Organochlorine and butyltin residues in deep-sea organisms collected from the western North Pacific,off-Tohoku,Japan

Organochlorine (OCs) and butyltin (BTs) residues were determined in deep-sea organisms collected from the western North Pacific, off-Tohoku, Japan. Among OCs, concentrations of polychlorinated biphenyls (PCBs) and DDTs (DDTs and its metabolites) were the highest in deep-sea organisms (maximum concentrations of 6700 and 13,000 ng/g lipid wt, respectively). Chlordane compounds (CHLs) were the next most abundant OCs, and hexachlorocyclohexanes (HCHs) and hexachlorobenzene (HCB) were the lowest. BTs were also detected at maximum concentrations of 570 ng/g wet wt. Concentrations of PCBs, CHLs and BTs in deep-sea organisms collected from the western North Pacific, off-Tohoku, were generally lower than those in deep-sea and shallow water organisms from Japanese coastal waters. On the other hand, considerable variations in the concentrations of OCs were found among deep-sea organisms analyzed. Several carnivorous fishes such as snubnosed eel, lanternshark and grenadiers accumulated some OCs such as PCBs, DDTs and CHLs at high concentrations of up to a few μg/g levels. In addition, the residue pattern of OCs and BTs in fishes showed a specific trend according to the sampling depth; higher concentrations of PCBs, DDTs and CHLs and lower concentrations of HCHs, HCB and BTs were found in fishes collected from greater depth (1000 m) compared to those from shallower waters. This trend is consistent with the results of our earlier study on mesopelagic myctophid fishes. Results of this study suggest vertical transport of hydrophobic OCs such as PCBs, DDTs and CHLs and its accumulation in benthic deep-sea organisms.     

Brominated flame retardants and organochlorine contaminants in winter flounder, harp and hooded seals, and North Atlantic right whales from the Northwest Atlantic Ocean

Various brominated flame retardants (BFRs), including polybrominated diphenyl ethers (PBDEs) and current-use, non-PBDE BFRs, as well as organochlorine (OC) pesticides and polychlorinated biphenyls (PCBs), were measured in winter flounder, harp and hooded seals, and North Atlantic right whales from the Eastern United States and Canada. The concentrations of PBDEs in winter flounder and right whales were similar in magnitude to the levels of PCBs, which was unlike the pattern observed in seals. In these marine mammals, the levels of PBDEs were orders of magnitude lower than the levels of OCs and PCBs detected. Evidence existed for the accumulation of methoxylated (MeO)-PBDEs of natural origin in seals and right whales. Current-use, non-PBDE BFRs (including hexabromocyclododecane, pentabromoethylbenzene, hexabromobenzene, and pentabromotoluene) were detected in winter flounder and marine mammals. Future research should focus on monitoring PBDEs, current-use, non-PBDE BFRs, and MeO-BDEs of natural origin in marine organisms from Massachusetts and Cape Cod Bays.     

Temporal trends of brominated flame retardants in coastal waters of Japan and South China: Retrospective monitoring study using archived samples from es-Bank, Ehime University, Japan

The present paper is a summary of studies conducted at the Center for Marine Environmental Studies, Ehime University, on temporal trends of brominated flame retardants (BFRs) in coastal waters of Japan and South China. Archived marine mammal fat tissues and dated sediment cores were used to evaluate temporal trends of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs) in relation to their usage in the region. The results indicate that environmental concentrations of these BFRs in Japan and South China increased significantly during the last several decades. Temporal trends in the contaminant concentrations were consistent with historical consumption of the corresponding BFRs. PBDE levels in marine mammals and sediments from Japan, after showing peak concentrations in the 1990s, appear to be leveling off in recent years, in accordance with the discontinued usage of Tetra- and Octa-BDEs in Japan from the 1990s. The change in concentration levels was also accompanied by changes in PBDE congener profiles, i.e. shift towards increased proportion of higher brominated BDEs. Furthermore, in recent years HBCD concentrations in marine mammals from Japan appear to exceed those of PBDEs, presumably reflecting increasing usage of HBCDs over PBDEs. In finless porpoises from the South China Sea, PBDE levels were much higher than HBCD concentrations both in the past and recent years, implying consumption of HBCDs was not as high as that of PBDEs in China. In dated sediment cores from Tokyo Bay, concentrations increased exponentially with doubling times of 4.6–7.9 years, 6.1–12 years and 7.1–12 years for BDE-209, ΣPBDEs and HBCDs, respectively.     

Contamination status and spatial distribution of organochlorine compounds in fishes from Nansei Islands,Japan

Two species of fishes (n = 52; tilapia and mullet) from industrialized and urbanized areas of Okinawa Island (Manko-Noha river, Hija river and Shikaza river) and from a remote area of Ishigaki Island (Anparu mudflat), Japan were collected between August 2005 and July 2006, and analyzed for five organochlorine compounds (OCs), viz., DDTs, PCBs, CHLs, HCHs and HCB. Concentrations and the contamination patterns of OCs in fishes varied between locations. Considerable residue levels of OCs, especially CHLs and DDTs were found in both fishes from the main Okinawa Island. These levels were relatively higher than the reported values for seafood from Japanese coasts, indicating that even now pollution sources of these contaminants still exist in this region. On the other hand, lower concentrations of OCs were detected in fishes from Ishigaki Island waters than those of other Japanese coastal waters, suggesting that this region is less contaminated by OC contaminants.     

Contamination status and spatial distribution of organochlorine compounds in fishes from Nansei Islands, Japan

Two species of fishes (n=52; tilapia and mullet) from industrialized and urbanized areas of Okinawa Island (Manko-Noha river, Hija river and Shikaza river) and from a remote area of Ishigaki Island (Anparu mudflat), Japan were collected between August 2005 and July 2006, and analyzed for five organochlorine compounds (OCs), viz., DDTs, PCBs, CHLs, HCHs and HCB. Concentrations and the contamination patterns of OCs in fishes varied between locations. Considerable residue levels of OCs, especially CHLs and DDTs were found in both fishes from the main Okinawa Island. These levels were relatively higher than the reported values for seafood from Japanese coasts, indicating that even now pollution sources of these contaminants still exist in this region. On the other hand, lower concentrations of OCs were detected in fishes from Ishigaki Island waters than those of other Japanese coastal waters, suggesting that this region is less contaminated by OC contaminants.     

Isomer specific determination of hexabromocyclododecanes (HBCDs) in small cetaceans from the South China Sea--Levels and temporal variation

A diastereoisomer (alpha, beta, and gamma) specific analytical method for measuring hexabromocyclododecanes (HBCDs) was developed using liquid chromatography-tandem mass spectrometry (LC-MS-MS). The method developed was applied to analyze blubber of small cetaceans to divulge the distribution and temporal variation of HBCDs in the Asian marine environment. HBCDs were detected in all the blubber samples of finless porpoises (Neophocaena phocaenoides) and Indo-Pacific humpback dolphins (Sousa chinensis) collected from the South China Sea during 1990-2001. Concentrations of HBCDs were higher in humpback dolphins (31-380 ng/g lipid) than in finless porpoises (4.7-55 ng/g lipid), which can be attributed to habitat differences. Average concentrations of alpha-HBCD in finless porpoises increased from 9.5 ng/g lipid in 1990 to 35 ng/g lipid in 2000/01. alpha-HBCD was predominant among the three isomers with some exceptions in finless porpoises collected in 1990. This is the first report on HBCDs contamination in marine mammals from Southeast Asia.     

Organochlorine pesticides in fish from the southern Baltic Sea: levels, bioaccumulation features and temporal trends during the 1995-2006 period

The levels of HCH isomers, HCB and summation DDTs were determined in five species of Baltic fish collected during 1995-2006. Some downward time trends of HCH isomer, pp'-DDE and pp'-DDD concentrations in Baltic fish were observed; in contrast, HCB and DDT concentrations did not exhibit any obvious trend. Concentrations of summation HCHs expressed on a lipid weight basis were very similar in all species studied. In contrast, concentrations of summation DDTs varied in tested species. The most abundant HCH isomer was beta-HCH and among DDT-related compounds, pp'-DDE prevailed. In our investigations the sampling sites were not a crucial factor for organochlorine pesticide concentrations and patterns observed in fish, but the occurrence of several inter-species differences in the bioaccumulation features of OC pesticides were observed. For cod there was a positive correlation between fish size (length) and summation DDT concentration. In herring, sprat and salmon samples, summation DDT concentrations were negatively correlated with fat content.     

Effects of age, sex and reproductive status on persistent organic pollutant concentrations in “Southern Resident” killer whales

“Southern Resident” killer whales (Orcinus orca) that comprise three fish-eating “pods” (J, K and L) were listed as “endangered” in the US and Canada following a 20% population decline between 1996 and 2001. Blubber biopsy samples from Southern Resident juveniles had statistically higher concentrations of certain persistent organic pollutants than were found for adults. Most Southern Resident killer whales, including the four juveniles, exceeded the health-effects threshold for total PCBs in marine mammal blubber. Maternal transfer of contaminants to the juveniles during rapid development of their biological systems may put these young whales at greater risk than adults for adverse health effects (e.g., immune and endocrine system dysfunction). Pollutant ratios and field observations established that two of the pods (K- and L-pod) travel to California to forage. Nitrogen stable isotope values, supported by field observations, indicated possible changes in the diet of L-pod over the last decade.     

Organohalogen contaminants in finless porpoises (Neophocaena phocaenoides) from Korean coastal waters: Contamination status, maternal transfer and ecotoxicological implications

Information on the occurrence of organochlorine compounds (OCs) and polybrominated diphenyl ethers (PBDEs) in marine mammals from Korea is scarce. In this study, OCs and PBDEs were determined in the blubber of 52 finless porpoises (Neophocaena phocaenoides) from Korean coastal waters. The highest contamination was found for DDTs, followed by PCBs, PBDEs, HCHs, CHLs and HCB. Concentrations of OCs in finless porpoises were lower than those reported worldwide, but PBDE contamination was comparable to other studies, due to ongoing use of PBDE products in Korea. Significant gender-specific differences were found for concentrations and accumulation profiles of OCs and PBDEs, due to maternal transfer and lactation of mature females. The BDEs 49 and 66 comprised 4-16% of total PBDEs in finless porpoises, which seems to be associated with debromination of higher BDEs. The DDT levels in Korean finless porpoises have almost reached the levels associated with immunosuppression in marine mammals.     

Polybrominated diphenyl ethers (PBDEs) and organochlorines in small cetaceans from Hong Kong waters: levels, profiles and distribution

Polybrominated diphenyl ethers (PBDEs) and organochlorine compounds (OCs) were determined in the blubber, liver and kidney of Indo-Pacific humpback dolphins (Sousa chinensis) and finless porpoises (Neophocaena phocaenoides) stranded in Hong Kong coastal waters during 1995–2001. Among the organohalogen compounds analyzed, DDTs were the most dominant contaminants with concentrations ranging from 9.9 to 470 μg/g lipid wt. PBDEs in Hong Kong cetaceans, which are reported for the first time, were detected in all the samples with values ranging from 0.23 to 6.0 μg/g lipid wt., with a predominance of BDE-47. Results from this study suggest PBDEs should be classified as priority pollutants in Asia. Higher concentrations were found in humpback dolphins than in finless porpoises, and this was attributed mainly to differences in habitat. Elevated residues of PCBs and DDTs in some cetaceans suggest these species may be at risk.     

Mercury in the ecosystem of Admiralty Bay,King George Island,Antarctica: Occurrence and trophic distribution

Mercury (Hg) can reach the environment through natural and human-related sources, threatening ecosystems all over the planet due to its well known deleterious effects. Therefore, Antarctic trophic webs, despite being relatively isolated, are not exempt of its influence. To evaluate Hg concentrations in an Antarctic ecosystem, different tissues from 2 species of invertebrates, 2 of fish, 8 of birds, 4 of pinnipeds and at least 5 of vegetation were investigated (n = 176). For animals, values ranged from 0.018 to 48.7 μg g^? 1 dw (whole Antarctic krill and Antarctic Fur Seal liver). They were generally correlated to trophic position (assessed by δ¹⁵N and δ¹³C) but also to cephalopods and myctophids consumption. For vegetation, values ranged from 0.014 to 0.227 μg g^? 1 dw (Colobanthus quitensis and an unidentified lichen), with lichens presenting significantly higher values than mosses, likely due to year-round exposure and absorption of animal derived organic matter, as hypothesized by literature.     

Summary of the fossil record of pinnipeds of Japan, and comparisons with that from the eastern North Pacific

Abstract The fossil pinniped record of the North Pacific Ocean includes both Phocidae and Otariidae ( sensu lato ), extends from the Late Oligocene to the Late Pleistocene, is taxonomically diverse, and is constantly becoming more complete owing to additional important discoveries. The earliest and most diverse fossil pinnipeds in the North Pacific are otariids, the phocids not appearing until the latest Pliocene. The theoretical center of otariid pinniped evolutionary history has been considered by some to be in the eastern North Pacific. New materials from the western North Pacific, however, including representatives of the subfamilies Enaliarctinae, Imagotariinae, Odobeninae and Otariinae, indicate that pinniped evolutionary patterns were basin-wide phenomena, and that a more complete record undoubtedly would reveal numerous trans-Pacific distributions. This would be expected considering the distributions of living species. The paucity of fossil Phocidae and their absence from pre-Pliocene deposits are consistent with theories that the family primarily evolved outside the North Pacific.     

History of anthropogenic nitrogen input to the German Bight/SE North Sea as reflected by nitrogen isotopes in surface sediments,sediment cores and hindcast models

The German Bight/SE North Sea is considered a hot-spot of river-induced eutrophication, but the scarce observational data of river nitrate loads prior to the 1970s complicate the assessment of target conditions for environmental management and legislation. Stable nitrogen isotope ratios (δ¹⁵N) in sediment records can be used to decipher historical river nitrate contributions. To better constrain pre-1970s conditions, we determined δ¹⁵N in archive sediment samples (1950–1969) and dated cores from the Helgoland depositional area. We also modeled the δ¹⁵N in past situations (1960 and 1860) using an N-isotope-tracking ecosystem model. The modeled spatial distribution of δ¹⁵N in sediments for 1960 conditions and the observed spatial pattern of δ¹⁵N in archive sediment samples (1950–1969) represent a period of moderate eutrophication. The modeled spatial distribution of δ¹⁵N in sediments for 1860 conditions (pre-industrial) showed a moderate δ¹⁵N gradient from the Elbe river mouth (δ¹⁵N<4‰) to the open sea (δ¹⁵N∼5‰). This pattern contrasts with the δ¹⁵N pattern in modern surface sediments, which exhibits a steep and inverted δ¹⁵N gradient from the Elbe river mouth (δ¹⁵N>9‰) to the open sea (δ¹⁵N<7‰). Modeled δ¹⁵N for 1860 conditions are consistent with δ¹⁵N values observed in dated sediment cores that span the last 900 years. Value of δ¹⁵N in sediment cores increased from approximately 1860 to 2000 by 2.5‰. The increasing trend reflects changes in the abundance and isotopic composition of riverine nitrate loads caused by anthropogenic activities. Sensitivity tests suggest that loads and isotopic ratios of nitrogen forms other than nitrate (ammonium and organic nitrogen) have minor impact on the modeled surface sediments, despite their higher abundance in the riverborne loads in the past. Our results suggest that eutrophication of the German Bight predates the 1960 period of documented rapidly increasing river loads. Pre-industrial levels of δ¹⁵N modeled with 28% of the modern annual (1990–1999) atmospheric loads and 10% of the modern annual river loads agree best with levels of δ¹⁵N (∼6‰) observed in sediments of the cores dated to 1860.     

An evaluation and improvement of tropical cyclone prediction in the western North Pacific basin from global ensemble forecasts

Forecasts of tropical cyclones(TCs) of the western North Pacific basin during the period of July to August 2018,especially of Rumbia(2018), Ampil(2018) and Jongdari(2018) that made landfall over Shanghai, have opposed great challenges for numerical models and forecasters. The predictive skill of these TCs are analyzed based on ensemble forecasts of ECMWF and NCEP. Results of the overall performance show that ensemble forecasts of ECMWF generally have higher predictive skill of track and intensity forecasts than those of NCEP. Specifically, ensemble forecasts of ECMWF have higher predictive skill of intensity forecasts for Rumbia(2018) and Ampil(2018) than those of NCEP, and both have low predictive skill of intensity forecasts for Jongdari(2018) at peak intensity. To improve the predictive skill of ensemble forecasts for TCs, a method that estimates adaptive weights for members of an ensemble forecast is proposed. The adaptive weights are estimated based on the fit of ensemble priors and posteriors to observations. The performances of ensemble forecasts of ECMWF and NCEP using the adaptive weights are generally improved for track and intensity forecasts. The advantages of the adaptive weights are more prominent for ensemble forecasts of ECMWF than for those of NCEP.     

Organohalogen contaminants in striped dolphins (Stenella coeruleoalba) from Japan: Present contamination status, body distribution and temporal trends (1978-2003)

Organohalogen contaminants including PCBs, DDTs, CHLs, HCHs, HCB, PBDEs and HBCDs were determined in striped dolphins (Stenella coeruleoalba) found stranded at Gogo-shima (n = 6, 2003) and collected from Taiji (n = 15, 1978-1992) in Japan. All target compounds were significantly detected in all the specimens, indicating ubiquitous contamination of oceanic cetaceans in northwest Pacific Ocean. Examination of body distribution of organohalogens in the six specimens from Gogo-shima showed no significant difference in concentrations among the analyzed tissues, except for brain, which had lower levels possibly due to the existence of blood-brain barrier. For evaluating temporal trends, archived blubber samples of adult male stripped dolphins collected in 1978, 1979, 1986 and 1992 were analyzed. Concentrations of PCBs, DDTs and HCHs did not change significantly during 1978-2003. In contrast, remarkable increasing trends of PBDEs and HBCDs were observed, suggesting growing consumption in Japan and surrounding countries in recent years.     

Identification of the natural product 2,3,4,5-tetrabromo-1-methylpyrrole in Pacific biota, passive samplers and seagrass from Queensland, Australia

Halogenated natural products (HNPs) are frequently detected in marine organisms. High HNP concentrations have previously been found in marine mammals from the Great Barrier Reef, Australia, including in the blubber of herbivorous dugongs (Dugong dugon). To identify the source of HNPs we initially focused on the analysis of Australian seagrass (Halophila ovalis) which serves as the principal food source for dugongs. GC/MS analysis of the seagrass indicated the presence of several organobromine compounds. One compound was identified as 2,3,4,5-tetrabromo-1-methylpyrrole (TBMP) by synthesis. Subsequent analysis of semipermeable membrane devices demonstrated that the photo-sensitive TBMP is widespread in the Great Barrier Reef (Queensland, Australia). The detection of larger TBMP concentrations in fish fillets from Chile and traces in mussels from New Zealand indicated that this potential HNP may be distributed throughout the Southern Pacific Ocean.     

Longitudinal distributions of two formation pathways of biogenic gases in continental deposits: A case study from Sebei 1 gas field in the Qaidam Basin, western China

The distribution of two formation pathways of biogenic methane, acetate fermentation and reduction of CO2, has been extensively studied. In general, CO2 reduction is the dominate pathway in marine envi- ronment where acetate is relatively depleted because of SRB consuming. While in terrestrial freshwater or brackish environment, acetate fermentation is initially significant, but decreases with increasing buried depth. In this paper, character of biogenic gases is profiled in the XS3-4 well of the Sebei 1 gas field in the Sanhu depression, Qaidam Basin. It indicates that those two pathways do not change strictly with increasing buried depth. CO2 reduction is important near the surface (between 50 m and 160 m), and at the mesozone (between 400 and 1650 m). While acetate fermentation is the primary pathway at two zones, from 160 to 400 m and from 1650 to 1700 m. δ 13C of methane generated in those two acetate fermentation zones varies greatly, owing to different sediment circumstances. At the sec- ond zone (160-400 m), δ 13C1 ranges from ?65‰ to ?30‰ (PDB), because the main deposit is mudstone and makes the circumstance confined. At the fourth zone of the well bottom (1650-1700 m), δ 13C1 is lighter than ?65‰ (PDB). Because the deposit is mainly composed of siltstone, it well connects with outer fertile groundwater and abundant nutrition has supplied into this open system. The high con- centration of acetate is a forceful proof. δ 13C of methane would not turn heavier during fermentation, owing to enough nutrition supply. In spite of multi-occurrence of acetate fermentation, the commercial gas accumulation is dominated by methane of CO2-reduction pathway. A certain content of alkene gases in the biogenic gases suggests that methanogensis is still active at present.     

The crater lake and hydrothermal system of Mount Pinatubo,Philippines: evolution in the decade after eruption

The June 1991 eruption of Mount Pinatubo, Philippines breached a significant, pre-eruptive magmatic-hydrothermal system consisting of a hot (>300 °C) core at two-phase conditions and surrounding, cooler (<260 °C) liquid outflows to the N and S. The eruption created a large, closed crater that accumulated hydrothermal upwellings, near-surface aquifer and meteoric inflows. A shallow lake formed by early September 1991, and showed a long-term increase in level of ~1 m/month until an artificial drainage was created in September 2001. Comparison of the temporal trends in lake chemistry to pre- and post-eruptive springs distinguishes processes important in lake evolution. The lake was initially near-neutral pH and dominated by meteoric influx and Cl–SO₄ and Cl–HCO₃ hydrothermal waters, with peaks in SO₄ and Ca concentrations resulting from leaching of anhydrite and aerosol-laden tephra. Magmatic discharge, acidity (pH~2) and rock dissolution peaked in late 1992, during and immediately after eruption of a lava dome on the crater floor. Since cessation of dome growth, trends in lake pH (increase from 3 to 5.5), temperature (decline from 40 to 26 °C), and chemical and isotopic composition indicate that magmatic degassing and rock dissolution have declined significantly relative to the input of meteoric water and immature hydrothermal brine. Higher concentrations of Cl, Na, K, Li and B, and lower concentrations of Mg, Ca, Fe, SO₄ and F up to 1999 highlight the importance of a dilute hydrothermal contribution, as do stable-isotope and tritium compositions of the various fluids. However, samples taken since that time indicate further dilution and steeper trends of increasing pH and declining temperature. Present gas and brine compositions from crater fumaroles and hot springs indicate boiling of an immature Cl–SO₄ geothermal fluid of near-neutral pH at approximately 200 °C, rather than direct discharge from magma. It appears that remnants of the pre-eruptive hydrothermal system invaded the magma conduit shortly after the end of dome emplacement, blocking the direct degassing path. This, along with the large catchment area (~5 km²) and the high precipitation rate of the area, led to a rapid transition from a small and hot acid lake to a large lake with near-ambient temperature and pH. This behavior contrasts with that of peak-activity lakes that have more sustained volcanic gas influx (e.g., Kawah Ijen, Indonesia; Poas and Rincón de la Vieja, Costa Rica).Editorial responsibility: H. Shinohara     

Organic carbon and nitrogen stable isotopes in the intertidal sediments from the Yangtze Estuary, China

The natural isotopic compositions and C/N elemental ratios of sedimentary organic matter were determined in the intertidal flat of the Yangtze Estuary. The results showed that the ratios of carbon and nitrogen stable isotopes were respectively −29.8‰ to − 26.0‰ and 1.6‰–5.5‰ in the flood season (July), while they were −27.3‰ to − 25.6‰ and 1.7‰–7.8‰ in the dry season (February), respectively. The δ¹³C signatures were remarkably higher in July than in February, and gradually increased from the freshwater areas to the brackish areas. In contrast, there were relatively complex seasonal and spatial changes in stable nitrogen isotopes. It was also reflected that δ¹⁵N and C/N compositions had been obviously modified by organic matter diagenesis and biological processing, and could not be used to trace the sources of organic matter at the study area. In addition, it was considered that the mixing inputs of terrigenous and marine materials generally dominated sedimentary organic matter in the intertidal flat. The contribution of terrigenous inputs to sedimentary organic matter was roughly estimated according to the mixing balance model of stable carbon isotopes.