDCIPP showed lower concentrations at time periods when women were likely to be outside the household. In contrast, no relevant associations between organophosphate metabolites in urine and food consumption data obtained through a 24 hour recall were seen. This suggests that the residential environment is a more important exposure pathway to PFRs than the diet.     

A comparative assessment of human exposure to tetrabromobisphenol A and eight bisphenols including bisphenol A via indoor dust ingestion in twelve countries

Tetrabromobisphenol A (TBBPA) and eight bisphenol analogues (BPs) including bisphenol A (BPA) were determined in 388 indoor (including homes and microenvironments) dust samples collected from 12 countries (China, Colombia, Greece, India, Japan, Kuwait, Pakistan, Romania, Saudi Arabia, South Korea, U.S., and Vietnam). The concentrations of TBBPA and sum of eight bisphenols (ƩBPs) in dust samples ranged from < 1 to 3600 and from 13 to 110,000 ng/g, respectively. The highest TBBPA concentrations in house dust were found in samples from Japan (median: 140 ng/g), followed by South Korea (84 ng/g) and China (23 ng/g). The highest ∑ BPs concentrations were found in Greece (median: 3900 ng/g), Japan (2600 ng/g) and the U.S. (2200 ng/g). Significant variations in BPA concentrations were found in dust samples collected from various microenvironments in offices and homes. Concentrations of TBBPA in house dust were significantly correlated with BPA and ∑ BPs. Among the nine target chemicals analyzed, BPA was the predominant compound in dust from all countries. The proportion of TBBPA in sum concentrations of nine phenolic compounds analyzed in this study was the highest in dust samples from China (27%) and the lowest in Greece (0.41%). The median estimated daily intake (EDI) of ∑ BPs through dust ingestion was the highest in Greece (1.6–17 ng/kg bw/day), Japan (1.3–16) and the U.S. (0.89–9.6) for various age groups. Nevertheless, in comparison with the reported BPA exposure doses through diet, dust ingestion accounted for less than 10% of the total exposure doses in China and the U.S. For TBBPA, the EDI for infants and toddlers ranged from 0.01 to 3.4 ng/kg bw/day, and dust ingestion is an important pathway for exposure accounting for 3.8–35% (median) of exposure doses in China.     

Can starling eggs be useful as a biomonitoring tool to study organohalogenated contaminants on a worldwide scale?

Large-scale international monitoring studies are important to assess emission patterns and environmental distributions of organohalogenated contaminants (OHCs) on a worldwide scale. In this study, the presence of OHCs was investigated on three continents (Europe, North America and Australasia), using eggs of starlings (Sturnus vulgaris and Sturnus unicolor) to assess their suitability for large-scale monitoring studies. To the best of our knowledge, this is the first study using bird eggs of the same species as a biomonitor for OHCs on an intercontinental scale. We found significant differences in OHC concentrations of the eggs among sampling locations, except for hexachlorocyclohexanes (HCHs). Mean concentrations of sum polychlorinated biphenyls (PCBs) in eggs ranged from 78 ± 26 ng/g lipid weight (lw) in Australia to 2900 ± 1300 ng/g lw in the United States. The PCB profile was dominated by CB 153 and CB 138 in all locations, except for New Zealand, where the contribution of CB 95, CB 101 and CB 149 was also high. The highest mean sum polybrominated diphenyl ether (PBDE) concentrations were found in Canada (4400 ± 830 ng/g lw), while the lowest mean PBDE concentrations were measured in Spain (3.7 ± 0.1 ng/g lw). The PBDE profile in starling eggs was dominated by BDE 47 and BDE 99 in all countries, but in Belgium, the higher brominated PBDEs had a higher contribution compared to other countries. For the organochlorine pesticides (OCPs), dichlorodiphenyltrichloroethanes (DDTs) ranged from 110 ± 16 ng/g lw in France to 17,000 ± 3400 ng/g lw in New Zealand, while HCHs and hexachlorobenzene were generally in low concentrations in all sampling locations. Chlordanes were remarkably high in eggs from the United States (2500 ± 1300 ng/g lw). The OCP profile in all countries was largely dominated by p,p′-DDE. In general, the worldwide trends we observed in starling eggs were in accordance with the literature on human and environmental OHC data, which suggests that there is potential for using starling eggs as a biomonitoring tool on a large geographical scale.     

Brominated flame retardants in the indoor environment — Comparative study of indoor contamination from three countries

Concentrations of more than 20 brominated flame retardants (FRs), including polybrominated diphenyl ethers (PBDEs) and emerging FRs, were measured in air, dust and window wipes from 63 homes in Canada, the Czech Republic and the United States in the spring and summer of 2013. Among the PBDEs, the highest concentrations were generally BDE-209 in all three matrices, followed by Penta-BDEs. Among alternative FRs, EHTBB and BEHTBP were detected at the highest concentrations. DBDPE was also a major alternative FR detected in dust and air. Bromobenzenes were detected at lower levels than PBDEs and other alternative FRs; among the bromobenzenes, HBB and PBEB were the most abundant compounds. In general, FR levels were highest in the US and lowest in the Czech Republic — a geographic trend that reflects the flame retardants' market. No statistically significant differences were detected between bedroom and living room FR concentrations in the same house (n = 10), suggesting that sources of FRs are widespread indoors and mixing between rooms. The concentrations of FRs in air, dust, and window film were significantly correlated, especially for PBDEs. We found a significant relationship between the concentrations in dust and window film and in the gas phase for FRs with log K_OA values < 14, suggesting that equilibrium was reached for these but not compounds with log K_OA values > 14. This hypothesis was confirmed by a large discrepancy between values predicted using a partitioning model and the measured values for FRs with log K_OA values > 14.     

Perfluorinated compounds in surface waters from Northern China: Comparison to level of industrialization

Inclusion of Perfluorooctane Sulfonate (PFOS) in the Stockholm Convention because of its exemptions, has resulted in increased annual production of PFOS-containing chemicals in China to accommodate domestic and overseas demands. Accordingly, concern about environmental contamination with perfluorinated compounds (PFCs), such as PFOS, has arisen. However, little information is available on the status and trends in the distribution, sources or risk of PFCs in aquatic environments of China. In the present study, forty two surface water samples collected from five regions with different levels of industrialization were monitored for concentrations of PFCs by use of solid phase extraction and LC/MS/MS. Mean concentrations (maximum concentration) of PFOA and PFOS, which were the dominant PFCs, were 1.2 (2.3) and 0.16 (0.52) ng/l for Guanting, 1.2 (1.8) and 0.32 (1.1) ng/l for Hohhot, 2.7 (15) and 0.93 (5.7) ng/l for Shanxi, 6.8 (12) and 2.6 (11) ng/l for Tianjin, 27 (82) and 4.7 (31) ng/l for Liaoning, respectively. The greatest concentrations of PFCs (121 ng/l), PFOA (82 ng/l) and PFOS (31 ng/l) were observed in Liaoning, which might originate from tributaries of the Liaohe River, the most polluted watershed in Northeast China. While, concentrations of PFCs in the Guanting and Hohhot regions were 3 to 20 fold less than those from Tianjin and Liaoning. This result is consistent with little contribution of PFCs being released from agricultural and non-industrial activities. The magnitudes of mass flow for PFOA and PFOS in decreasing order were: Guanting < Hohhot < Tianjin < Liaoning < Shanxi and Guanting < Hohhot < Shanxi < Tianjin < Liaoning. The larger mass flows of PFOS were accompanied by relatively larger magnitudes of PFOA. Concentrations of both PFOA and PFOS in waters from all regions were less than suggested allowable concentrations. However, the relatively greater concentrations of PFCs in Tianjin and Liaoning suggest that further studies characterizing their sources and potential risk to both humans and wildlife are needed.     

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.     

Spatiotemporal analysis and human exposure assessment on polycyclic aromatic hydrocarbons in indoor air,settled house dust,and diet: A review

This review summarizes the published literature on the presence of polycyclic aromatic hydrocarbons (PAH) in indoor air, settled house dust, and food, and highlights geographical and temporal trends in indoor PAH contamination. In both indoor air and dust, ΣPAH concentrations in North America have decreased over the past 30 years with a halving time of 6.7 ± 1.9 years in indoor air and 5.0 ± 2.3 years in indoor dust. In contrast, indoor PAH concentrations in Asia have remained steady. Concentrations of ΣPAH in indoor air are significantly (p < 0.01) higher in Asia than North America. In studies recording both vapor and particulate phases, the global average concentration in indoor air of ΣPAH excluding naphthalene is between 7 and 14,300 ng/m³. Over a similar period, the average ΣPAH concentration in house dust ranges between 127 to 115,817 ng/g. Indoor/outdoor ratios of atmospheric concentrations of ΣPAH have declined globally with a half-life of 6.3 ± 2.3 years. While indoor/outdoor ratios for benzo[a]pyrene toxicity equivalents (BaP_eq) declined in North America with a half-life of 12.2 ± 3.2 years, no significant decline was observed when data from all regions were considered. Comparison of the global database, revealed that I/O ratios for ΣPAH (average = 4.3 ± 1.3), exceeded significantly those of BaP_eq (average = 1.7 ± 0.4) in the same samples. The significant decline in global I/O ratios suggests that indoor sources of PAH have been controlled more effectively than outdoor sources. Moreover, the significantly higher I/O ratios for ΣPAH compared to BaP_eq, imply that indoor sources of PAH emit proportionally more of the less carcinogenic PAH than outdoor sources. Dietary exposure to PAH ranges from 137 to 55,000 ng/day. Definitive spatiotemporal trends in dietary exposure were precluded due to relatively small number of relevant studies. However, although reported in only one study, PAH concentrations in Chinese diets exceeded those in diet from other parts of the world, a pattern consistent with the spatial trends observed for concentrations of PAH in indoor air. Evaluation of human exposure to ΣPAH via inhalation, dust and diet ingestion, suggests that while intake via diet and inhalation exceeds that via dust ingestion; all three pathways contribute and merit continued assessment.     

4-Nonylphenol and bisphenol A in Swedish food and exposure in Swedish nursing women

4-Nonylphenol (NP) and bisphenol A (BPA) are phenolic substances used in high volumes by the industry. Studies on cells and in experimental animals have shown that both these compounds can be classified as estrogenic hormone disrupters. Information about the exposure of humans to NP and BPA is still scarce, especially regarding levels in human blood. The first aim of this study was to investigate possible sources of NP and BPA exposure from food, by analyzing the levels of NP and BPA from a Swedish food market basket, based on the Swedish per capita food consumption. A second aim was to investigate blood serum levels of NP and BPA, as well as NP-ethoxylates, among young women in Sweden (n = 100). Moreover, associations between food consumption and blood NP and BPA levels were studied. In food, NP was to some extent found at levels above limit of quantification (LOQ 20 ng/g fresh weight) in fruits, cereal products, vegetables, and potatoes. BPA levels above LOQ (2 ng/g fresh weight) were found in fish, meats, potatoes, and dairy products. The estimated mean intakes per capita were (medium bound) 27 μg NP/day and 3.9 μg BPA/day, showing that food is a source of BPA and NP in the general Swedish population. In blood serum, free NP above limit of detection (LOD 0.5 ng/g) was detected in 46% of the study participants while detectable levels of total NP (LOD 0.8 ng/g) were observed in 43%. The corresponding percentages for BPA were 25% and 22%, respectively. The results indicate that there is a continuous source of exposure to NP and BPA that is high enough for free NP and BPA to be detected in some consumers. Among the participants with quantifiable levels of free and total NP (n = 38), 85% (median, range: 38–112%) of the NP was present as free NP. For BPA 76% (49–109%) was detected as free BPA (n = 15). All women had levels of ethoxylates of NP below LOD (0.1–0.7 ng/g). A significantly higher total consumption of fruits and vegetables was reported in questionnaires by participants with NP levels at or above LOD than among women with levels below LOD. This result is supporting the market basket results of relatively high NP levels in these types of food.     

Perfluoroalkyl acids in subarctic wild male mink (Neovison vison) in relation to age,season and geographical area

This study investigates the influence of biological and environmental factors on the concentrations of perfluoroalkyl acids (PFAAs) in a top predator; the American mink. Perfluorobutane sulfonate (PFBS), perfluorohexane sulfonate (PFHxS), perfluorooctane sulfonate (PFOS) and perfluoroalkyl carboxylates (PFCAs) with C₈–C₁₃ perfluorinated carbon chains were analyzed in livers from wild male mink liver (n = 101) from four areas in Sweden representing two inland environments (rural and highly anthropogenic, respectively) and two different coastal environments. Mean PFOS concentrations were 1250 ng/g wet weight and some mink from the urban inland area had among the highest PFOS concentrations ever recorded in mink (up to 21 800 ng/g wet weight). PFBS was detected in 89% of the samples, but in low concentrations (mean 0.6 ng/g ww). There were significant differences in PFAA concentrations between the geographical areas (p < 0.001–0.01). Age, body condition and body weight did not influence the concentrations significantly, but there was a seasonal influence on the concentrations of perfluorodecanoic acid (PFDA) and perfluoroundecanoic acid (PFUnDA) (p < 0.01 and p < 0.05, respectively), with lower concentrations in autumn samples than in samples taken in the winter and spring. It is thus recommended to take possible seasonal differences into account when using mink exposure data. The overall results suggest that the mink is a suitable sentinel species for assessing and monitoring environmental levels of PFAAs.     

Evaluation of air quality indicators in Alberta,Canada – An international perspective

There has been an increase in oil sands development in northern Alberta, Canada and an overall increase in economic activity in the province in recent years. An evaluation of the state of air quality was conducted in four Alberta locations – urban centers of Calgary and Edmonton, and smaller communities of Fort McKay and Fort McMurray in the Athabasca Oil Sands Region (AOSR). Concentration trends, diurnal hourly and monthly average concentration profiles, and exceedances of provincial, national and international air quality guidelines were assessed for several criteria air pollutants over the period 1998 to 2014. Two methods were used to evaluate trends. Parametric analysis of annual median 1 h concentrations and non-parametric analysis of annual geometric mean 1 h concentrations showed consistent decreasing trends for NO₂ and SO₂ (< 1 ppb per year), CO (< 0.1 ppm per year) at all stations, decreasing for THC (< 0.1 ppm per year) and increasing for O₃ (≤ 0.52 ppb per year) at most stations and unchanged for PM_2.5 at all stations in Edmonton and Calgary over a 17-year period. Little consistency in trends was observed among the methods for the same air pollutants other than for THC (increasing in Fort McKay < 0.1 ppm per year and no trend in Fort McMurray), PM_2.5 in Fort McKay and Fort McMurray (no trend) and CO (decreasing < 0.1 ppm per year in Fort McMurray) over the same period. Levels of air quality indicators at the four locations were compared with other Canadian and international urban areas to judge the current state of air quality. Median and annual average concentrations for Alberta locations tended to be the smallest in Fort McKay and Fort McMurray. Other than for PM_2.5, Calgary and Edmonton tended to have median and annual average concentrations comparable to and/or below that of larger populated Canadian and U.S. cities, depending upon the air pollutant.     

Multimycotoxin analysis in urines to assess infant exposure: A case study in Cameroon

This study was conducted to investigate mycotoxin exposure in children (n = 220, aged 1.5–4.5 years) from high mycotoxin contamination regions of Cameroon and to examine the association between the mycotoxin levels (in total 18 analytes) and several socio-demographic factors and anthropometric characteristics. A cross-sectional study was conducted in six villages in Cameroon with 220 children. Mycotoxins and their metabolites were detected in 160/220 (73%) urine samples.There were significant differences in the mean contamination levels of ochratoxin A (p = 0.01) and β-zearalenol (p = 0.017) between the two agro-ecological zones investigated. Likewise significant differences were observed in the mean levels of aflatoxin M₁ (p = 0.001) across the weaning categories of these children. The mean concentration of aflatoxin M₁ detected in the urine of the partially breastfed children (1.43 ng/mL) was significantly higher (p = 0.001) than those of the fully weaned children (0.282 ng/mL).Meanwhile, the mean concentrations of deoxynivalenol (3.0 ng/mL) and fumonisin B₁ (0.59 ng/mL) detected in the urine of the male children was significantly (p value 0.021 for deoxynivalenol and 0.004 for fumonisin B₁) different from the levels detected in the urine of female children; 0.71 ng/mL and 0.01 ng/mL for deoxynivalenol and fumonisin B₁ respectively. In this study, there was no association between the different malnutrition categories (stunted, wasting and underweight) and the mycotoxin concentrations detected in the urine of these children.However, there is sufficient evidence to suggest that children in Cameroon under the age 5 are exposed to high levels of carcinogenic substances such as fumonisin B₁, aflatoxin M₁ and ochratoxin A through breastfeeding. To the best of our knowledge, this is the first report of its kind carried out in West Africa to determine multi-mycotoxin exposure in infants.     

Exploring the fate,transport and risk of Perfluorooctane Sulfonate (PFOS) in a coastal region of China using a multimedia model

Perfluorooctane Sulfonate (PFOS) and related substances have been widely applied in both industrial processes and domestic products in China. Exploring the environmental fate and transport of PFOS using modeling methods provides an important link between emission and multimedia diffusion which forms a vital part in the human health risk assessment and chemical management for these substances. In this study, the gridded fugacity based BETR model was modified to make it more suitable to model transfer processes of PFOS in a coastal region, including changes to PFOS partition coefficients to reflect the influence of water salinity on its sorption behavior. The fate and transport of PFOS in the Bohai coastal region of China were simulated under steady state with the modified version of the model. Spatially distributed emissions of PFOS and related substances in 2010 were estimated and used in these simulations. Four different emission scenarios were investigated, in which a range of half-lives for PFOS related substances were considered. Concentrations of PFOS in air, vegetation, soil, fresh water, fresh water sediment and coastal water were derived from the model under the steady-state assumption. The median modeled PFOS concentrations in fresh water, fresh water sediment and soil were 7.20 ng/L, 0.39 ng/g and 0.21 ng/g, respectively, under Emission Scenario 2 (which assumed all PFOS related substances immediately degrade to PFOS) for the whole region, while the maximum concentrations were 47.10 ng/L, 4.98 ng/g and 2.49 ng/g, respectively. Measured concentration data for PFOS in the Bohai coastal region around the year of 2010 were collected from the literature. The reliability of the model results was evaluated by comparing the range of modeled concentrations with the measured data, which generally matched well for the main compartments. Fate and transfer fluxes were derived from the model based on the calculated inventory within the compartments, transfer fluxes between compartments and advection fluxes between sub-regions. It showed that soil and costal water were likely to be the most important sinks of PFOS in the Bohai costal region, in which more than 90% of PFOS was stored. Flows of fresh water were the driving force for spatial transport of PFOS in this region. Influences of the seasonal change of fresh water fluxes on the model results were also analyzed. When only seasonal changes of the fresh water flow rates were considered, concentrations of PFOS in winter and spring were predicted to be higher than that under annual average conditions, while the concentrations in summer and autumn were lower. For PFOS fluxes entering the sea, opposite conclusions were drawn compared to the concentrations. Environmental risks from the presence of PFOS in fresh water were assessed for this region through comparison with available water quality criteria values. The predicted concentrations of PFOS in the Bohai coastal region provided by the model were lower than the water quality criteria published by the United States Environmental Protection Agency and Chinese researchers, while the concentrations in more than 80% of the sampling locations exceeded the European Union Water Framework Directive Environmental Quality Standards values. Seasonal variations of flow rate might cause a significant increase in environmental risks.     

Persistent organic pollutants in the Scheldt estuary: Environmental distribution and bioaccumulation

Levels of polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and organochlorine pesticides (OCPs) were determined in the sediment and several species (European flounder, Platichthys flesus; common sole, Solea solea; Chinese mitten crab, Eriocheir sinensis; shore crab, Carcinus maenas; brown shrimp, Crangon crangon; blue mussel, Mytilus edulis and bristle worms, Polychaeta) from 7 locations in the Scheldt estuary (SE, the Netherlands–Belgium). Overall POP levels in the sediment were low. The average PCB and PBDE concentrations were respectively 31.5 and 115 ng/g dry weight (dw). Highest sediment loads were measured in the vicinity of Antwerp (368 ng PCBs/g dw), a location with intense harbor and industrial activities. Pollution concentrations in the tissues of biota were species-specific. Blue mussels contained the highest lipid concentrations (2.74 ± 0.55%) and reached the highest contamination levels (from 287 to 1688 ng PCBs/g ww, from 2.09 to 12.4 ng PBDEs/g ww). Lowest tissue loads were measured in brown shrimp (from 3.27 to 39.9 ng PCBs/g ww, from 0.05 to 0.47 ng PBDEs/g ww). The PCB congener profile in most of the species was similar with the pattern found in the sediment. PCB 153 was the most abundant congener (16.5–25.7% in biota, 10.4% in sediment). In the sediment, the total amount of PBDEs consisted for more than 99% of BDE 209. Congener BDE 47 had the highest concentrations in all sampled species (38.5–70.1%). Sediment POP loadings and tissue concentrations were poorly correlated, indicating that a simple linear or non-linear relationship is insufficient to describe this relationship, possible caused by the complexity of the bioaccumulation processes and the variability in exposure. Because of the high PCB levels, regular consumption of fish and seafood, especially mussels, from the Scheldt estuary should be avoided.     

Emission of artificial sweeteners,select pharmaceuticals,and personal care products through sewage sludge from wastewater treatment plants in Korea

Concern over the occurrence of artificial sweeteners (ASWs) as well as pharmaceuticals and personal care products (PPCPs) in the environment is growing, due to their high use and potential adverse effects on non-target organisms. The data for this study are drawn from a nationwide survey of ASWs in sewage sludge from 40 representative wastewater treatment plants (WWTPs) that receive domestic (WWTP_D), industrial (WWTP_I), or mixed (domestic plus industrial; WWTP_M) wastewaters in Korea. Five ASWs (concentrations ranged from 7.08 to 5220 ng/g dry weight [dw]) and ten PPCPs (4.95–6930 ng/g dw) were determined in sludge. Aspartame (concentrations ranged from 28.4 to 5220 ng/g dw) was determined for the first time in sewage sludge. The median concentrations of ASWs and PPCPs in sludge from domestic WWTPs were 0.8–2.5 and 1.0–3.4 times, respectively, the concentrations found in WWTPs that receive combined domestic and industrial wastewaters. Among the five ASWs analyzed, the median environmental emission rates of aspartame through domestic WWTPs (both sludge and effluent discharges combined) were calculated to be 417 μg/capita/day, followed by sucralose (117 μg/capita/day), acesulfame (90 μg/capita/day), and saccharin (66 μg/capita/day). The per-capita emission rates of select PPCPs, such as antimicrobials (triclocarban: 158 μg/capita/day) and analgesics (acetaminophen: 59 μg/capita/day), were an order of magnitude higher than those calculated for antimycotic (miconazole) and anthelmintic (thiabendazole) drugs analyzed in this study. Multiple linear regression analysis of measured concentrations of ASWs and PPCPs in sludge revealed that several WWTP parameters, such as treatment capacity, population-served, sludge production rate, and hydraulic retention time could influence the concentrations found in sludge.     

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.     

Levels of selected persistent organic pollutants in blood from delivering women in seven selected areas of São Paulo State,Brazil

Persistent organic pollutants (POPs) present in the living environment are thought to have detrimental health effects on the population, with pregnant women and the developing foetus being at highest risk. We report on the levels of selected POPs in maternal blood of 155 delivering women residing in seven regions within the São Paulo State, Brazil.The following selected POPs were measured in the maternal whole blood: 12 polychlorinated biphenyls (PCBs) congeners (IUPAC Nos. 99, 101, 118, 138, 153, 156, 163, 170, 180, 183, 187, 194); dichlordiphenyltrichloroethane p,p′-DDT, diphenyldichloroethylene p,p′-DDE and other pesticides such as hexachlorocyclohexanes (α-HCH, β-HCH, γ-HCH), hexachlorobenzene (HCB), chlordane derivatives cis-chlordane, trans-chlordane, oxy-chlordane, cis-nonachlor and trans-nonachlor.Statistical comparisons between regions were performed only on compounds having concentrations above LOD in 70% of the samples. PCB118 congener was found to be highest in the industrial site (mean 4.97 ng/g lipids); PCB138 congener concentration was highest in the Urban 3 site (mean 4.27 ng/g lipids) and congener PCB153 was highest in the industrial and Urban 3 sites with mean concentration of 7.2 ng/g lipids and 5.89 ng/g lipids respectively. Large differences in levels of p,p′-DDE between regions were observed with the Urban 3 and industrial sites having the highest concentrations of 645 ng/g lipids and 417 ng/g lipids, respectively; β-HCH was found to be highest in the Rural 1 site; the γ-HCH in Rural 1 and industrial; the HCB in the Rural 1 and industrial sites and oxy-chlordane and t-NC in the Rural 2 sites. An association between levels of some contaminants and maternal age and parity was also found.     

Hydroxylated PCB metabolites (OH-PCBs) in archived serum from 1950–60s California mothers: A pilot study

We are studying participants selected from the Child Health and Development Studies (CHDS), a longitudinal birth cohort of over 20,000 California pregnancies between 1959 and 1967, for associations between maternal body burden of organochlorine contaminants and thyroid function. We designed a pilot study using 30 samples selected among samples with high and low PCB concentrations to evaluate the feasibility of measuring OH-PCBs in the larger study population. GC-ECD and GC-NCI/MS were used to determine PCBs and OH-PCBs as methyl derivatives, respectively. Maternal serum levels of Σ₁₁PCBs and Σ₈OH-PCB metabolites varied from 0.74 to 7.99 ng/mL wet wt. with a median of 3.05 ng/mL, and from 0.12 to 0.98 ng/mL wet wt. with a median of 0.39 ng/mL, respectively. Average concentrations of Σ₈OH-PCB metabolites in the high PCB group were significantly higher than those in the low PCB group (p < 0.05). The levels of OH-PCB metabolites were dependent on PCB levels (r = 0.58, p < 0.05) but approximately an order of magnitude lower (p < 0.05). The average ratio of Σ₈OH-PCBs to Σ₁₁PCBs was 0.14 ± 0.08. The primary metabolite was 4-OH-CB187 followed by 4-OH-CB107. Both of these metabolites interfere with the thyroid system in in vitro, animal, and human studies. OH-PCBs were detectable in all archived sera analyzed, supporting the feasibility to measure OH-PCB metabolites in the entire cohort.