Occurrence and accumulation features of polycyclic aromatic hydrocarbons and synthetic musk compounds in finless porpoises (Neophocaena phocaenoides) from Korean coastal waters

Reports of the occurrence and accumulation patterns of polycyclic aromatic hydrocarbons (PAHs) and synthetic musk compounds (SMCs) in marine mammals are scarce. In this study, the concentrations and accumulation profiles of PAHs and SMCs were determined in blubber from finless porpoises in Korean coastal waters. Total concentrations of PAHs and SMCs ranged from 6.0 to 432 (mean: 160) ng/g lipid weight and from 17 to 144 (mean: 52) ng/g lipid weight, respectively. Residue levels of PAHs were lower than those reported from other studies, while residue levels of SMCs were relatively higher than those reported in other studies. Naphthalene was the most abundant PAH and HHCB was the dominant SMC observed in finless porpoises. The concentrations of PAHs and SMCs were not correlated with each other, but were significantly correlated within the same chemical groups. No correlations were found between body size and residue levels of PAHs and SMCs.     

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.     

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.     

Accumulation of butyltin compounds in cetaceans from Korean coastal waters

Data on the occurrence and accumulation profiles of butyltins (BTs), including tributyltin (TBT), in marine mammals are scarce. This is the first study to investigate residue levels and accumulation patterns of BTs in cetaceans from Korean coastal waters. The total concentrations of BTs (sum of mono- to tri-butyltins) in minke whales (Balaenoptera acutorostrata) and long-beaked common dolphins (Delphinus capensis) ranged from 15.7 to 297 ng/g wet weight (mean: 100 ng/g wet weight) and from 59.0 to 412 ng/g wet weight (mean: 228 ng/g wet weight), respectively. Dibutyltin (DBT) accounted for 63% of the total BTs in all cetacean samples. Significant species-specific differences in BT concentrations, possibly due to the differences in their habitat and diet, were found between the two cetacean species. The concentrations of DBT and TBT in most cetacean samples exceeded the threshold value for cytotoxic effects in cetaceans, implying potentially adverse health risks from exposure to BTs.     

葛洲坝至胭脂坝长江干流段江豚活动规律

长江江豚是我国一级保护野生动物,也是长江生态系统的指示性物种,其种群数量恢复情况及活动规律一直备受关注。本文选择长江宜昌段江豚活动频繁的葛洲坝下游至胭脂坝江段为研究区域,于2021年6月-2022年5月采用定点目测、水上流动监测与无人机监测相结合的方法分区监测长江江豚的游泳行为,分析长江江豚的活动规律,构建了长江江豚出水头次的零膨胀泊松回归模型,识别影响长江江豚出水头次的关键因素,建立长江江豚出水头次与各因素间的相关关系。结果表明:(1)葛洲坝至胭脂坝长江干流段监测到最大江豚出水头次为19头次,长江江豚集群规模以2~3头最为常见,占比达58.1%;长江江豚主要表现出4种行为特征,各行为占比从大到小依次为:玩耍＞休息＞摄食＞抚幼。(2)长江江豚在葛洲坝下游近坝区(A区,葛洲坝至至喜长江大桥)出水头次最多,且在秋冬季节累计出水头次多于春夏季节,冬季累计出水头次最高,达252头次。(3)长江江豚出水头次与电站下泄流量呈显著负相关;浊度增大,长江江豚出水的概率减小。本文研究结果对长江江豚生态保护策略及长江十年禁渔效果评估具有重要参考价值。     

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.     

Contamination status of POPs and BFRs and relationship with parasitic infection in finless porpoises (Neophocaena phocaenoides) from Seto Inland Sea and Omura Bay,Japan

Contamination status of brominated flame retardants (BFRs) and persistent organic pollutants (POPs) in blubber of finless porpoises (Neophocaena phocaenoides) stranded along the coasts of Seto Inland Sea and Omura Bay in Japan were investigated. Levels of PCBs, DDTs and CHLs were significantly higher than those of HCHs, HCB, PBDEs and HBCDs. Concentrations of PBDEs and HBCDs, as well as organochlorine compounds in males increased with body length (p < 0.05). Among 14 PBDE congeners analyzed, BDE-47 was the predominant, which is similar to those generally reported in biota. PBDEs, HBCDs and PCBs showed no obvious temporal trend in concentrations during the study period, suggesting continuous environmental release of these chemicals. On the other hand, levels of DDT, CHLs and HCHs have decreased. Concentrations of PCBs in liver trematode infected individuals were significantly higher than those in not infected individuals, implying there could be a relationship between contaminant levels and parasitic infection.     

Contamination level of mercury in red meat products from cetaceans available from South Korea markets

Levels of total mercury (T-Hg) were surveyed in red meat (n=73) and liver (n=3) from toothed whales, dolphins and porpoises (odontocetes) sold for human consumption in the coastal cities of South Korea. High concentrations of T-Hg were found in the liver products of finless porpoises (18.7 and 156 microg/wet g) and common dolphins (13.2 microg/wet g). The T-Hg concentrations in red meat products were highest in the false killer whale (9.66+/-12.3 microg/wet g, n=9), bottlenose dolphin (10.6+/-12.6 microg/wet g, n=3) and killer whale (13.3 microg/wet g, n=1), and lowest in Cuvier's beaked whale and the harbour porpoise (0.4-0.5 microg/wet g). Thus, most of the products that originated from odontocetes exceeded the safety limit of 0.5 microg/wet g for T-Hg set by the South Korean health authorities for the fishery industry. Pregnant women and other vulnerable sectors of the population living in South Korea should therefore limit their consumption of odontocete products.     

Contamination status of POPs and BFRs and relationship with parasitic infection in finless porpoises (Neophocaena phocaenoides) from Seto Inland Sea and Omura Bay, Japan

Contamination status of brominated flame retardants (BFRs) and persistent organic pollutants (POPs) in blubber of finless porpoises (Neophocaena phocaenoides) stranded along the coasts of Seto Inland Sea and Omura Bay in Japan were investigated. Levels of PCBs, DDTs and CHLs were significantly higher than those of HCHs, HCB, PBDEs and HBCDs. Concentrations of PBDEs and HBCDs, as well as organochlorine compounds in males increased with body length (p<0.05). Among 14 PBDE congeners analyzed, BDE-47 was the predominant, which is similar to those generally reported in biota. PBDEs, HBCDs and PCBs showed no obvious temporal trend in concentrations during the study period, suggesting continuous environmental release of these chemicals. On the other hand, levels of DDT, CHLs and HCHs have decreased. Concentrations of PCBs in liver trematode infected individuals were significantly higher than those in not infected individuals, implying there could be a relationship between contaminant levels and parasitic infection.     

Contamination status and accumulation profiles of organotins in sea otters (Enhydra lutris) found dead along the coasts of California, Washington, Alaska (USA), and Kamchatka (Russia)

Organotin compounds (OTs) including mono- to tri-butyltins, -phenyltins, and -octyltins were determined in the liver of adult sea otters (Enhydra lutris) found dead along the coasts of California, Washington, and Alaska in the USA and Kamchatka, Russia. Total concentrations of OTs in sea otters from California ranged from 34 to 4100ng/g on a wet weight basis. The order of concentrations of OTs in sea otters was total butyltins>total octyltins> or = total phenyltins. Elevated concentrations of butyltins (BTs) were found in some otters classified under 'infectious-disease' mortality category. Concentrations of BTs in few of these otters were close to or above the threshold levels for adverse health effects. Total butyltin concentrations decreased significantly in the livers of California sea otters since the 1990s. Based on the concentrations of organotins in sea otters collected from 1992 to 2002, the half-lives of tributyltin and total butyltins in sea otters were estimated to be approximately three years.     

Specific accumulation and temporal trends of organochlorine contaminants in Dall's porpoises (Phocoenoides dalli) from Japanese coastal waters

Organochlorine compounds (OCs) such as polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethane and its metabolites (DDTs), chlordane related compounds, hexachlorocyclohexane isomers (HCHs), hexachlorobenzene (HCB), tris(4-chlorophenyl) methane (TCPMe) and tris(4-chlorophenyl) methanol were determined in the blubber of Dall's porpoises (Phocoenoides dalli) collected from Japanese coastal waters in 1998/1999. Among OCs analyzed, PCBs were the predominant contaminants with concentrations ranging from 1.5 to 39 microg/g on a wet weight basis. OCs concentrations were relatively low and less variable in mature females possibly due to the lactational excretion from their bodies, while in males the concentrations were increased with body length. Concentrations and compositions of DDTs and HCHs showed significant differences between the truei-type population off the Pacific coast of northern Japan and dalli-type from the Sea of Japan/Okhotsk, suggesting its usefulness to discriminate different populations. OCs levels detected in truei-type porpoises collected in 1998/1999 were lower than those collected in 1984, except TCPMe. On the other hand, except DDTs, the residue levels of other organochlorines in dalli-type porpoises showed no significant decrease since 1984.     

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.     

Temporal and life history related trends of perfluorochemicals in harbor porpoises from the Danish North Sea

Eighty-five stranded or bycaught harbor porpoises collected from the Danish North Sea between 1980 and 2005 were analyzed for perfluorochemicals in the liver. PFOS was the predominant compound, making up on average 88.9% of the ∑PFC, followed by PFOSA (7.8%). PFUnA (1.9%) and PFDA (1.2%) were detected in most samples. PFHxS, PFNA and PFOA were only found in a minority of the samples. We found substantial differences in PFC concentrations among life history stages, the highest concentrations were found in neonates, suckling juveniles and lactating females. Such differences should be considered when PFC levels in wildlife are evaluated. The high concentrations found in young porpoises are of concern as PFCs have known toxic effects on the development of the central nervous system and reproductive organs. Despite efforts to reduce PFC emissions, a decreasing temporal trend of concentrations was not detected for any compound. PFCA concentrations were found to be increasing.     

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.     

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.     

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, SigmaPBDEs and HBCDs, respectively.     

Total and organic mercury in the Black Sea harbour porpoise Phocoena phocoena relicta.

This paper reports on mercury (Hg) concentrations in different tissues (liver, muscle, kidney, blubber and brain) of harbour porpoises Phocoena phocoena found dead in the Black Sea between 1997 and 1999, mainly bycaught in fishing nets (n = 79). Total Hg and organic Hg (MeHg) were determined. The main factor affecting Hg accumulation was, as expected, age, with MeHg concentration increasing with age. Accumulation of high concentrations of inorganic Hg in the liver was probably due to a slow demethylation process implying the formation of tiemannite (HgSe). In older adults, liver concentrations reached 35 microg g(-1) dry weight ('ppm') total Hg and 3 microg g(-1) dw MeHg. A geographical comparison with existing data from other regions showed a generally low Hg contamination of Black Sea porpoises, one order of magnitude lower than, e.g. in the North Sea.     

Butyltin Contamination in Marine Mammals – A Review

In order to understand organotin accumulation in marine mammals, the present study determined the concentrations of butyltins (BTs) in various tissues and organs and described their distribution patterns relative to sex, age and geographical factors. Both cetaceans and pinnipeds showed higher BTs concentrations in the liver amongst various tissues and organs. In addition, noticeably high concentrations were found in the hair of pinnipeds, indicating possible excretion of BTs through shedding. BTs composition in mammals and their prey organisms suggested that pinnipeds have a stronger capacity to degrade BTs as compared to cetaceans. No age trends of BTs concentrations were observed in pinnipeds, while cetaceans showed increasing levels in immature growth stages. Comparing butyltin concentrations in various marine mammals, cetaceans retained higher butyltin concentrations than pinnipeds. These specific accumulation patterns found in marine mammals are probably attributable to the lower breakdown capacity of BTs in cetaceans and the significant excretion of BTs through shedding in pinnipeds. Unlike organochlorines, comparable residue levels of butyltins were found in male and female marine mammals. Such a trend suggests that butyltins are less transferable through gestation and lactation from mother to fetus/pup. On a global perspective, residue levels were found to be prominent in the coastal waters of developed nations. The present contamination by BTs may pose a considerable toxic threat to some coastal species of cetaceans. A relatively high percentage of BTs in total tin was found in the liver of cetaceans. This finding suggests that the hepatic tin in cetaceans exists predominantly in organic forms such as butyltin compounds, implying further that tin residues in marine mammals mostly reflects input from anthropogenic sources.     

Occurrence of hydroxylated polychlorinated biphenyls in the brain of cetaceans stranded along the Japanese coast

Levels of hydroxylated polychlorinated biphenyls (OH-PCBs) and PCBs were measured in the brain of melon-headed whales (MW: Peponocephala electra), striped dolphins (SD: Stenella coeruleoalba) and finless porpoises (FP: Neophocaena phocaenoides) stranded along the Japanese coast during 2002-2003. Levels of OH-PCBs (including identified and unknown OH-P(5)CB, -H(6)CB, -H(7)CB and O(8)CB congeners) in the brain of MW, SD and FP were in the range of 20-290, 21-330 and 170-240pg/g wet wt., respectively. Observed OH-PCB levels were 2-3 orders of magnitude lower than PCBs in the same individuals. OH-PCBs/PCBs ratios in MW, SD and FP brain were lower than those in blood of humans and wildlife and in the brain of polar bears reported previously. OH-PCBs were also detected in maternal and fetal brain of SD (1 pair), suggesting transfer of OH-PCBs into the fetal brain of odontocete cetaceans. When fetus/dam concentration ratios of OH-PCB congeners detected in maternal and fetal brain were estimated, the values were higher than those of PCB congeners, implying that OH-PCBs in maternal blood could be more easily transferred into fetal brain via placenta than PCBs.     

Occurrence of anthropogenic and naturally-produced organohalogenated compounds in tissues of Black Sea harbour porpoises

Harbour porpoises are one of the three cetacean species inhabiting the Black Sea. This is the first study to report on polybrominated diphenyl ethers (PBDEs) and naturally-produced compounds, methoxylated PBDEs (MeO-PBDEs) and polybrominated hexahydroxanthene derivatives (PBHDs), in tissues (kidney, brain, blubber, liver, muscle) of male harbour porpoises (11 adults, 9 juveniles) from the Black Sea. Lipid-normalized concentrations decreased from muscle > blubber > liver > kidney > brain for the sum of polychlorinated biphenyls (PCBs) and for the sum of PBDEs. Among the naturally-produced compounds, levels of PBHDs were higher than of MeO-PBDEs, with tri-BHD and 6-MeO-BDE 47 being the dominant compounds for both groups, respectively. Concentrations of naturally-produced compounds decreased from blubber to brain, similarly to the sum of DDT and metabolites (DDXs). Concentrations of DDXs were highest, followed by PCBs, HCB, PBHDs, PBDEs and MeO-PBDEs. Levels of PCBs and PBDEs in blubber were lower than concentrations reported for harbour porpoises from the North Sea, while concentrations of DDXs were higher.