Organophosphorus flame retardants and plasticizers in the atmosphere of the North Sea

Air samples collected in the German part of the North Sea from March to July 2010 were investigated for organophosphorus compounds (OPs) being applied as flame retardants and plasticizers. The ∑₈OPs concentration ranged from 110 to 1400 pg m⁻³ while tris(2-chloroisopropyl) phosphate (TCPP) dominated all samples with individual concentrations up to 1200 pg m⁻³. The highest concentrations were observed in continental air masses showing the high influence of industrialized regions including production sites on atmospheric emissions and concentrations. The occurrence of OPs even in oceanic/Arctic air masses shows that OPs can undergo long-range atmospheric transport. Dry particle-bound deposition fluxes from 9 to 240 ng m⁻² d⁻¹ for ∑₈OPs were estimated leading to a minimum annual flux of 710 ± 580 kg y⁻¹ OPs into the German North Sea. This study presents the first occurrence of OPs in the marine atmosphere together with important information on their long-range transport potential.     

Characterization of polychlorinated biphenyls and brominated flame retardants in sludge,sediment and fish from municipal dumpsite at Surabaya,Indonesia

We investigated the PCBs, PBDEs and HBCDs contamination in sludge, sediments and fish from various locations including raw leachate pond, leachate treatment plans (LTPs), control wells and reference site at open landfill of municipal dumpsite, Surabaya City, Indonesia. 62 PCBs and 14 PBDEs congeners, and 3 HBCDs isomers were identified and quantified using GC–MS and LC–MS/MS, respectively. Concentration ranges and median (value in parentheses) of PCBs, PBDEs and HBCDs were from not detected (ND) to 60 (3.9) ng g⁻¹ dw, 0.0075 to 45 (4.5) ng g⁻¹ dw and ND to 2.8 (0.052) ng g⁻¹ dw in sludge and sediments, respectively. While in two polled of fish samples were 30–55 ng g⁻¹ lw, 6.6–11 ng g⁻¹ lw and 1.6–3.3 ng g⁻¹ lw, respectively. Among the sampling sites, the highest level of PCBs and PBDEs were detected in sludge from raw leachate pond. However, PCBs and PBDEs levels were showing decreased in LTP-1 that could be due to the bacterial degradation but not in LTP-2, HBCDs were more stable in both LTPs. Levels of PCBs and BFRs in sludge at the present study were lower than those reported in sewage sludge reported from some other countries. PCBs profiles were mainly composed in that order by CB-138, -153, -180, -101, -118 and -28, while by BDE-47, -99, -100, -153, -154 and -28 for PBDEs in sludge, sediments and fish. Profiles of HBCDs were predominantly composed by γ- and α-isomers in sludge and fish, respectively. Debromination, dechlorination, commercial formulations used and congener-specific accumulation of those contaminants are the factors influenced the profiles.     

Organochlorines, brominated flame retardants and mercury levels in six seabird species from the Gulf of St. Lawrence (Canada): Relationships with feeding ecology, migration and molt

Concentrations of organochlorines (OCs), brominated flame retardants (BFRs) and mercury (Hg) were measured in eggs of six seabird species breeding in the Gulf of St. Lawrence, Canada. Stable nitrogen (δ¹⁵N) and carbon (δ¹³C) isotopes were used as ecological tracers to measure trophic level and connectivity with benthos, respectively. Concentrations, patterns as well as ecological tracers varied significantly between species. The sum of polychlorinated biphenyls (ΣPCBs) was the most important group measured in all seabird species based on concentration followed generally by the sum of chlorinated pesticides (ΣCPs), the sum of brominated flame retardants (ΣBFRs) and finally total Hg (THg). ΣPCBs, ΣCPs and ΣBFRs increased with trophic level, whereas THg did not. Only ΣBFRs increased with a higher connectivity with the benthos. Seabird species resident to the Great Lakes-St. Lawrence ecosystem showed higher Hg and BFR levels than migratory species. Molt patterns were used to explain variations of contaminant levels.     

Organophosphorus flame retardants in house dust from the Philippines: occurrence and assessment of human exposure

The use of organophosphorus flame retardants (PFRs) as flame retardants and plasticizers has increased due to the ban on common polybrominated diphenyl ether mixtures. However, only limited information on PFR contamination is available so far from Southeast Asia. In the present study, residual levels of PFRs in house dust and exposure through dust ingestion were investigated in the Philippines. House dust samples (n?=?37) were collected from Malate (residential area) and Payatas (municipal dumping area) in the Philippines and analyzed using ultra-high-performance liquid chromatography coupled with tandem mass spectrometry. Among the targeted seven PFRs, triphenyl phosphate (TPP) was the predominant compound. Median levels of ΣPFRs in Malate (530 ng/g) were two times higher (p?<?0.05) than in Payatas (240 ng/g). The estimated daily intake of PFRs in the Philippines (of areas studied) via house dust ingestion was below the guideline values. House dust may be an important contributor in the overall exposure of humans to TPP even when considering dietary sources. To our knowledge, this is a first report on PFR contamination in house dust from developing country. PFRs were ubiquitously detected in the home environments in the Philippines. Although estimated exposure levels through dust ingestion were below the guideline, it was suggested that toddlers are at higher risk. Therefore, further investigations to understand the behavior of PFRs in house and other microenvironments and overall exposure pathways for the country’s populace to PFRs are necessary.     

PBDE flame retardants and PCBs in migrating Steller sea lions (Eumetopias jubatus) in the Strait of Georgia, British Columbia, Canada

Polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) were measured in blubber biopsy samples from 22 live-captured Steller sea lions (Eumetopias jubatus) that had just entered the Strait of Georgia, British Columbia, Canada, for their overwintering feeding season. ∑PBDE ranged from 50 μg kg⁻¹ (lipid weight) in adult females to 3780 μg kg⁻¹ in subadult individuals. ∑PCBs ranged from 272 μg kg⁻¹ in adult females to 14 280 μg kg⁻¹ in subadult individuals. While most PBDE and PCB congeners were transferred through milk to pups, PCBs with log K_OW > 7.0 (PCBs 206, 207, 208 and 209) appeared constrained, resulting in a lighter mixture in pups compared to adult females. The ratio of individual PCB congeners by metabolic group (Groups I, II, III, IV and V) to PCB-153 regressed against length of males suggested poor biotransformation of these compounds (slopes did not differ from zero, p > 0.05). PBDE congeners 49, 99, 153 and 183 appeared bioaccumulative (slopes of ratio BDE/PCB 153 versus length were higher than zero, p < 0.05), but the dominance of the single congener, BDE-47 (64% of total PBDEs), likely due in part to debromination pathways, reduced our ability to explore congener-specific dynamics of PBDEs in these pinnipeds. With 80% of our Steller sea lions exceeding a recent toxicity reference value for PCBs, the fasting-associated mobilization of these contaminants raises concerns about a heightened vulnerability to adverse effects during annual migrations.     

Contamination and bioaccumulation of benzotriazole ultraviolet stabilizers in fish from Manila Bay, the Philippines using an ultra-fast liquid chromatography-tandem mass spectrometry

Methyl methacrylate (MMA) is grafted on multiwalled carbon nanotubes (MWCNTs) by using N₂ plasma technique. The MMA grafted MWCNTs (MWCNT-g-pMMA) are characterized by using Raman spectroscopy, powder X-ray diffraction, X-ray photoelectron spectroscopy, thermo gravimetric analysis-differential thermal analysis (TGA-DTA), and potentiometric acid-base titration method. The application of MWCNT-g-pMMA in the removal of 4,4′-dichlorinated biphenyl (4,4′-DCB) from large volumes of aqueous solutions is investigated under ambient conditions. The results indicate that the adsorption of 4,4′-DCB on MWCNT-g-pMMA is much higher than that of 4,4′-DCB on MWCNTs, and the adsorbed 4,4′-DCB is difficult to be thermally decomposed from MWCNT-g-pMMA according to the TGA-DTA analysis. MWCNT-g-pMMA are suitable materials in the preconcentration and immobilization of polychlorinated biphenyls (PCBs) from large volumes of aqueous solutions in environmental pollution cleanup.     

Levels and sources of brominated flame retardants in human hair from urban, e-waste, and rural areas in South China

Human hair and indoor dust from urban, e-waste, and rural areas in south China were collected and analyzed for brominated flame retardants (BFRs). BFRs concentrations in hair from occupational e-waste recycling workers were higher than those from non-occupational exposed residents in other sampling areas. Polybrominated diphenyl ethers (PBDEs) and decabromodiphenyl ethane (DBDPE) are two major BFRs in hair samples. The PBDE congener profiles in hair from the e-waste area are different from those from urban and rural areas with relatively higher contribution of lower brominated congeners. DBDPE, instead of BDE209, has become the major BFR in non-e-waste recycling areas. Significant correlations were found between hair level and dust level for DBDPE and BTBPE but not for PBDEs. The different PBDE congener profiles between dust and hair may suggest that exogenous exposure to the PBDE adsorbed on dust is not a major source of hair PBDEs.     

Occurrence and seasonal variation of alkylphenols in marine organisms from the coast of Taiwan

The occurrence and distribution of alkylphenols (APs, i.e., 4-tert-octylphenol (4-t-OP) and 4-nonlyphenol isomers (4-NP)) in oysters (Crassostrea gigas), snails (Thais clavigera), coastal water and coastal sediments of the western coast of southern Taiwan are investigated. Alkylphenols were present in all matrices of interest: in water, ranging from 61 to 370 ng/l, in sediments, ranging from 27 to 190 ng/g, and in biota samples (i.e., oyster and snail), ranging from 20 to 5190 ng/g. Statistical analysis indicated that the probability distribution of most determined concentrations in oyster and snail samples was log-normal distribution. The bioaccumulation of APs resulted in a seasonal variation with respect to their compositions and concentrations in oyster and snail samples. For oysters, concentrations of APs in winter exceeded those in summer. In contrast, those in snails in summer exceeded those in winter. Estimated biomagnification factors of APs from snails to oysters ranged from 1.4 to 4.3 in summer, and 0.5 to 0.8 in winter on the dry weight basis. The results suggested that seasonally mediated physiological changes, such as dilution caused by growth, biotransformation and metabolism, may affect the bioaccumulation of APs in according to season and organism.     

Levels and bioaccumulation of organochlorine pesticides (OCPs) and polybrominated diphenyl ethers (PBDEs) in fishes from the Pearl River estuary and Daya Bay, South China

Fifty fish samples were collected from the Pearl River estuary (PRE) and Daya Bay, South China and were analyzed for DDTs, HCHs, chlordanes and polybrominated biphenyl ethers (PBDEs). Except the high concentrations of DDT observed in fishes, the concentrations of HCHs, chlordanes and PBDEs were low when compared to other regions. BDE-47 was the predominant PBDE congener and the BDE-209 concentrations were relatively low, despite its high concentration in surface sediments. The absence of significant increase of DDT, HCH, chlordane and PBDE concentrations towards higher delta15N values, as well as the lack of a significant correlation (p<0.1) between log concentrations (lipid normalized) and delta15N, may indicate a weak biomagnification of these chemicals in the food webs. Good agreement was observed between their concentrations and lipid contents of the organisms. Bioconcentration was suggested to be responsible for the accumulation of OCPs and PBDEs in the lower trophic organisms in the studied subtropical waters.     

Spatial and temporal distribution of polycyclic aromatic hydrocarbons (PAHs) in sediments from Daya Bay, South China

The spatial and temporal distribution of polycyclic aromatic hydrocarbons (PAHs) has been investigated in Daya Bay, China. The total concentration of the 16 USEPA priority PAHs in surface sediments ranged from 42.5 to 158.2 ng/g dry weight with a mean concentration of 126.2 ng/g. The spatial distribution of PAHs was site-specific and combustion processes were the main source of PAHs in the surface sediments. Total 16 priority PAH concentration in the cores 8 and 10 ranged from 77.4 to 305.7 ng/g and from 118.1 to 319.9 ng/g respectively. The variation of the 16 PAH concentrations in both cores followed the economic development in China very well and was also influenced by input pathways. Some of the PAHs were petrogenic in core 8 while pyrolytic source was dominant in core 10. In addition, pyrolytic PAHs in both cores were mainly from the coal and/or grass and wood combustion.     

Polychlorinated biphenyls (PCBs) in marine fishes from China: Levels, distribution and risk assessment

Muscle tissues of large yellow croakers (Pseudosciaena crocea) and sliver pomfret (Pampus argenteus) from nine coastal cities of East China including Dalian, Tianjin, Qingdao, Shanghai, Zhoushan, Wenzhou, Fuzhou, Quanzhou and Xiamen were analyzed for polychlorinated biphenyl (PCB) concentrations. Thirty-six PCB congeners were quantified in the fishes, of which 11 congeners were dioxin-like PCBs. The total PCB concentrations of the present study were at the low end of the global range, which may be related to the smaller usage and shorter consumption history of PCBs in China. PCBs 18, 29, 52, 66, 101, 104, 138, 153, 180 and 194 were the major constituents found in the fish samples. Regression analysis showed a strong positive correlation (R² = 0.800; p < 0.001) between total dioxin-like PCBs and total PCB concentrations, and that total PCB concentrations explain 80% of the variability in total dioxin-like PCB concentrations. Among the species investigated, significantly higher concentrations of total PCBs were found in croakers than in pomfrets, which may be attributed to their different feeding and living habits. No significant difference in total PCB concentrations among the cities was observed; principal component analysis (PCA) of PCB profiles indicated that PCB pollution came from similar sources in the sampling areas and that there may be other PCB sources in Dalian and Wenzhou. The calculated carcinogenic risks (CRs) from the two species based on a low consumption group and high consumption group were all greater than 10⁻⁶, suggesting that daily exposure to dioxin-like PCBs via fish consumption results in a lifetime cancer risk of greater than one in one million. In contrast, the hazard quotients (HQs) of noncancer risks were all less than unity.     

Characterization of polychlorinated biphenyls and brominated flame retardants in surface soils from Surabaya, Indonesia

In this study, soil contamination by PCBs, PBDEs, HBCDs and two novel BFRs such as 1,2-bis-(2,4,6-tribromopenoxy) ethane (BTBPE) and decabromodiphenyl ethane (DBDPE) in various locations such as industrial, urban, rural, dumping site and agricultural areas of Surabaya, Indonesia has been characterized in order to evaluate their contamination status, profiles, potential sources, fate and behavior. Range and median concentrations of PCBs, PBDEs, HBCDs, BTBPE and DBDPE were ND - 9.6 (1.2), 0.069 - 24 (7.4), ND - 1.8 (0.48), ND - 1.7 (0.14) and ND - 7.6 (2.2) ng g⁻¹ dw, respectively. Industrial, urban and dumping areas were inventoried as the main sources of these pollutants. Decreasing gradient levels were observed for these contaminants from industrial district, urban, dumping site, rural and agricultural areas, in that order. Furthermore, organic carbon contents and proximity to the point sources were found as the major controlling factors. Contaminant profiles were characterized by the predominance of hexa-, hepta- and penta-homologues for PCBs; deca-, nona- and octa- for PBDEs and α-isomer for HBCDs. Product mixtures such as Ar1260/KC600 and Ar1254/KC500 for PCBs, deca- and octa-BDEs for PBDEs were the possible common formulations used in study area. To our knowledge, this is a first comprehensive study on characterization of soil contamination by PCBs, PBDEs and HBCDs together with two novel BFRs in a highly industrialized city located in tropical region. This study provides baseline information for establishing national monitoring programs in Indonesia.     

Multiresidue determination of carbamate,organochlorine, organophosphorus,and dicarboximide pesticides in lettuce by GC/MS

An extraction method based on matrix solid-phase dispersion was developed to determine pirimicarb, methyl parathion, malathion, procymidone, α -endosulfan and β -endosulfan in lettuce using gas chromatography-mass spectrometry. The best results were obtained using 4.0 g of lettuce, 2.0 g of silica as dispersant sorbent, 0.1 g of activated carbon as clean up sorbent and acetonitrile as eluting solvent. The method was validated using lettuce samples fortified with pesticides at six different concentration levels (0.1 to 2.0 mg/kg). Average recoveries (7 replicates) ranged from 50 to 120 %, with relative standard deviations between 0.6 and 8.0 %. Detection and quantification limits for lettuce ranged from 0.01 to 0.02 mg/kg and 0.04 to 0.10 mg/kg, respectively.     

Levels and temporal trends of chlorinated pesticides, polychlorinated biphenyls and brominated flame retardants in individual human breast milk samples from Northern and Southern Norway

Human breast milk samples from primipara women from Northern (Troms?) (N=10) and Southern Norway (Oslo) (N=19) collected in 2000-2001 were analysed with respect to hexachlorobenzene (HCB), hexachlorocyclohexane (HCHs), chlordanes (CHLs), DDTs, mirex, toxaphenes (CHBs), polychlorinated biphenyls (PCBs), polybrominated diphenylethers (PBDEs) and hexabromocyclododecane (HBCD). CHBs, PBDEs and HBCD were only analysed in the Troms? samples. Sum-PCBs and sum-DDTs were the major organochlorines (OCs) (170 and 110 ng g(-1) lipid weight (lw), respectively). Other OCs were found in levels of approximately 10- to 300-fold lower than sum-PCBs. Overall, the concentrations of OCs followed the decreasing order of PCBs>DDTs>HCB>HCHs approximately CHLs>CHBs>mirex. Concentrations of sum-HCHs were significantly higher in breast milk from Oslo compared to Troms? (p<0.05). The PCB profile was dominated by PCB-153, -138 and -180. The PBDE pattern was dominated by PBDE-47 and PBDE-153. The median level of sum-PBDEs was 4.1 ng g(-1) lw. PBDE-209 was detected in all analysed samples (median 0.13 ng g(-1) lw). The estimated daily intake (EDI) for the median (range) of sum mono-ortho (mo) PCBs(8) was 3.7 (1-9) pg TEQ kg(-1) body weight per day for breast fed infants in Norway. This exceeded the TDI by a factor of 1.8 (1-4) based only on intake of mono-ortho PCBs. The present study shows that concentrations of OCs in primipara breast milk have decreased 50-60% since 1991, and that this trend is continuing.     

Distribution and bioaccumulation of steroidal and phenolic endocrine disrupting chemicals in wild fish species from Dianchi Lake, China

The distribution and bioaccumulation of steroidal and phenolic endocrine disrupting chemicals (EDCs) were studied in various tissues of wild fish species from Dianchi Lake, China. In muscle tissue, 4-tert-octylphenol, 4-cumylphenol, 4-nonlyphenol and bisphenol A were detected in fish from each sampling site, with maximal concentrations of 4.6, 4.4, 18.9 and 83.5 ng/g dry weight (dw), respectively. Steroids (estrone, 17β-estradiol 17α-ethynylestradiol and estriol) were found at lower levels (<11.3 ng/g dw) and less frequently in muscle samples. The highest concentrations of steroids and phenols were found in liver, followed by those in gill and the lowest concentration was found in muscle. The field bioconcentration factors (BCFs) of phenols were calculated in fish species ranged from 18 to 97. Moreover, the measured tissue concentrations were utilized in order to estimate water concentration of steroids (4.4-18.0 ng/L). These results showed that steroidal and phenolic EDCs were likely ubiquitous contaminants in wild fish.     

Concentrations, distribution, and bioaccumulation of synthetic musks in the Haihe River of China

Seven typical synthetic musks (SMs) in the samples from the surface water, sediment and fish of the Haihe River were measured. The SM concentrations in the sediment and surface water of the Haihe River were significantly lower than those in the Dagu Drainage River and Chentaizi Drainage River (p < 0.05). Along the flow direction, the SM concentrations in surface water and sediment tended to increase from the upstream to the downstream of Dagu Drainage River. The Bioaccumulation factors (BAFs) of galaxolide (HHCB) and tonalide (AHTN) were calculated at high levels in the muscles of crucian carp, common carp, and silver carp. Most of the biota-sediment accumulation factors (BSAFs) for HHCB and AHTN were higher than 1.7, suggesting magnification possibly exist in the musk bioaccumulations of the three fishes in the Haihe River. No significant differences in HHCB/AHTN ratios were observed among the water, fish, and sediment samples (p > 0.05). However, the HHCB/AHTN values in the Haihe River were much lower than those in the Dagu Drainage River and Chentaizi Drainage River (p < 0.05). Compared with several typical persistent organic pollutants (POPs), the musk concentrations were higher or comparable in the Haihe River.     

Levels and distribution of polybrominated diphenyl ethers in plant, shellfish and sediment samples from Laizhou Bay in China

Polybrominated diphenyl ethers (PBDEs) are potentially harmful and persistent environmental pollutants. PBDEs concentrations are reported in plant, shellfish and sediment samples collected from Chinese Laizhou Bay. The summation operator(11)PBDE concentrations in plant and shellfish samples from Laizhou Bay were in the range of 70-5900ngg(-1) and 230-720ngg(-1) lipid, respectively. The summation operator(11)PBDEs concentrations in river sediment intervals samples ranged from 1.3 to 1800ng g(-1) dry weight. Pearson correlation analyses were performed on concentrations of PBDEs congeners of different sediment sample intervals. There were significant positive correlations for BDE 28 and BDE 100 (r=0.945, p<0.01), BDE 47 and BDE 99 (r=0.879, p<0.01), BDE 153 and BDE 154 (r=0.934, p<0.01), nona-BDEs and BDE 209 (r>0.934, p<0.01). BDE 209 was the predominant congener in all analyzed samples, consistent with the fact that deca-BDE technical mixtures are the dominant PBDEs product in Laizhou Bay. Data showed that PBDEs should be considered as an increasing pollution problem in the Laizhou Bay region.     

A nationwide survey of 20 legacy brominated flame retardants in indoor dust from China: continuing occurrence,national distribution,and implication for human exposure

Environmental Science and Pollution Research - Despite the restrictions on polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDDs), these chemicals are still ubiquitous...     

Occurrence and distribution of antibiotics in coastal water of the Bohai Bay, China: impacts of river discharge and aquaculture activities

The presence of 21 antibiotics in six different groups was investigated in coastal water of the Bohai Bay. Meantime, to illuminate the potential effects caused by the river discharge and aquaculture activities, wastewater from three breeding plants and surface water from six rivers flowing into the Bohai Bay were also analyzed for the selected antibiotics. The result revealed that measured antibiotics in the North Bobai Bay were generally higher than those in the South, highlighting the remarkable effects of high density of human activities on the exposure of antibiotics in environment. The antibiotics found in the six rivers were generally higher than those in the Bohai Bay reflecting the important antibiotics source of river discharge. This study reveals that the high consumption of some antibiotics in aquaculture activities may pose high ecological risk to the bay.     

Levels and distribution of polybrominated diphenyl ethers (PBDEs) in marine fishes from Chinese coastal waters

Concentrations of polybrominated diphenyl ethers (PBDEs) in yellow croakers (Pseudosciaena crocea) and silver pomfrets (Pampus argenteus) collected from nine coastal cities along the eastern China coastline were investigated. PBDE congeners with mono- to hexa-brominated substitutions were detected in the samples, indicating their ubiquitous distribution in the marine environment of China. The total PBDE concentration averaged 3.04 ng g⁻¹ lipid wt, a level that was relatively lower than in other regions of the world, especially North America where Penta-BDE was extensively used. Geographically, the highest concentration of PBDEs was found in Xiamen, and the PBDE levels in yellow croakers were significantly higher than those in pomfrets in most of the selected cities, a pattern which may be related to the different feeding habits of the two species. The congener profiles of PBDEs were found to be different from the commonly detected pattern in fishes from other regions of the world (i.e., BDE47 > BDE99, BDE100 > BDE153, BDE154). BDE47 and BDE154 were the predominant congeners in both species, accounting for more than 60% of the total PBDE concentrations. The reasons for the relatively high proportion of BDE154 may be due to the debromination of higher brominated congeners such as BDE183 and BDE209 by these two species.