Hee-Gu Choi

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.

Human exposure to PCDDs, PCDFs and dioxin-like PCBs associated with seafood consumption in Korea from 2005 to 2007.

Concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DLPCBs) were measured in 26 seafoods commonly consumed by the Korean population. The total toxic equivalent (TEQ) concentrations in seafood samples ranged from 0.01 to 6.76 pg TEQ/g wet wt, which were comparable with those found in other countries. The predominant congeners found in seafood samples were 2, 3, 4, 7, 8-PeCDF and 2, 3, 7, 8-TCDF for PCDD/Fs and PCB 118 for DLPCBs. Dietary intakes of PCDD/Fs and DLPCBs from seafood consumption were estimated for various age groups and gender in Korea. The dietary intake of PCDD/Fs and DLPCBs from seafood consumption for the general population was estimated to be 1.23 pg TEQ/kg bw/day, values that are in the range of those reported for other countries. Mackerel, tuna and hairtail contributed to the highest TEQ intakes, which collectively accounted for 66% of the total intake. Among the eight age groups investigated, 3-6 year old children had the highest TEQ exposure, followed by 50-64 years, 30-39 years and <2 years. Considering contributions of seafood consumption to the total dietary intake studies, the dietary TEQ intakes to the general population appear to be below the threshold values by international organizations. The present study may be useful for risk management for dioxins and dioxin-like contaminants in Korean seafood.

Congener‐specific characterization and sources of polychlorinated dibenzo‐p‐dioxins, dibenzofurans and dioxin‐like polychlorinated biphenyls in marine sediments from industrialized bays of Korea

Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (DLPCBs) were determined in 122 coastal sediments from heavily industrialized areas in Korea. Toxic equivalent (TEQ) concentrations of PCDD and PCDF (PCDD/F) and DLPCB ranged from 0.44 to 38.5 pg/g dry weight and from 0.01 to 38.4 pg/ g dry weight, respectively. Overall PCDD/F and DLPCB concentrations were elevated in estuarine and inner bay locations close to industrial complexes, indicating that these contaminants derived from local discharges. Concentrations of PCDD/F measured in the present study were comparable to those in industrialized areas of other countries. Nonparametric multidimensional scaling ordination and congener-specific characterization showed that combustion processes occurring in industrial complexes, including the steel industry, are the major source of PCDD/Fs in Korean coastal waters. There were no significant correlations among PCDD/ Fs, DLPCBs, and total organic carbon; however, there was moderate correlation between PCDD/Fs and DLPCBs in some coastal bays, suggesting that these chemicals have similar sources and movements in these locations.

Historical trends of PCDDs, PCDFs, dioxin-like PCBs and nonylphenols in dated sediment cores from a semi-enclosed bay in Korea: tracking the sources.

Two sediment cores, one at middle of the bay (core 1) and another at an outfall of a wastewater treatment plant (WWTP; core 2) were collected in Masan Bay, Korea, to investigate the historical records of contamination by polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), dioxin-like polychlorinated biphenyls (dl-PCBs), and nonylphenols (NPs). Vertical profiles of PCDD/Fs, dl-PCBs, and NPs in the two cores, dated using (210)Pb technique, were different but they had similar vertical profiles within the same core. The overall concentrations of these contaminants were greater in core 2 (0.05-110ng TEQkg(-1) dry wt for PCDD/Fs; 0.02-4.4ng TEQkg(-1) dry wt for dl-PCBs; 1.0-470microgkg(-1) dry wt for NPs) than in core 1 (0.72-8.0ng TEQkg(-1) dry wt for PCDD/Fs; 0.03-1.4ng TEQkg(-1) dry wt for dl-PCBs; 1.3-110microgkg(-1) dry wt for NPs). In particular, PCDD/F concentrations in core 2 were an order of magnitude greater than the concentrations in core 1. The highest concentrations of all target contaminants in cores1 and 2 were found at the surface layer (dated as 2005) and at 8-10cm ( approximately 2000), respectively. For sediment core 2, rapid changes in the concentrations and sources of target contaminants coincide with the establishment and operation of a WWTP; this suggested that discharges from WWTP contributed to contamination by PCDD/Fs, dl-PCBs and NPs in the bay. Analysis of data by non-parametric multidimensional scaling ordination showed that both the cores were influenced by different PCDD/F sources over time. Inventories and fluxes of PCDD/Fs, dl-PCBs, and NPs have rapidly increased since establishment of the WWTP, indicating that the discharge of WWTP is an important source of sediment contamination in aquatic environment.

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.

Nationwide monitoring of nonylphenolic compounds and coprostanol in sediments from Korean coastal waters.

Urbanized and industrialized communities have various anthropogenic activities and produce considerable amounts of municipal effluents, which are discharged along with a wide variety of pollutants to coastal waters. Municipal effluents are one of the major sources of pollutants to estuaries and coastal waters. The anthropogenic contaminants present in these effluents include complex mixtures of household, industrial and agricultural compounds and their degradation products. Among these contaminants, some can persist in natural waters and potentially have acute and chronic effects on aquatic organisms. In Korea, many industrial complexes and cities have been developed along the coastlines. Rapid population growth and urbanization have caused negative impacts on nearby marine ecosystem because of increasing input of wastewaters to rivers and the coastal environment. Some industrialized bays in Korea have serious contaminations by toxic pollutants, necessitating the development and implementation of proper management plans (Hong et al., 2005; Moon et al., 2007, 2008a; Yim et al., 2007; Choi et al., 2009). Therefore, it is important to measure the types and magnitude of contaminants in wastewaters discharged to the marine environment of Korea. Nonylphenolic compounds (NPs) are a group of nonionic surfactants widely used in a variety of industrial processes, and residential and commercial cleaning products since the 1940s. These contaminants are frequently found in effluents from industrial areas (Bennie et al., 1997; Li et al., 2004; Choi et al., 2005; Rule et al., 2006) and have been used as a marker for industrial contamination (Diez et al., 2006; Lara-Martin et al., 2008). NPs also act as endocrine disrupters (Lee et al., 2003; Soares et al., 2008). In Korea, all NPs (11,200 tons in 2004) are imported, and used primarily as surfactants (60%), followed by additives for paints and epoxy resins (12%), copper laminates (9%), ink binder (5%), agricultural pesticides (2%), and other uses (MOE, 2006). The Korean government has managed nonylphenol (NP) and nonylphenol polyethoxylates (NPEOs) as priority chemicals since 2001. A ban on their use for kitchen cleaners was introduced in 2002, and then for all domestic applications in 2007. Thus, the contribution of industrial applications of NPs has increased relative to domestic applications. Some studies have reported that NP levels in creeks of industrial areas in Korea were much higher than those in creaks adjacent to municipal areas (Li et al., 2004, 2008; Choi et al., 2005). Coprostanol (Cop), a fecal sterol, has been widely used as an indicator of domestic wastewater contamination in the aquatic environment because of its occurrence at high concentrations in human feces (40–60% of total fecal sterols excreted; Chan et al., 1998). Distribution profiles of fecal sterols together with other related sterols can provide useful information on source identification in the marine environment (Leeming and Nichols, 1996; Mudge and Lintern, 1999). Wastewater markers can facilitate assessment of wastewater discharges. NPs and fecal sterols have

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.

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.

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.

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.