Monitoring of trace metals in coastal sediments around Korean Peninsula.

Spatial distributions and temporal variations of trace metals in Korean coastal sediments were investigated by determining seven metals (As, Cd, Cr, Cu, Hg, Pb, and Zn) in sediment collected from 71 stations between 2004 and 2010 (n=491). High metal concentrations were found in the southeastern coast, where there are many cities and industrial complexes, indicating that metal concentrations in Korean coastal sediment are significantly influenced by human activities associated with urbanization and industrialization. However, metal concentrations in sediment did not markedly vary temporally, which was because the coast is managed sustainably and because of the characteristics of the sediment environments. Based on the sediment quality guidelines and geoaccumulation index, Korean coastal sediments are practically unpolluted with Cd, Cr, Cu, Hg, Pb and Zn but moderately polluted with As. More intensive monitoring is required to determine the potential As sources and to understand the As geochemical cycles in Korean coastal sediments.

The effect of low oxygen conditions on biogeochemical cycling of nutrients in a shallow seasonally stratified bay in southeast Korea (Jinhae Bay).

The formation and distribution of oxygen-deficient water mass (ODW) in Jinhae Bay exhibited seasonal patterns similar to those of the summer thermocline, indicating a close mutual relationship, and the influence of ODW formation conditions appeared prominently in the bottom water. The principal factors analysis indicate that dissolved oxygen and NO2 in the bottom water during the time of ODW formation were highly correlated with NH3 and dissolved inorganic phosphorus. The findings clearly illustrate the effects on ODW of seasonal physical and chemical changes. ODW that formed in the bottom water of Jinhae Bay during summer produced high concentrations of nutrients in the bottom water; since the growth of phytoplankton was limited by the strong stratification and low concentrations of dissolved oxygen (<3mg/L) in the bottom layer, these nutrients (especially NH3 and DIP) were retained and accumulated, serving as a major source of nutrients during the dry winter.

Development of a one-step integrated pressurized liquid extraction and cleanup method for determining polycyclic aromatic hydrocarbons in marine sediments.

A rapid and accurate one-step integrated pressurized liquid extraction (PLE) and cleanup method was developed and validated for 34 polycyclic aromatic hydrocarbons in marine sediments, giving an extract that could be analyzed by gas chromatography-mass spectrometry without further cleanup. Marine sediment (5 g) was loaded into the stainless-steel extraction cell above activated copper (5 g) and activated silica gel (5 g). An extraction temperature of 100°C and two 5 min extraction cycles using a 4:1 (v/v) hexane-dichloromethane mixture gave a good extraction efficiency. The integrated method gave extracts that were as clean as those obtained using PLE, followed by separate activated copper and silica gel cleanups. The method was validated, in terms of its accuracy, precision, and application using a certified reference material (NIST SRM 1944), marine sediments spiked at low and high concentrations, and contaminated harbor sediments. The mean recoveries were 92% and 94% for the low and high spike concentrations, respectively, and the accuracy was good (giving a mean of 86% of the certified reference material concentrations). The method developed gave a precision and accuracy equal to or better than the precision and accuracy found using PLE with separate cleanups. The method developed gives a shorter sample preparation time and uses much less solvent than PLE and separate cleanups.

Temporal trends (2004-2009) of imposex in rock shells Thais clavigera collected along the Korean coast associated with tributyltin regulation in 2003 and 2008.

We investigated the temporal trend in contamination of butyltin compounds (BTs) along the Korean coast using imposex and tributyltin (TBT) burden in gastropods (Thais clavigera) as a biomonitor. Thais clavigera were collected from 26 locations with different shipping activities between 2004 and 2009 after restrictions on TBT-based antifouling paints were imposed in Korea. In the present study, imposex indices and TBT tissue concentrations significantly decreased over time from 2004 to 2009, confirming the effectiveness of TBT regulation. However, imposex in 2009 samples was still found. Significantly high imposex indices and TBT tissue residues were found in large ports containing commercial and ferry services compared with small ports and background areas. Imposex indices in background areas had decreased to zero, suggesting recovery from imposex caused by BT contamination. These results suggest that recovery from TBT contamination occurs faster in areas with very low maritime activities than areas with high maritime activities.

Severe pollution of PCDD/Fs and dioxin-like PCBs in sediments from Lake Shihwa, Korea: tracking the source.

Concentrations of polychlorinated dibenzo-p-dioxins, dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) were determined in surface sediments from Lake Shihwa and from creeks that discharge into this artificial lake. The toxic equivalents (TEQs) in sediments ranged from 1.0 to 1770 pg/g dry weight, which were some of the highest values ever reported so far for coastal sediments on a global basis. The concentrations of PCDD/Fs and DL-PCBs decreased with increasing distance from the creeks to offshore regions of the lake. Based on a multivariate statistical analysis and congener profiles, it was found that high contamination by PCDD/Fs in creek sediments collected around Lake Shihwa was associated with releases from chlor-alkali processes. Significant correlations were found for total organic carbon content and the concentrations of highly chlorinated PCDD/F congeners. This is the first report to document chlor-alkali processes as a significant source of PCDD/F contamination in Korean coastal waters.

Contamination and potential sources of polybrominated diphenyl ethers (PBDEs) in water and sediment from the artificial Lake Shihwa, Korea.

Concentrations of polybrominated diphenyl ethers (PBDEs) were determined in water and sediment collected from the artificial Lake Shihwa and surrounding creeks. Total concentrations of 23 PBDE congeners in water and sediment ranged from 0.16 to 11.0ngL(-1) and from 1.3 to 18700ngg(-1)dryweight, respectively. The concentrations of BDE 209 in water and sediment were 1-2 orders of magnitude higher than the total concentrations of other PBDE congeners. The concentrations of total PBDEs and BDE 209 in sediments were the highest compared to previously reported worldwide levels. The highest concentrations of PBDEs in water and sediments were found in creeks near industrial complexes. The PBDE concentrations gradually decreased with increasing distance from the creeks to the inshore and then offshore regions of the lake. BDE 209 was a major congener, accounting for 80% of the total PBDEs in water and sediment, consistent with a high consumption of deca-BDE for the brominated flame retardant market in Korea. Non-parametric multidimensional scaling ordination showed that surrounding creeks are major pathways of PBDE contamination associated with deca-BDE technical mixtures used in industrial complexes around Lake Shihwa. A significant correlation between total organic carbon and total PBDE concentration was found in sediments, and the correlation coefficients for individual PBDE congeners relatively increased from lower to higher brominated congeners.

Polybrominated diphenyl ethers, polychlorinated biphenyls, and organochlorine pesticides in adipose tissues of Korean women.

Studies on residue levels and accumulation profiles of persistent organic pollutants (POPs) in human adipose tissues of Korean populations are scarce. In this study, concentrations and accumulation features of polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), and polybrominated diphenyl ethers (PBDEs) were measured in adipose tissues of Korean women age 40-68 years. The highest concentrations were found for PCBs and DDTs, which were 1-2 orders of magnitude greater than the concentrations of hexachlorocyclohexanes, chlordanes, and PBDEs. The concentrations of PCBs and OCPs were lower than those reported for other countries. However, PBDE concentrations were greater than those reported for other countries, suggesting that ongoing exposure to PBDEs is a concern in Korea. The profiles of PBDEs were characterized by the predominance of BDE 209, followed by nona- and octa-BDEs, which are consistent with the consumption patterns of products containing PBDEs in Korea. The concentrations of PCBs and some OCPs were significantly correlated with each other, whereas PBDEs showed low or moderate correlations with other POPs, suggesting differences in exposure routes and biotransformation potentials of the compounds studied. The concentrations of organochlorines and PBDEs were not correlated with subjects' age and body mass index. The results of this study provide baseline information on POPs in adipose tissues of the general population in Korea.

Intake and potential health risk of butyltin compounds from seafood consumption in Korea.

Concentrations of butyltin compounds (BTs) were determined in 47 species of seafood commonly consumed in Korea to investigate intakes of BTs from seafood consumption and the potential health risks to the Korean population. The concentrations of BTs (the sum of dibutyltin and tributyltin) in seafood ranged from less than the limit of detection to 96.3 ng/g wet weight, which are levels similar to those reported for other countries. The intake of BTs from seafood consumption by the general population was estimated to be 17.2 ng/kg body weight/day. Fish accounted for 50% of the total intakes of BT, and the next contributor was cephalopods (26%). The estimated intakes for males and females were 18.6 and 15.7 ng/ kg body weight/day, respectively. Among the age groups investigated, children (<2 years and 3-6 years) had higher intakes of BTs compared with adults. The estimated intake of BTs for Korean population groups was 5-8% of the tolerable daily intake of 250 ng/ kg body weight/day set by the European Food Safety Authority. Our results suggest that the Korean population is not expected to exceed the threshold value for adverse health effects.

Accumulation of PAHs and synthetic musk compound in minke whales (Balanoptera acutorostrata) and long-beaked common dolphins (Delphinus capensis) from Korean coastal waters.

Information on the occurrence and accumulation profiles of polycyclic aromatic hydrocarbons (PAHs) and synthetic musk compounds (SMCs) in marine mammals is scarce. In the present study, we recorded the concentrations and profiles of PAHs and SMCs in liver tissue and blubber from minke whales and common dolphins from Korean coastal waters. The overall concentrations of PAHs and SMCs in blubber from both cetacean species were approximately three to five times higher than those in liver tissues. Residue levels of PAHs were lower, whereas levels of SMCs were relatively higher than those reported in other studies. Lack of species- and sex-dependent differences in the concentrations of PAHs and SMCs were found. Naphthalene and 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-r-2-benzopyran (HHCB) were predominant compounds in all the samples for PAHs and SMCs, respectively. The concentrations of PAHs and SMCs were significantly correlated with each other, but were not correlated with body size of cetaceans. The present data provide valuable information on the exposure of Korean cetaceans to PAHs and SMCs.

Contamination of nonylphenolic compounds in creek water, wastewater treatment plant effluents, and sediments from Lake Shihwa and vicinity, Korea: comparison with fecal pollution.

Nonylphenolic compounds (NPs), coprostanol (COP), and cholestanol, major contaminants in industrial and domestic wastewaters, were analyzed in creek water, wastewater treatment plant (WWTP) effluent, and sediment samples from artificial Lake Shihwa and its vicinity, one of the most industrialized regions in Korea. We also determined mass discharge of NPs and COP, a fecal sterol, into the lake, to understand the linkage between discharge and sediment contamination. Total NP (the sum of nonylphenol, and nonylphenol mono- and di-ethoxylates) were 0.32-875 µg L(-1) in creeks, 0.61-87.0 µg L(-1) in WWTP effluents, and 29.3-230 µg g(-1) TOC in sediments. Concentrations of COP were 0.09-19.0 µg L(-1) in creeks, 0.11-44.0 µg L(-1) in WWTP effluents, and 2.51-438 µg g(-1) TOC in sediments. The spatial distributions of NPs in creeks and sediments from the inshore region were different from those of COP, suggesting that Lake Shihwa contamination patterns from industrial effluents differ from those from domestic effluents. The mass discharge from the combined outfall of the WWTPs, located in the offshore region, was 2.27 kg d(-1) for NPs and 1.00 kg d(-1) for COP, accounting for 91% and 95% of the total discharge into Lake Shihwa, respectively. The highest concentrations of NPs and COP in sediments were found in samples at sites near the submarine outfall of the WWTPs, indicating that the submarine outfall is an important point source of wastewater pollution in Lake Shihwa.

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.

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.

Monitoring of organic contaminants in sediments from the Korean coast: Spatial distribution and temporal trends (2001-2007).

Spatial and temporal trends of organic contaminants in sediments along the Korean coast were estimated through a nationwide environmental monitoring program from 2001 to 2007. The concentrations of organic contaminants in sediments along the Korean coast were relatively low or moderate compared with foreign studies. The mean detection frequencies of organic contaminants during the seven years were highest for PAHs and PCDD/Fs, followed by PCBs, DDTs, TBT and HCHs in decreasing order. Based on published sediment quality guidelines, the ecological risks of persistent organic pollutants in sediments along the Korean coast were low, despite exceedances of the ERL at 2-6 sites for DDTs, and the TEL at 9-18 sites for PCDD/Fs. Nonparametric tests to assess temporal trends revealed significant decreasing trends for PCBs and PCDD/Fs at four and three sites, respectively (p<0.05). These results reflect the effects of regulations on the use of those contaminants.

Molecular and biochemical modulation of heat shock protein 20 (Hsp20) gene by temperature stress and hydrogen peroxide (H2O2) in the monogonont rotifer, Brachionus sp.

The monogonont rotifer, Brachionus sp. has been regarded as a potential model for reproductive physiology, evolution, and environmental genomics. To uncover the role of the heat shock protein upon temperature stress and hydrogen peroxide (H2O2) exposure, we cloned heat shock protein 20 (Hsp20) and determined its modulatory response under different temperatures and H2O2 concentrations. Under different temperature stresses (10 °C and 37 °C), the rotifer Brachionus sp. Hsp20 (Br-Hsp20) gene was highly expressed over time, and reached the maximum level 90 min after exposure, indicating that Br-Hsp20 gene would be involved in the chaperoning process to protect proteins at both low and high temperatures. To test the ability of thermotolerance of the recombinant Br-Hsp20-containing transformed Escherichia coli, we expressed the recombinant Br-Hsp20 protein with 1mM IPTG for 18 h at 30 °C, exposed them at 54 °C with time course (10 to 60 min), and measured cell survival. In this elevated temperature shock (54 °C), the cell survival was significantly higher at the Br-Hsp20 transformed E. coli, compared to the control (vector only). To analyze the modulatory effect of Br-Hsp20 gene on oxidative stress, we initially exposed 0.1 mM H2O2 over time and measured antioxidant enzyme activities along with the expression level of Br-Hsp20 mRNA. Upon H2O2 exposure, Br-Hsp20 gene was time-dependently upregulated and glutathione peroxidase (GPx), glutathione S-transferase (GST), and glutathione reductase (GR) activities were also elevated at the 12h-exposed group in a dose-dependent manner, indicating that the Br-Hsp20 gene would be an important gene in response to oxidative and temperature stress. Here, we demonstrated the role of the Hsp20 gene in the rotifer, Brachionus sp. providing a better understanding of the ecophysiology at environmental stress in this species.

Contamination status and accumulation features of PCDDs, PCDFs and dioxin-like PCBs in finless porpoises (Neophocaena phocaenoides) from Korean coastal waters.

Data on the concentrations and accumulation profiles of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) in cetaceans are scarce. In this study, concentrations and accumulation profiles of PCDD/Fs and DL-PCBs were measured in the blubber of finless porpoises (Neophocaena phocaenoides) collected from Korean coastal waters. Total dioxin-like toxic equivalent (TEQ) concentrations (6.5-31 pg/g lipid weight) in finless porpoises were lower than those reported for cetaceans and pinnipeds from other countries. Significant gender-specific differences were found in the concentrations and accumulation profiles of PCDD/Fs and DL-PCBs and this difference was associated with maternal and lactation transfer of contaminants from mature females to their fetus. All of the PCDD/F homologue groups were detected in all of the samples and the proportions of PCDFs were higher than those of PCDDs. The dominant congeners found in finless porpoise blubber were 2,3,4,7,8-PeCDF, 1,2,3,4,7,8-HxCDF and OCDD for PCDD/Fs and PCB 118 for DL-PCBs. The accumulation profiles of PCDD/Fs in finless porpoise in our study were different from those found for cetaceans from other countries. Total TEQ levels in finless porpoises in Korea were below the suggested threshold values for adverse health effects in marine mammals.

Perfluorinated compounds in minke whales (Balaenoptera acutorostrata) and long-beaked common dolphins (Delphinus capensis) from Korean coastal waters.

This is the first study to report the concentrations and accumulation profiles of PFCs in marine mammals from Korea. The concentrations and profiles of 10 PFCs in the liver of minke whales and common dolphins from Korean coastal waters were recorded in this study. The mean concentrations of PFOS and PFUnDA were 3-20 times higher than that found for other PFCs analyzed. The concentrations of PFOS in cetaceans from Korea were relatively lower than those reported in other countries. Inter-species differences in the concentrations of PFOS, PFOSA and PFNA were found between two cetacean species, while no difference was observed in the concentrations of PFDA, PFUnDA and PFDoDA between the species. The dominant PFC compounds found in cetaceans were PFUnDA and PFOS, accounting for 70-80% of the PFCs. The accumulation profiles and correlation analysis indicated that two cetacean species have different exposure routes and metabolic capacity for PFCs.

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.

Chlorinated and brominated contaminants including PCBs and PBDEs in minke whales and common dolphins from Korean coastal waters.

Information on the occurrence and distribution of polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs) and polybrominated diphenyl ethers (PBDEs) in marine mammals from Korean coastal waters is not available to date. This is the first study to investigate concentrations and accumulation of PCBs, OCPs, and PBDEs in liver and blubber of minke whales and common dolphins from Korean coastal waters. The concentrations of organochlorines and PBDEs in blubber were several times higher than in liver. The concentrations of PCBs and OCPs were generally low, but the concentrations of PBDEs were similar to those reported for cetaceans elsewhere. The accumulation profiles of OCPs differed between liver and blubber, while the profiles of PCBs and PBDEs were relatively similar in both tissues. The concentrations of PCBs, DDTs, CHLs and PBDEs in common dolphins were significantly higher than those in minke whales, while there were no inter-species differences for HCHs and HCB. The predominant OCP, PCB and PBDE congeners in cetaceans were p,p'-DDE, PCB 153 and BDE 47, respectively. The concentrations of PCBs and DDTs in Korean cetaceans were close to the threshold for adverse health effects.

Concentrations and accumulation features of PCDDs, PCDFs and dioxin-like PCBs in cetaceans from Korean coastal waters.

Despite several studies that report accumulation of polychlorinated biphenyls (PCBs) and DDT in marine mammals worldwide, very few have examined polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like PCBs. In particular, no earlier studies have reported concentrations and accumulation profiles of persistent organic pollutants (POPs) in marine mammals from Korea. In this study, concentrations and accumulation features of PCDD/Fs and dioxin-like PCBs were measured in liver and blubber of minke whales and long-beaked common dolphins collected from Korean coastal waters. The concentrations of PCDFs and dioxin-like PCBs in blubber were 3-10 times higher than the concentrations measured in liver, but PCDDs were higher in liver than blubber. Total toxic equivalent (TEQ) concentrations in blubber of minke whales and common dolphins from Korean coastal waters were similar to, or higher than those reported for cetaceans and seals from other countries. Homologue and congener profiles of PCDD/Fs were different between livers and blubbers, while the profiles of dioxin-like PCBs were similar between the tissues. Concentrations of PCDD/Fs and dioxin-like PCBs in liver and blubber of dolphins were significantly higher than those measured in whales, due to differences in habitat and diet. The relative contribution of individual chemical groups to total TEQs was different between the two cetacean species, suggesting different exposures and metabolic activity. The TEQ levels in minke whales did not exceed the threshold level suggested for immunomodulation, while TEQs in all dolphin samples exceeded the suggested threshold level, implying potential adverse health effects from exposure to PCDD/Fs and PCBs.

Temporal trend of butyltins in seawater, sediments, and mussels from Busan Harbor of Korea between 2002 and 2007: tracking the effectiveness of tributylin regulation.

Butyltins were determined in seawater, sediments, and mussels (Mytilus edulis) collected from Busan Harbor, the largest commercial harbor in Korea, to assess the contamination status and the effectiveness of tributylin (TBT) restriction. TBT concentrations were found to be 7.6 +/- 8.3 ng Sn/L in seawater, 387 +/- 606 ng Sn/g dry weight (wt) in sediments, and 322 +/- 167 ng Sn/g dry wt in mussels, and are comparable to those in the largest harbors worldwide. TBT levels were highest at locations near shipyards and related facilities. Busan Harbor was characterized by the long-term history of butyltin contamination, based on the lowered TBT/DBT ratios in environmental matrices. The temporal trend of TBT levels decreased significantly in seawater and mussels from 2002 to 2007, probably as a consequence of the legislative action in Korea (MOE Regulation 154/2000). However, TBT in sediments did not show any trend, suggesting a long half-life for TBT, about 17 years, in sediments.