Accumulation status of persistent organochlorines in albatrosses from the North Pacific and the Southern Ocean

Current status of contamination by persistent organochlorines (OCs) such as polychlorinated biphenyles (PCBs), dichlorodiphenyl trichloroethane and its metabolites (DDTs), isomers of hexachlorocyclohexane (HCHs), hexachlorobenzene (HCB) and chlordane compounds (CHLs) were examined in 61 individuals belonging to eight albatross species collected from the North Pacific and the Southern Ocean. Generally high OC concentrations were found in albatrosses from the North Pacific than those from the Southern Oceans. Black-footed albatrosses had noticeably high PCBs and DDTs concentrations with mean values of 92 and 33 micrograms/g wet weight in subcutaneous fat, respectively. Among the other OCs, concentration of CHLs was higher than that of HCB in North Pacific albatrosses. HCHs accumulation was the lowest among all the OCs analyzed. Species-specific differences were observed for HCB, CHLs and DDTs in some species in the Southern Ocean. No significant difference of gender and age-related accumulation was observed in total OCs. However, PCB concentrations were higher in mature birds than those from immature ones in the Southern Ocean. Species-specific accumulation patterns of OCs in albatrosses were closely related with their feeding, migration, age and geographical ranges.     

Butyltins in muscle and liver of fish collected from certain Asian and Oceanian countries

Concentrations of butyltin residues were determined in muscle tissue of fish collected from local markets and sea food shops in India, Bangladesh, Thailand, Indonesia, Vietnam, Taiwan, Australia, Papua New Guinea and the Solomon Islands. Contamination levels were determined in the Asia-Pacific region and human exposure was estimated. Similarly, corresponding liver samples of fish muscle collected in Australia, Papua New Guinea and the Solomon Islands were analyzed to obtain information on partitioning of butyltin compounds between muscle and liver tissues. Butyltin compounds were detected in most of the samples which suggested widespread contamination in Asia and Oceania. The concentrations of butyltin compounds were, on average, an order of magnitude higher in liver than in muscle. Residue concentration of Sigmabutyltin in liver was found to be correlated significantly (p < 0.02) with those in muscle. Intensive ship-scrapping activities, sewage disposal and antifouling paints are considered the major sources of butyltins in this region. Increased proportions of MBT over DBT and TBT in samples from most locations indicated degradation of TBT to MBT in fish tissues during storage at 4 degrees C in the dark over 1-2 years. The possibility that fish have been subject to increased exposure to MBT and that TBT degrades to MBT quite rapidly in tropical environments are also considered. Butyltin concentrations in fish from Asia and Oceania were lower than those reported for Japan, Canada and the USA. Although the number of samples analyzed from each country was small, it is tentatively suggested that intake of butyltins by humans via consumption of fish in these countries was < 25% of the tolerable daily intake of 250 ng kg bw(-1) day(-1). To our knowledge, this is the first study reporting on butyltin pollution in developing Asian countries.     

Specific accumulation of polychlorinated biphenyls and organochlorine pesticides in Japanese common squid as a bioindicator

Organochlorines (OCs) representing Persistent Organic Pollutants (POPs) such as PCBs (polychlorinated biphenyls), DDTs (DDT and its metabolites), CHLs (chlordane compounds), HCHs (hexachlorocyclohexane isomers) and HCB (hexachlorobenzene) were determined in the liver of Japanese common squid (Todarodes pacificus) collected from the waters around Japan (Japan Sea and western North Pacific Ocean). Among OCs concentrations, PCBs (upto 5600 ng/g lipid wt.) were the highest, and those of other OCs were in the order of DDT> CHLs > HCHs > HCB. Studies on growth trend and seasonal variation of OCs in this species suggest a rapid reflection of the pollution levels in seawater where and when they were collected, regardless of body-length and time of collection. These results indicate that Japanese common squid is a suitable bioindicator for monitoring OCs pollution in waters around Japan. With regard to the geographical distribution of OCs in this species collected from waters around Japan, OCs concentrations in specimens from Japan Sea were higher than those from the Pacific Ocean. This result might reflect some existing of local pollution sources of OCs around Japan Sea, and slower water exchange between Japan Sea and open ocean.     

Widespread contamination by tris(4-chlorophenyl)methane and tris(4-chlorophenyl)methanol in cetaceans from the North Pacific and Asian coastal waters

For understanding global distribution, transport and behavior of tris(4-chlorophenyl)methane (TCPMe) and tris(4-chlorophenyl)methanol (TCPMOH), the two newly identified microcontaminants, the present study determined their concentrations and other persistent organochlorines (OCs) in the blubber of nine species of adult male cetaceans collected from various locations in the North Pacific Ocean and coastal waters of some Asian countries, during 1985-97. Concentrations of TCPMe and TCPMOH were found to be highest in northern right whale dolphins, which may be attributable to wide distribution of this species, including some heavily polluted areas such as coastal California. Elevated residue levels of TCPMe and TCPMOH were observed in both off-shore and coastal species, suggesting widespread contamination of these compounds in the marine environment. Higher contamination of TCPMe and TCPMOH was found in cetaceans from temperate and cold waters than those from tropical regions. The latitudinal distribution of TCPMe and TCPMOH in cetaceans from the North Pacific and Asian coastal waters was similar to that of DDTs, suggesting less transportable nature of TCPMe and TCPMOH in the marine environment. Data on the occurrence of TCPMe and TCPMOH further indicated high bioaccumulation potential of these compounds, which was comparable to DDTs. Relative concentrations of TCPMe/TCPMOH in cetaceans were apparently higher than those observed in seals, suggestive of lower metabolic capacity for these compounds in cetaceans than in pinnipeds, which is similar to classic contaminants like polychlorinated biphenyls and DDTs.     

In vitro inhibition of hepatic cytochrome P450 and enzyme activity by butyltin compounds in marine mammals

The present study attempted to examine the in-vitro inhibition of hepatic microsomal P450 content and activity by butyltins in marine mammals and discussed on their possible effects in animals in the wild. Decreases in P450 content and the activities of ethoxyresorufin O-deethylase (EROD, catalyzed by CYPIA subfamily) and penthoxyresorufin O-depentylase (PROD, catalyzed by CYP2B subfamily) by tributyltin (TBT) were observed in in-vitro experiments using hepatic microsomes of a pinniped and a cetacean. Among P450 family, EROD activity is more sensitive to TBT than P450 content and PROD activity, indicating a specific mode of action of TBT on different P450 forms. On the other hand, dibutyltin and monobutyltin have no inhibitory effect on EROD activity at concentrations less than 0.5 mM, indicating that the inhibition of enzyme activity in hepatic microsome of marine mammal is mainly by TBT. TBT concentrations that affect P450 contents and activities are above 10 times higher than the values found in the liver of various marine mammals.     

Specific accumulation of 20 trace elements in great cormorants (Phalacrocorax carbo) from Japan

This study is to elucidate the specific accumulation of 20 trace elements in tissues/organs of great cormorants from two different colonies (Lake Biwa and Mie) in Japan. In the body distribution of trace elements, some elements revealed tissue-specific accumulation such as most of the burden of Mo, Ag and Cd in liver, Tl and Cd in kidney, Cu, Rb and Cs in muscle, and V, Sr and Ba in bone. Gender-related variation was not observed in both populations for most of the trace elements, except for higher hepatic Sr in males from Lake Biwa. Hepatic V, muscular Hg and Tl, and Cd in liver, kidney and muscle increased with growth. Comparison of trace element levels in tissues between the two colonies showed that Cr, Rb, Sr, Cd, Cs, Ba and Tl levels were higher in Lake Biwa than in Mie, whereas Zn, Co and Hg in Mie samples were greater than Lake Biwa. Variations of elemental levels in stomach contents also showed similar patterns, thus, showing that dietary sources tended to be the main factor for these regional variations. Toxic Hg and Cd concentrations in the liver of cormorants from the two colonies were lower than those from other areas, implying relatively low exposure to these metals in the present study sites. Concentrations of V, Co, Ag, Cd, Cs, Hg, Tl, Pb and Bi in liver remained more or less at the same level between 1993 and 2003, while hepatic Cr, Mn, Cu, Zn, Se, Rb, Sr and Ba showed apparent decrease, which might be related to the biological factors.     

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.     

Gain and loss rates and biological half-life of PCBs and DDE in the bodies of adelie penguins

The gain and loss rates and the biological half-life of polychlorinated biphenyls (PCBs) and p,p'-DDE in wild birds were calculated using the values on burdens of these compounds in the bodies of adelie penguins in a previous report (Subramanian et al., 1986). The daily loss rate of PCBs (0.26%) was found to be higher than DDT compounds (0.12%) resulting in the longer biological half-life of the latter compounds (580 days) than PCBs (270 days). Hence, once DDT compounds are absorbed they are more persistent in the organisms' bodies due to their high lipophilicity and comparatively less metabolisable nature than PCBs.     

Risk reduction concept to provide design criteria for Emergency Systems for onshore LNG plants

The functional safety requirement is widely applied in the process plant industry in accordance with the international standards, such as IEC and ISA. The requirement is defined as safety integrity level (SIL) based on the risk reduction concept for protection layers, from original process risk to tolerable risk level. Although the standards specify both, the Prevention System and the Emergency System, as level of protection layers, the standards specify in detail only the use of the Prevention System (i.e., Safety Instrumented System (SIS)). The safety integrity level is not commonly allocated to the Emergency System (e.g., Fire and Gas System, Emergency Shutdown System and Emergency Depressuring System). This is because the required risk reduction can be normally achieved by only the Prevention System (i.e., SIS and Pressure Safety Valve (PSV)). Further, the risk reduction level for the Emergency System is very difficult to be quantified by the actual SIL application (i.e., evaluated based on the single accident scenario, such as an accident from process control deviation), since the escalation scenarios after Loss of Containment (LOC) greatly vary depending on the plant design and equipment. Consequently, there are no clear criteria for evaluating the Emergency System design. This paper aims to provide the functional safety requirement (i.e., required risk reduction level based on IEC 61508 and 61511) as design criteria for the Emergency System.In order to provide clear criteria for the Emergency System evaluation, a risk reduction concept integrated with public’s perception of acceptable risk criteria is proposed and is applied to identify the required safety integrity level for the Emergency System design. Further, to verify the safety integrity levels for the Emergency Systems, the probabilistic model of the Emergency Systems was established considering each Emergency System (e.g., Fire and Gas System, Emergency Shutdown System and Emergency Depressuring System) relation as the Overall Emergency System. This is because the Overall Emergency System can achieve its goal by the combined action of each individual system, including inherent safe design, such as separation distance.The proposed approach applicability was verified by conducting a case study using actual onshore Liquefied Natural Gas Plant data. Further, the design criteria for Emergency Systems for LNG plants are also evaluated by sensitivity analysis.     

Silver speciation in liver of marine mammals by synchrotron X-ray absorption fine structure and X-ray fluorescence spectroscopies

The chemical form of Ag in the livers of five species of marine mammals was examined using X-ray absorption fine structure (XAFS) and X-ray fluorescence (XRF) spectroscopies. The XAFS analysis suggested that Ag(2)Se was present in the livers of the Franciscana dolphin (Pontoporia blainvillei), Dall's porpoise (Phocoenoides dalli), and Baird's beaked whale (Berardius bairdii), whereas Ag(2)S was present in the livers of the striped dolphin (Stenella coeruleoalba) and pygmy killer whale (Feresa attenuata). XRF spectroscopy results revealed that the distribution patterns of Ag and Se in a thin section of the liver of the Franciscana dolphin were the same; this also implied that Ag was associated with Se in the liver. Thus, the interaction of Ag with Se or S may offer significant protection against the toxicity of Ag in marine mammals. The formation of either Ag(2)Se or Ag(2)S might depend on the Hg levels in the liver. Ag(2)Se was observed in liver samples with relatively high Ag/Hg ratio, whereas liver samples with low Ag/Hg ratio contained Ag(2)S.