Hydroxylated polybrominated diphenyl ethers (OH-PBDEs) in biosolids from municipal wastewater treatment plants in China

Hydroxylated polybrominated diphenyl ethers (OH-PBDEs) along with methoxylated polybrominated diphenyl ethers (MeO-PBDEs) have been frequently identified as natural compounds in marine environment and also assumed as metabolites of PBDEs. In the present study, nine OH-PBDE, nine MeO-PBDE and 10 PBDE congeners were studied in the sewage sludge collected from 36 municipal wastewater treatment plants (WWTPs) in 27 cities of China. The results suggest that OH-PBDEs and PBDEs are ubiquitous in sewage sludge in China, however, methoxylated PBDEs were not detectable. Composition profiles of detected OH-PBDE congeners were different depending on the sampling location. ΣOH-PBDEs in WWTPs sludge ranged from 0.04 to 2.24 ng g^?1 dry weight (mean: 0.35 ng g^?1 dry weight). The total amount of the two most prominent congeners (6-OH-BDE-47 + 2′-OH-BDE-68) accounted for about 53.3–100% of the sum of all six identified congeners. A significant linear relationship was found between 6-OH-BDE-47 and 2′-OH-BDE-68. A distinct geographical distribution of ΣOH-PBDEs was observed with greater concentrations of OH-PBDEs at coastal areas than inland regions in China.     

Debrominated,hydroxylated and methoxylated metabolism in maize (Zea mays L.) exposed to lesser polybrominated diphenyl ethers (PBDEs)

A hydroponic experiment was conducted to investigate the debrominated, hydroxylated and methoxylated metabolism of polybrominated diphenyl ethers (PBDEs, BDE-15, -28 and -47) in maize. A total of six debrominated metabolites (de-PBDEs), seven hydroxylated PBDEs (OH-PBDEs, including two unidentified OH-di-PBDEs and one unidentified OH-tri-PBDE) and four methoxylated PBDEs (MeO-PBDEs) were determined in the exposed plants. The metabolic products were detected in maize only after 12 h of exposure to the PBDEs. However, the concentration of each type of the metabolites (de-PBDEs, OH-PBDEs or MeO-PBDEs) decreased at the later exposure time, possibly due to further metabolism. The removal of a bromine atom or the introduction of a hydroxyl/methoxy group was easier at the ortho-positions on the biphenyl structure than at the para-positions. Concentration ratios of the total debrominated, hydroxylated or methoxylated metabolites to the parent congener (BDE-28 or -47) generally followed the order of leaves > stems ≫ roots, and MeO-PBDEs > de-PBDEs ≫ OH-PBDEs. These results suggest that metabolism occurred preferentially in leaves and stems than in roots. Less transformation and shorter elimination half-life of OH-PBDEs would contribute to the lower concentrations of OH-PBDEs than of de-PBDEs or MeO-PBDEs in maize.     

Dietary assessment of human exposure to PBDEs in South Korea

This study was conducted to measure the concentration of PBDEs in various food stuffs from Korea and to estimate levels of PBDE intake from food for the Korean population according to geographical location and age. 20 types of food samples were collected from four heavily populated cities (Seoul, Gwangju, Daejeon, Pusan) and one rural city (Gangneung) and were analyzed for 19 polybrominated diphenyl ether congeners (BDE 15, 17, 28, 33, 47, 49, 66, 71, 85, 99, 100, 119, 126, 138, 153, 154, 183, and 209).No significant differences in total PBDE levels in foods were found among four large cities (Gwangju; 10.91 ng g^?1 wet weight (ww), Seoul; 7.66 ng g^?1 ww, Daejeon; 6.91 ng g^?1 ww, Pusan; 6.87 ng g^?1 ww) and one rural city (Gangneung; 8.72 ng g^?1 ww). Daily dietary intake of PBDEs does not appear to be related to the extent of urbanization.Total dietary intake of PBDE for the average general population was 72.30 ng d^?1 (not detected (ND) = 0) which was similar to other countries. In all food groups, the largest contribution to PBDE intake was from fish and shellfish (48.96 ng d^?1). Total PBDE consumed per kilogram of body weight was estimated to range from 2.70 ng kg^?1 d^?1 for infants 1 through 2 years of age to 0.85 ng kg^?1 d for 65 years and older and was highest in young children and decreased with increasing age.     

High concentrations of persistent organic pollutants including PCBs,DDT, PBDEs and PFOS in little brown bats with white-nose syndrome in New York,USA

White-nose syndrome (WNS) is a condition associated with white fungal growth on ears, wings, and nose of hibernating bats; this condition has recently resulted in high bat mortality in the northeastern United States. Nevertheless, the pathogenesis of morbidity and mortality are still unknown. Elevated exposure to toxic contaminants could be a contributing factor via the consequent immunosuppression and endocrine disruption. In this study, diseased little brown bats (Myotis lucifugus) were collected from several hibernacula in eastern New York State in 2008. Fat tissues of bats were analyzed for polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls (PBBs), and organochlorine pesticides (OCPs; DDT, chlordanes, HCB, and HCH), and liver was analyzed for perfluorinated compounds (PFCs). A reference population of little brown bats, not affected by WNS, was also collected from a cave in Kentucky for the analysis of trace organic contaminants. Concentration of PCBs in fat tissues of bats from New York ranged from 1900 ng g^?1 to 35 000 ng g^?1, lipid wt, with the highest concentrations found in bats collected from caves in Albany County. High concentrations of PCBs were also found in bats from Kentucky (17 100–18 400 ng g^?1, lipid wt). Total PBDE concentrations in fat tissues ranged from 520 ng g^?1 to 10 900 ng g^?1, lipid wt, in bats from New York and from 4300 ng g^?1 to 13 000 ng g^?1, lipid wt, in bats from Kentucky. High concentrations of DDT (26 900 ng g^?1, lipid wt), chlordanes (6350 ng g^?1, lipid wt), and HCB (260 ng g^?1, lipid wt) were found in bats from New York. Concentrations of hexabromobiphenyl congener 153 (PBB 153) in bats from New York ranged from 8.6 ng g^?1 to 12 4000 ng g^?1, lipid wt. Concentrations of PFCs were on the order of a few tens to a few hundreds of nanograms per gram liver, on a wet weight basis. Overall, high concentrations of PCBs, PBDEs, DDT, and chlordanes were found in fat tissues of diseased bats from New York, although the concentrations in bats from non-diseased, reference population, from Kentucky were also high.     

Atmospheric distribution of polycyclic aromatic hydrocarbons and deposition to Galveston Bay,Texas, USA

Estimates of the atmospheric deposition to Galveston Bay of polycyclic aromatic hydrocarbons (PAHs) are made using precipitation and meteorological data that were collected continuously from 2 February 1995 to 6 August 1996 at Seabrook, TX, USA. Particulate and vapor phase PAHs in ambient air and particulate and dissolved phases in rain samples were collected and analyzed. More than 95% of atmospheric PAHs were in the vapor phase and about 73% of PAHs in the rain were in the dissolved phase. Phenanthrene and napthalene were the dominant compounds in air vapor and rain dissolved phases, respectively, while 5 and 6 ring PAH were predominant in the particulate phase of both air and rain samples. Total PAH concentrations ranged from 4 to 161 ng m⁻³ in air samples and from 50 to 312 ng l⁻¹ in rain samples. Temporal variability in total PAH air concentrations were observed, with lower concentrations in the spring and fall (4–34 ng m ⁻³) compared to the summer and winter (37–161 ng m⁻³). PAHs in the air near Galveston Bay are derived from both combustion and petroleum vaporization. Gas exchange from the atmosphere to the surface water is estimated to be the major deposition process for PAHs (1211 μg m^{− 2} yr^{− 1}), relative to wet deposition (130 μg m⁻² yr^{− 1}) and dry deposition (99 μg m⁻² yr^{− 1}). Annual deposition of PAHs directly to Galveston Bay from the atmosphere is estimated as 2  t yr⁻¹.     

Polychlorinated biphenyls (PCBs) and Polybrominated Diphenyl ethers (PBDEs) in three fish species from an estuary in the southeastern coast of Brazil

Polychlorinated biphenyls (PCBs) and Polybrominated Diphenyls Ethers (PBDEs) are two highly lipophilic classes of persistent organic pollutants able to resist degradation and with the ability to bioaccumulate through the food chain. In Brazil, there are still few studies on PCBs and PBDEs in aquatic organisms. In this study, we determined the levels of PBDEs and PCBs in three different fish species from the Ilha Grande Bay, located in the southern state of Rio de Janeiro, Brazil. PBDEs levels were very low, with values below the limit of quantification. PCBs concentrations ranged from 2.29 to 27.60 ng g^?1 ww in muscle and from 3.41 to 34.22 ng g^?1 ww in liver of the three investigated fish species. Significant positive correlations were established between PCBs concentration and fish biometric variables in mullet (length and lipid content) and a statistically significant change between seasons in croaker was observed.     

Anthropogenic and naturally occurring polybrominated phenolic compounds in the blood of cetaceans stranded along Japanese coastal waters

We determined the residue levels and patterns of hydroxylated polybrominated diphenyl ethers (OH-PBDEs), and related compounds, such as PBDEs, methoxylated PBDEs (MeO-PBDEs), and bromophenols (BPhs) in the blood of eleven cetacean species stranded along the Japanese coasts. The dominant OH- and MeO-PBDE isomers found in all cetaceans were 6OH-BDE47 and 6MeO-BDE47. Additionally, 2,4,6-triBPh was dominant isomer in all cetaceans. In contrast, specific differences in the distribution of para- and meta- OH-PBDE isomers and some BPhs (potential PBDEs metabolites) were found among the cetaceans.Residue levels of ΣMeO-PBDEs and 6OH-BDE47 + 2′OH-BDE68, and 2,4,6-triBPh and 6OH-BDE47 + 2′OH-BDE68 showed a significant positive correlation. These results may suggest that the large percentages of OH-PBDEs, MeO-PBDEs and 2,4,6-triBPh might share common source (i.e. biosynthesis by marine organisms), or metabolic pathway in cetacean species. Significant correlations were found between the concentrations of BDE99 and 2,4,5-triBPh. This result suggested that 2,4,5-triBPh in cetaceans could be a metabolite of BDE99.     

Bioaccumulation of polybrominated diphenyl ethers in harbor seals from the northwest Atlantic

Polybrominated diphenyl ethers (PBDEs) were analyzed in blubber of harbor seals (Phoca vitulina concolor) collected between 1991 and 2005 along the northwest Atlantic. ∑PBDE concentrations (mono- to hexa-BDEs) detected in blubber samples (n = 42) ranged from 80 to 25 720 ng g⁻¹ lw, (overall mean 2403 ± 5406 ng g⁻¹ lw). By age, mean ∑PBDE concentrations were: 3645 ± 7388, 2945 ± 5995, 1385 ± 1265, and 326 ± 193 ng g⁻¹ lw in pups, yearlings, adult males, and adult females, respectively. Unlike the trend for PCBs, no decreasing gradient from urban to rural/remote areas was observed for PBDEs in these samples, likely reflecting inputs from local sources. No significant temporal trend was observed for PBDEs in harbor seals between 1991 and 2005, although congener profiles shifted over time. Tetra-BDE-47 was the dominant congener, followed by BDEs-99, -100, -153, -154, and -155 in varying order, suggesting exposure to the penta-BDE product. In adult males, the hexa-BDEs contributed more to the total (22%) than BDEs-99 and -100 (14%), and concentrations of BDE-155 were elevated compared with -154. Higher BDEs were detected in a subset of seals (n = 12) including hepta-BDE-183, the marker for the octa-BDE mixture, and octa-BDE-197, along with several unidentified hepta- and octa- congeners. BDE-209 was detected in seal blubber at concentrations ranging from 1.1 to 8 ng g⁻¹ lw, indicating that deca-BDE is bioavailable in this marine food web. This is the first study to document the accumulation of BDE-209 at measurable levels in wild harbor seals. While the PBDE patterns in blubber indicate exposure to all three BDE commercial mixtures, the data also suggest that BDE-209 debromination by seal prey fish may contribute to the loading of lower brominated congeners (hexa- to octa-BDEs) in these seals.     

Influence of water quality parameters on occurrence of polybrominated diphenyl ether in sediment and sediment to biota accumulation

Polybrominated diphenyl ether (PBDE) concentrations in sediment and fish from 12 principal rivers in Taiwan were investigated to determine their association with water quality parameters as well as the biota-sediment accumulation factor (BSAF) in fish with different living patterns. The highest PBDE concentration in sediment was found in the Bajhang River (261 ng g^?1 dry weight (d.w.)) and the lowest in the Beinan River and the Da-an River (0.17 ng g^?1 d.w.). The PBDE concentrations in fish samples ranged from 1.28 ng g^?1 d.w. (Oreochromis niloticus niloticus) in the Yanshuei River to 33.7 ng g^?1 d.w. (Varico rhinos barbatulus) in the Da-an River. We conclude that PBDEs contamination in sediment was significantly affected by NH₃–N, pH, and DO. The BSAF results showed a parabolic trend from low- to high-brominated BDEs. Fish easily accumulated the congeners BDE-47, -100, -119, -126, and -154 from sediment. The BSAF decreased in the following order: PeBDE > HxBDE > TeBDE > other BDEs. Principle component analysis showed that demersal fish have different PBDE sources than do pelagic fish. We conclude that living and feeding habits are critical factors affecting PBDE accumulation in fish.     

Polychlorinated biphenyl spatial patterns in San Francisco Bay forage fish

Industrialized waterways frequently contain nearshore hotspots of legacy polychlorinated biphenyl (PCB) contamination, with uncertain contribution to aquatic food web contamination. We evaluated the utility of estuarine forage fish as biosentinel indicators of local PCB contamination across multiple nearshore sites in San Francisco Bay. Topsmelt (Atherinops affinis) or Mississippi silverside (Menidia audens) contamination was compared between 12 targeted sites near historically polluted locations and 17 probabilistically chosen sites representative of ambient conditions. The average sum of 209 PCB congeners in fish from targeted stations (441 ± 432 ng g^?1 wet weight, mean ± SD) was significantly higher than probabilistic stations (138 ± 94 ng g^?1). Concentrations in both species were comparable to those of high lipid sport fish in the Bay, strongly correlated with spatial patterns in sediment contamination, and above selected literature thresholds for potential hazard to fish and wildlife. The highest concentrations were from targeted Central Bay locations, including Hunter’s Point Naval Shipyard (1347 ng g^?1; topsmelt) and Stege Marsh (1337 ng g^?1; silverside). Targeted sites exhibited increased abundance of lower chlorinated congeners, suggesting local source contributions, including Aroclor 1248. These findings indicate that current spatial patterns in PCB bioaccumulation correlate with historical sediment contamination due to industrial activity. They also demonstrate the utility of naturally occurring forage fish as biosentinels of localized PCB exposure.     

Occurrence and congener specific profiles of polybrominated diphenyl ethers and their hydroxylated and methoxylated derivatives in breast milk from Catalonia

The presence of polybrominated diphenyl ethers (PBDEs) from mono to hepta brominated and 11 hydroxylated (OH-) and methoxylated (MeO-) PBDEs was examined in 37 breast milk samples collected from 11 mothers living in Barcelona. An extraction method based on accelerated solvent extraction followed by gas chromatography coupled to high resolution mass spectrometry was used to inequivocally identify all target compounds at the low pg g(-1) lw level. Data obtained were examined for absolute and relative concentrations and specific PBDE, OH- and MeO-PBDE congener patterns. Sigma PBDE concentration ranged between 1,161 and 1,372,797 pg g(-1) lw and BDEs 47, 99, 100, 153 and 183 accounted for more than 80% of the total PBDEs. All tri and tetra OH- and MeO-PBDEs compounds were detected at levels between 6 and 14,984 pg g(-1)lw. The median ratio OH/PBDE and MeO-PBDEs/PBDEs was from 2.9% to 1.6%, respectively, suggesting either that PBDE metabolism to OH- and MeO- derivatives is not an important degradation route in humans or either OH- and MeO-PBDEs are rapidly excreted. No significant correlation was observed between PBDEs and OH- and MeO-PBDE, although OH- and OMe-PBDEs co-occurred in mothers' milk (R(2)=0.5349). According to the daily intake of PBDEs and OH- and MeO-PBDEs, which was between 0.47 and 363 ng d(-1) (excluding a smoking donor), potential health risks associated with these compounds are assessed.     

Origin of low-molecular-weight dicarboxylic acids and their concentration and size distribution variation in suburban aerosol

The concentrations and size distributions of low molecular weight dicarboxylic acids in suburban particulate matter collected in early and mid-autumn 2002 and early and mid-summer 2003 in Tainan, Taiwan, were analyzed. PM_2.5 contained, on average, 449.3 ng m⁻³ oxalic acid, 53.0 ng m⁻³ malic acid, 45.5 ng m⁻³ maleic acid, 29.6 ng m⁻³ succinic acid, 20.8 ng m⁻³ malonic acid, and 11.6 ng m⁻³ tartaric acid. Bar tartaric acid, concentrations were higher during the day, indicating that these acids are photochemical products. Furthermore, the malonic acid–succinic acid ratio of 0.79 during daytime and 0.60 during nighttime demonstrates that more succinic acid is converted to malonic acid during daytime, and that aerosol dicarboxylic acids predominantly originate from photochemical oxidation during daytime. The concentration peak of oxalic acid occurred in the condensation and droplet modes (0.32–1.0 μm), as did that of sulfate. In early summer, succinic acid, malonic acid, and oxalic acid major concentration peaks occurred at 0.32–0.54 μm, indicative of the relationship created by photochemical decomposition of succinc acid into malonic acid into oxalic acid. This photochemical decomposition accelerated in mid-summer such that most concentration peaks for succinic and malonic acids also occurred at 0.32–1.0 μm. Mid-summer is also the wettest period of the four in Tainan, with 85% RH. As a result of hygroscopic reactions in mid-summer, malonic acid and oxalic acid major concentration peaks shifted from 0.32–0.54 μm or 0.54–1.0 μm to 1.0–1.8 μm, thus extending the range in which these species were found to larger particle sizes, and this shift was highly correlated with a shift in succinic acid size distribution. This latter observation offers additional evidence that succinic acid is photochemically decomposed into malonic acid and oxalic acid and that the presence of malonic and oxalic acids in the wet mid-summer atmosphere is made more obvious via hygroscopic growth. Close correlation between succinic acid and Na⁺ and succinic acid and NO₃⁻ in the coarse mode is related to sea spray.     

Seasonal variations of hydroxylated and methoxylated brominated diphenyl ethers in blue mussels from the Baltic Sea

Hydroxylated polybrominated diphenyl ethers (OH-PBDEs) and methoxylated polybrominated diphenyl ethers (MeO-PBDEs) found at high levels in the Baltic biota are mainly natural products, but can also be formed through metabolism or abiotic oxidation of polybrominated diphenyl ethers (PBDEs). The formation of OH-PBDEs is of concern since there is growing evidence of phenolic toxicity. This study investigates seasonal variations in levels of OH-PBDEs and MeO-PBDEs, focusing on an exposed species, the blue mussel (Mytilus edulis), sampled in the Baltic Sea in May, June, August and October of 2008. Both the OH-PBDE and MeO-PBDE levels in the mussels showed seasonal variations from May to October, the highest concentration of each congener appearing in June. The seasonal variation was more marked for OH-PBDEs than in MeO-PBDEs, but all congeners showed the same trends, except 6-MeO-BDE47 and 2′-MeO-BDE68, which did not significantly decline in concentrations after June. Biotic or abiotic debromination is suggested as a possible reason for the rapid decrease in methoxylated penta- and hexa-BDE concentrations observed in blue mussels from June to August, while the tetraBDE concentrations were stable. In addition, 1,3,7/1,3,8-tribrominated dibenzo-p-dioxins showed the same seasonal variation. The seasonal variations indicates natural formation and are unlikely to be due to transformation of anthropogenic precursors. The levels of PBDEs were fairly constant over time and considerably lower than those of the OH-PBDEs and MeO-PBDEs. The timing of the peaks in concentrations suggests that filamentous macro-algae may be important sources of these compounds found in the blue mussels from this Baltic Sea location.     

Pesticides analysed in rainwater in Alsace region (Eastern France): Comparison between urban and rural sites

Current-used pesticides commonly applied in Alsace region (Eastern France) on diverse crops (maize, vineyard, vegetables, etc.) were analysed, together with Lindane, in rainwater between January 2002 and June 2003 simultaneously on two sites situated in a typical rural (Erstein, France) and urban area (Strasbourg, France).Rainwater samples were collected on a weekly basis by using two automatic wet only collectors associated with an open collector for the measurement of rainwater height.Pesticides were analysed by GC-MSMS and extracted from rainwater by SPME. Two runs were performed. The first one was performed by using a PDMS (100 μm) fibre for pesticides where direct injection into GC is possible (alachlor, atrazine, azinphos-ethyl, azinphos-methyl, captan, chlorfenvinphos, dichlorvos, diflufenican, α- and β-endosulfan, iprodione, lindane, metolachlor, mevinphos, parathion-methyl, phosalone, phosmet, tebuconazole, triadimefon and trifluralin). The second run was performed by using PDMS/DVB fibre and this run concerns pesticides where a preliminary derivatisation step with pentafluorobenzylbromide (PFBBr) is required for very low volatiles (bromoxynil,2,4-MCPA, MCPP and 2,4-D) or thermo labiles (chlorotoluron, diuron and isoproturon) pesticides.Results showed that the more concentrated pesticides detected were those used as herbicides in large quantities in Alsace region for maize crops (alachlor, metolachlor and atrazine). Maximum concentrations for these herbicides have been measured during intensive applications periods on maize crops following by rapid decrease immediately after use.For Alachlor, most important peaks have been observed between 21 and 28 April 2003 (3327 ng L⁻¹ at Erstein and 5590 ng L⁻¹ at Strasbourg). This is also the case for Metolachlor where most important peak was observed during the same week.Concentrations of pesticides measured out of application periods were very low for many pesticides and some others where never detected during this period. This is the case for diflufenican which was detected only during application. Two important peaks of concentrations were observed; a first one (101 ng L⁻¹) in Erstein in November 2002 (4–11 November) and a second one (762 ng L⁻¹) also in Erstein (28 April–15 May).The same behaviour can be seen for chlorfenvinphos and phosalone which have been detected, respectively, 2 and 4 times in Erstein and Strasbourg at high concentrations (28 April 2003–15 May 2003, 187 ng L⁻¹ of phosalone and 157 ng L⁻¹ of chlorfenvinphos in Erstein).MCPP, 2,4 MCPA and 2,4-D have been detected at high concentrations in rainwater but for the other pesticides very episodically and mainly during their use in agriculture. Maximal concentrations of MCPP and 2,4 MCPA have been measured in Erstein between 28 April and 15 May (904 and 746 ng L⁻¹, respectively).Comparison between rural and urban sites showed that concentrations in rural areas are generally higher except for pesticides commonly applied in urban areas like Diuron.No seasonal phenomenon was observed for Diuron. This herbicide has been detected in practically all of the rainwater samples in Strasbourg (40/41) with a maximum of 1025 ng L⁻¹ (16–23 September 2002) in 38 samples on 41 in Erstein with a maximum of 317 ng L⁻¹ (15–23 October 2002). The total concentration of Diuron measured between 4 March 2002 and 20 July 2003 is of 4721 ng L⁻¹ in Strasbourg and 5025 ng L⁻¹ in Erstein. This result shows that wet deposition of Diuron in urban and rural sites was equivalent and can be explained by the “urban use” of this molecule together with its potential persistence.     

Hexabromocyclododecanes in surface sediments and a sediment core from Rivers and Harbor in the northern Chinese city of Tianjin

In the present study, hexabromocyclododecanes (HBCDs) were investigated in the sediment from Haihe River (HR), Dagu Dainage Canal (DDC) and Tianjin Harbor (TH) at Bohai Bay using a total of 51 samples of surface sediments and a sediment core collected from May to September in 2010, and its diastereomer- and enantiomer-specific profiles were analyzed. The concentration of total HBCDs were generally high, with mean value and ranges of 31.0 and 1.35–634 ng g^?1 dw, respectively. The contamination followed the order of TH > DDC > HR. Higher levels (up to 634 ng g^?1 dw) occurred in the lower reach of HR and DDC located in an industrial area of Tianjin. This is the first time to report so high concentration of HBCDs in sediment in Southeast Asia. The γ-diastereomer dominated in most samples (44 out of 51), and this is in agreement with the diastereomer distribution pattern in industrial products, while α-HBCD was the dominant diastereomer in the other seven samples. However, only few samples exhibited γ-diastereomer ratio similar to that (75–89%) in technical products, indicating the inter-transformation and variable degradation of the different isomers. The high ratio of γ-diastereomer could be used as an indicator for fresh contamination input. Enantiomeric factors (EFs) of HBCD isomers in most of the samples were statistically different from technical products (p < 0.05), showing a trend of more easily enrichment of the (?)-HBCD-enantiomer compared to the (+)-HBCD-enantiomer. The δ- and ε-diastereomers were frequently detected but at low level. The HBCDs in the sediment core showed several peaks, and the greatest value occurred in 2005, when a plastic manufacture plant using HBCD was set up nearby.     

Reproductive performance in East Greenland polar bears (Ursus maritimus) may be affected by organohalogen contaminants as shown by physiologically-based pharmacokinetic (PBPK) modelling

Polar bears (Ursus maritimus) feed mainly on ringed seal (Phoca hispida) and consume large quantities of blubber and consequently have one of the highest tissue concentrations of organohalogen contaminants (OHCs) worldwide. In East Greenland, studies of OHC time trends and organ system health effects, including reproductive, were conducted during 1990–2006. However, it has been difficult to determine the nature of the effects induced by OHC exposures on wild caught polar bears using body burden data and associated changes in reproductive organs and systems. We therefore conducted a risk quotient (RQ) evaluation to more quantitatively evaluate the effect risk on reproduction (embryotoxicity and teratogenicity) based on the critical body residue (CBR) concept and using a physiologically-based pharmacokinetic (PBPK) model. We applied modelling approaches to PCBs, p,p′-DDE, dieldrin, oxychlordane, HCHs, HCB, PBDEs and PFOS in East Greenland polar bears based on known OHC pharmacokinetics and dynamics in laboratory rats (Rattus rattus). The results showed that subcutaneous adipose tissue concentrations of dieldrin (range: 79–1271 ng g⁻¹ lw) and PCBs (range: 4128–53 923 ng g⁻¹ lw) reported in bears in the year 1990 were in the range to elicit possible adverse health effects on reproduction in polar bears in East Greenland (all RQs ⩾ 1). Similar results were found for PCBs (range: 1928–17 376 ng g⁻¹ lw) and PFOS (range: 104–2840 ng g⁻¹ ww) in the year 2000 and for dieldrin (range: 43–640 ng g⁻¹ lw), PCBs (range: 3491–13 243 ng g⁻¹ lw) and PFOS (range: 1332–6160 ng g⁻¹ ww) in the year 2006. The concentrations of oxychlordane, DDTs, HCB and HCHs in polar bears resulted in RQs < 1 and thus appear less likely to be linked to reproductive effects. Furthermore, sumRQs above 1 suggested risk for OHC additive effects. Thus, previous suggestions of possible adverse health effects in polar bears correlated to OHC exposure are supported by the present study. This study also indicates that PBPK models may be a supportive tool in the evaluation of possible OHC-mediated health effects for Arctic wildlife.     

Bioanalytical and instrumental analysis of estrogenic activities in drinking water sources from Yangtze River Delta

The estrogenic activities of source water from Yangtze River, Huaihe River, Taihu Lake and groundwater in Yangtze River Delta in the dry and wet season were determined by use of reporter gene assays based on African green monkey kidney (CV-1) cell lines. Higher estrogenic activities were observed in the dry season, and the estrogenic potentials in water samples from Taihu Lake were greater than other river basins. None of the samples from groundwater showed estrogen receptor (ER) agonist activity. The 17β-Estradiol (E2) equivalents (EEQs) of water samples in the dry season ranged from 9.41 × 10^?1 to 1.20 × 10¹ ng E2 L^?1. In the wet season, EEQs of all the water samples were below the detection limit as 9.00 × 10^?1 ng E2 L^?1 except for one sample from Huaihe River. The highest contribution of E2 was detected in Yangtze River as 99% of estrogenic activity. Nonylphenol (NP, 100% detection rate) and octylphenol (OP, 100% detection rate) might also be responsible for the estrogenic activities in water sources. Potential health risk induced by the estrogenic chemicals in source water may be posed to the residents through water drinking.     

Air–water exchange fluxes of polycyclic aromatic hydrocarbons in the tropical coast,Taiwan

Air–water exchange fluxes of polycyclic aromatic hydrocarbons (PAHs) were simultaneously measured in air and water samples from two sites on the Kenting coast, located at the southern tip of Taiwan, from January to December 2010. There was no significant difference in the total PAH (t-PAH) concentrations in both gas and dissolved phases between these two sites due to the less local input which also coincided to the low levels of t-PAH concentration; the gas and dissolved phases averaged 1.29 ± 0.59 ng m^?3 and 2.17 ± 1.19 ng L^?1 respectively. The direction and magnitude of the daily flux of PAHs were significantly influenced by wind speed and dissolved PAH concentrations. Individual PAH flux ranged from 627 ng m^?2 d^?1 volatilization of phenanthrene during the rainy season with storm–water discharges raising dissolved phase concentration, to 67 ng m^?2 d^?1 absorption of fluoranthene during high wind speed periods. Due to PAH annual fluxes through air–water exchange, Kenting seawater is a source of low molecular weight PAHs and a reservoir of high molecular weight PAHs. Estimated annual volatilization fluxes ranged from 7.3 μg m^?2 yr^?1 for pyrene to 50 μg m^?2 yr^?1 for phenanthrene and the absorption fluxes ranged from ?2.6 μg m^?2 yr^?1 for chrysene to ?3.5 μg m^?2 yr^?1 for fluoranthene.     

Impact of mineral components and selected trace metals on ambient PM10 concentrations

PM10 levels of the mineral components Si, Al, Fe, Ca, Mg and some trace metals were measured at three different sites in the urban area of Vienna (Austria). Observed trace metal concentrations varied between less than 0.1 ng m^?3 (Cd) and approximately 200 ng m^?3 (Zn), mineral components showed enhanced concentrations ranging from 0.01 μg m^?3 (Ca) to 16.3 μg m^?3 (Si). The contribution of the respective mineral oxides to PM10 mass concentrations accounted on average for 26.4 ± 16% (n = 1090) of the PM10 mass, with enhanced rates in spring and autumn (monthly averages of up to 40%) and decreased contributions in the cold season (monthly averages below 10%). The atmospheric occurrence of Al, Ti and Sr could be assigned to crustal sources, whereas for the elements Ba, Ca, Fe, Mg, Mn and V an increased contribution of non-crustal origin was observed. PM10 levels of As, Cd, Co, Cr, Cu, Ni, Pb, Sb, Sn and Zn were predominantly derived from man-made emissions. Intersite comparison indicated that urban PM10 mass concentrations and PM10 levels of As, Pb and Zn were predominantly influenced from the transport of aerosols from outside into the city, whereas for the elements Ba, Mg, Ca, Cu and Fe a distinctly increased impact of local emissions was observed. The contribution of these urban emissions to total PM10 concentrations was estimated by calculating the so-called “urban impact”, which was found to be 32.7 ± 18% (n = 392) in the case of PM10 mass concentrations. The investigated elements accounted on average for 31.3 ± 19% (n = 392) of the observed PM10 mass increase. The mean values for the “urban impacts” of individual elements varied between 25.5% (As) and 77.0% (Ba).