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.     

Persistent organochlorines in raccoon dogs (Nyctereutes procyonoides) from Japan: Hepatic sequestration of oxychlordane

The present study determined the accumulation features of persistent organochlorines (OCs) such as polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethane and its metabolites (DDTs), hexachlorocyclohexane isomers (HCHs), hexachlorobenzene (HCB), and chlordane compounds (CHLs) in wild raccoon dogs (RDs; Nyctereutes procyonoides) collected from Kanagawa prefecture in Japan during 2001. In livers of RDs, CHLs were remarkably dominant (20 times higher than PCBs) followed by PCBs>DDTs>HCHs>HCB, whereas the chemicals in muscles were in the order of CHLs>PCBs>HCHs>DDTs>HCB. The accumulation pattern of OCs in RDs was different from those in Japanese humans and avian species reported previously, which generally accumulate higher levels of DDTs and PCBs than CHLs. This result indicates that RDs have been exposed to relatively high levels of CHLs and have high metabolic and elimination capacity for DDTs. In fact, CHL levels in RDs were higher than those in humans and some avian species, while DDT levels in RDs were much lower than other animals. In particular, extremely high accumulation levels of oxychlordane, which is a metabolite from chlordanes and nonachlors, were observed in RD livers. The higher toxic potency of oxychlordane than parent compounds may suggest that RDs are at high risk by this metabolite. On lipid weight basis, PCBs, HCHs and HCB levels were almost similar in livers and muscles, suggesting that the tissue distribution of these compounds principally followed the lipid-dependent accumulation. However, accumulation levels of oxychlordane and p,p'-DDD in livers were significantly higher than those in muscles, and concentration ratios of liver to muscle (L/M ratios) of these compounds were greater than 1.0 in all the specimens. This phenomenon was similar to PCDD/DF congener accumulation patterns observed previously in RDs. When relationships between hepatic TEQs and L/M ratios were examined for oxychlordane and p,p'-DDD, L/M ratios for these compounds significantly increased with hepatic TEQ levels, suggesting their hepatic sequestration in TEQs-dependent manner.     

Decomposition of dichloromethane and in situ alkali absorption of resulting halogenated products by a packed-bed non-thermal plasma reactor

For an effective decomposition and removal of organic halogenated compounds, a packed-bed non-thermal plasma reactor with in situ absorption of the resulting halogenated products by alkaline sorbent incorporated was proposed. In the plasma reactor, α-Al₂O₃ particles of 1 and 3 mm (mean particle diameter) were packed as solid dielectric medium to enhance the plasma power density in the reactor. Further, alkaline sorbent of Ca(OH)₂ was doped onto the surface of α-Al₂O₃ particles, in order to remove halogenated products by in situ absorption with Ca(OH)₂. A high-voltage and high-frequency pulsed power of −15 to 15 kV and 1 kHz was applied to the wire electrode of the plasma reactor by means of a DC power source. In the present study, as the sample of an organic halogenated compound that is most popularly used, we selected dichloromethane (CH₂Cl₂), and 500 ppm of the initial concentration of CH₂Cl₂ was fed into the reactor accompanied by air at a fixed flow rate of 500 × 10⁻⁶ m³ min⁻¹ at room temperature. As a result, it was recognized that the amount of CH₂Cl₂ decomposed by non-thermal plasma in an α-Al₂O₃ particle bed increased with an increase in plasma input power. The ratio of decomposition of CH₂Cl₂ was almost 100% at 13 kV of electric power and 1 kHz frequency, and CO₂, CH₃Cl, COCl₂, HCl, and Cl₂ were observed as the major reaction products. On the other hand, when CH₂Cl₂ was introduced into the plasma reactor where α-Al₂O₃ particles doped with Ca(OH)₂ were packed, the ratio of decomposition of CH₂Cl₂ became higher, compared to the case that α-Al₂O₃ particles were not doped with Ca(OH)₂. Moreover, there were no halogenated by-product gases detected in the outlet gas from the reactor. As the solid reaction products, CaClOH and Ca(ClO)₂·4H₂O were detected on Ca(OH)₂ by X-ray diffraction. From these findings, it was recognized that CH₂Cl₂ was decomposed more effectively without producing unwanted harmful halogenated by-products in the proposed non-thermal plasma reactor where α-Al₂O₃ particles doped with Ca(OH)₂ sorbent were packed.     

Levels of trace elements in green turtle eggs collected from Hong Kong: Evidence of risks due to selenium and nickel

Concentrations of 22 trace elements were determined in green turtle (Chelonia mydas) eggs collected from Hong Kong. Concentrations of selenium, lead and nickel in these eggs were generally higher than those reported in other studies. The predicted no effect concentrations (PNEC; ng/g wet weight) of Pb (1000), Se (340 and 6000 for the worst-case and best-case scenarios, respectively) and Ni (17) in the green turtle eggs were estimated. Hazard quotients (HQs) estimate that Se (HQs: 0.2-24.5) and Ni (HQs: 4.0-26.4) may pose some risks to the turtles. Our study also found that concentrations of Ag, Se, Zn, Hg and Pb in the shell of the turtle eggs were significantly correlated with levels in the whole egg contents (yolk+albumen). Once the precise relationships of specific elements are established, egg-shell concentrations may be used as a non-lethal, non-invasive, surrogate for predicting whole egg burden of certain contaminants in marine turtles.     

Accumulation of organochlorine pesticides and polychlorinated biphenyls in sediments, aquatic organisms, birds, bird eggs and bat collected from South India

Concentrations of polychlorinated biphenyls (PCBs), DDT and its metabolites (DDTs), HCH isomers (HCHs), chlordane compounds (CHLs) and hexachlorobenzene (HCB) were determined in sediment, soil, whole body homogenates of resident and migratory birds and their prey items (including fish, green mussel, snail, earthworm, crabs, prawn, lizard and frogs), bird eggs and bats collected from southern India during 1995 and 1998. Accumulation pattern of organochlorines (OCs) in biota was, in general, in the order, HCHs > DDTs > PCBs > CHLs = HCB. Magnitude of OC concentrations increased in the order of sediments < green mussel < earthworm < from < lizard < fish < bird egg < bats < birds tissues. Biomagnification features of OCs were examined in resident and migrant birds to evaluate the exposure levels of these chemicals in wintering grounds of migrant birds. Accumulation of DDTs in migratory birds during wintering in India may be of concern due to the great biomagnification potential of DDTs. Eggs of some resident species contained noticeable concentrations of OCs. Concentrations of OCs in three species of bats analyzed in this study were lower than that found in passerine birds. In addition to OCs, butyltin compounds were also detected at low concentrations in bats.     

Trace elements and stable isotopes (delta13C and delta15N) in shallow and deep-water organisms from the East China Sea

Trace elements (22) and stable isotope ratios (δ¹⁵N and δ¹³C) were analyzed in marine organisms from shallow (SW) and deep-water (DW) of the East China Sea to understand biomagnification and prey source of trace elements. In the benthic marine organisms from DW, δ¹⁵N values were negatively correlated with Ba, Cu, Ag, Mo, Sr, As, and Co concentrations. This may be due to the specific accumulation in lower trophic animals and/or the biodilution through the food web in DW. Relationships between δ¹⁵N and concentrations of Co, Cr, Bi, and Tl in fish and Ag, Bi, V, Hg, and Tl in crustaceans showed positive correlations, suggesting that trophic position was affecting the concentrations of those elements in phyla, with higher trophic animals retaining higher concentrations than the lower trophic animals. Positive correlations between δ¹³C and Rb were observed in marine organisms. Therefore, Rb may be a possible substitute of δ¹³C as tracer of prey source in the East China Sea although further investigation is required.     

Characterization of trace constituents in landfill gas and a comparison of sites in Asia

Because landfill gas (LFG) contains an abundance of methane, the utilization of LFG as a renewable energy source is becoming popular in many countries. LFG, however, contains various trace constituents, some of which may pose problems during utilization. For example, siloxanes and halogenated volatile organic compounds (VOCs) can cause difficulties when present in the fuel of gas engines. In addition, many VOCs and mercury have harmful effects on human health, especially on the health of workers at landfill sites and people living near the landfills. Energy recovery from LFG is expected to make great progress in the near future, particularly in Asia, but we found little information on the trace constituents of LFG in this region. Therefore, we sought to characterize the trace components in LFG generated in two landfill sites in China and one site in Japan, to determine the typical concentrations of these trace components in LFG, and to compare their concentrations among landfill sites in Asia. We concluded that the trace components in LFG at the sites studied were mainly siloxanes generated from sewage sludge and harmful benzene, toluene, ethylbenzene, and xylene compounds from petroleum products.     

Organochlorine and butyltin residues in walleye pollock (Theragra chalcogramma) from Bering Sea, Gulf of Alaska and Japan Sea

Persistent organochlorine (OC) and toxic butyltin compounds (BTs) were determined in walleye pollock (Theragra chalcogramma) collected from Gulf of Alaska, Bering Sea and Japan Sea, during 1991 and 1992. Polychlorinated biphenyls (PCBs) and dichlorodiphenyltrichloroethane (DDTs) and its metabolites were the most abundant compounds ranging up to 3200 and 2500 ng/g on lipid weight, respectively, followed by chlordane compounds (CHLs), hexachlorocyclohexane isomers (HCHs) and hexachlorobenzene (HCB) in the liver of walleye pollock. Concentrations of HCHs and HCB in walleye pollock from these remote areas were higher than those in fishes from the western North Pacific and Japanese coastal waters, indicating atmospheric transport of these compounds to higher latitude regions such as Bering Sea and Gulf of Alaska and/or local input around northern Japan Sea. The concentrations of other OCs were generally comparable to those in fishes from North Pacific Ocean and Japanese waters but significantly lower than in cod-like fishes from North Atlantic and European countries. Among sampling locations, walleye pollock from Japan Sea showed higher concentrations of DDTs and HCHs compared to fishes from Bering Sea and Gulf of Alaska, suggesting greater input of these compounds around Japan Sea. Slower declining trend of DDTs and CHLs and an increasing pattern of PCBs concentrations were found in walleye pollock from Bering Sea during 1982-1992. This may imply a continuous input of these compounds by long-range transport and/or long-term persistency in these cold regions. Compared to the fishes from Japan Sea, walleye pollock from Bering Sea and Gulf of Alaska showed higher proportions of alpha-HCH and p,p'-DDE in the composition of HCH isomers and DDT compounds, respectively. This suggests selective transportability of these compounds during long-range transport to higher latitude remote areas. Concentrations of tributyltin (TBT) in the muscle of walleye pollock ranged from 1.1 to 5.5 ng/g on wet weight. Concentrations of TBT in deep-sea walleye pollock from Gulf of Alaska and Bering Sea were lower than those in Japan Sea.     

Brominated flame retardants and polychlorinated biphenyls in human breast milk from several locations in India: potential contaminant sources in a municipal dumping site

This study investigated the status of contamination of organohalogen compounds (OCs) such as polychlorinated biphenyls (PCBs) and brominated flame retardant (BFRs), including polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs) in human milk samples from several locations in India. The levels of OCs were significantly higher in the milk of mothers living in and near municipal dumping site than other locations indicating that the open dumping sites for municipal wastes act as potential sources of these contaminants in India. The PCB concentrations observed in this study tended to decrease compared to those in the matched locations reported previously, probably due to the restriction of technical PCB usage in India. PBDE levels in human milk were two to three folds lower than those of PCBs in all the sampling locations investigated. Congener profiles of PCBs and PBDEs were different between samples from the dumping site mothers and general populations in other areas suggesting the presence of region-specific sources and pathways. HBCDs were detected in human milk from only two sites, with much lower concentrations and detection frequencies compared to PCBs and PBDEs. When hazard quotients (HQs) of PCBs and PBDEs were estimated for infant health risk, the HQs in some milk samples from the dumping site exceeded the threshold value (HQ > 1) of PCBs, indicating the potential risk for infants in the specific site.