Jinsoon Park

Perfluorinated compounds in water, sediment, soil and biota from estuarine and coastal areas of Korea

Soil, sediment, water, and biota collected from the western coast of Korea were analyzed to determine occurrence and sources of perfluorinated compounds (PFCs). PFCs were significantly concentrations of PFCs were measured in some water and biological samples, while concentrations of PFCs in soils and sediments were relatively low. The most widely detected compound was found to be perfluorooctanesulfonate (PFOS), with a maximum concentration in water of 450 ng/L and in fish of 612 ng/g, dw. PFOS concentrations in water and biota were both less than those thought to cause toxicity. However, in both cases concentrations were within a factor of 10 of the toxicity threshold concentration. Concentrations of PFCs were significantly greater downstream than those upstream on the same river, suggesting point sources. Overall, the detection of PFCs at relatively great concentrations in various environmental matrixes from this region of Korea suggests that further studies characterizing PFCs and their potential risk to both humans and wildlife are needed.

Perfluorinated compounds in surface waters from Northern China: Comparison to level of industrialization

Inclusion of Perfluorooctane Sulfonate (PFOS) in the Stockholm Convention because of its exemptions, has resulted in increased annual production of PFOS-containing chemicals in China to accommodate domestic and overseas demands. Accordingly, concern about environmental contamination with perfluorinated compounds (PFCs), such as PFOS, has arisen. However, little information is available on the status and trends in the distribution, sources or risk of PFCs in aquatic environments of China. In the present study, forty two surface water samples collected from five regions with different levels of industrialization were monitored for concentrations of PFCs by use of solid phase extraction and LC/MS/MS. Mean concentrations (maximum concentration) of PFOA and PFOS, which were the dominant PFCs, were 1.2 (2.3) and 0.16 (0.52)ng/l for Guanting, 1.2 (1.8) and 0.32 (1.1)ng/l for Hohhot, 2.7 (15) and 0.93 (5.7)ng/l for Shanxi, 6.8 (12) and 2.6 (11)ng/l for Tianjin, 27 (82) and 4.7 (31)ng/l for Liaoning, respectively. The greatest concentrations of PFCs (121 ng/l), PFOA (82 ng/l) and PFOS (31 ng/l) were observed in Liaoning, which might originate from tributaries of the Liaohe River, the most polluted watershed in Northeast China. While, concentrations of PFCs in the Guanting and Hohhot regions were 3 to 20 fold less than those from Tianjin and Liaoning. This result is consistent with little contribution of PFCs being released from agricultural and non-industrial activities. The magnitudes of mass flow for PFOA and PFOS in decreasing order were: Guanting<Hohhot<Tianjin<Liaoning<Shanxi and Guanting<Hohhot<Shanxi<Tianjin<Liaoning. The larger mass flows of PFOS were accompanied by relatively larger magnitudes of PFOA. Concentrations of both PFOA and PFOS in waters from all regions were less than suggested allowable concentrations. However, the relatively greater concentrations of PFCs in Tianjin and Liaoning suggest that further studies characterizing their sources and potential risk to both humans and wildlife are needed.

Distributions and bioconcentration characteristics of perfluorinated compounds in environmental samples collected from the west coast of Korea.

As part of an ongoing study of the status and trends of contaminants in the Yellow Sea, during May of 2009, the concentrations of perfluorinated compounds (PFCs) were determined in water (n=15), sediment (n=12), soil (n=13), and biota (n=74) from estuarine and coastal areas along the west coast of Korea. Of the 12PFCs monitored, PFOS and PFOA were the most frequently detected compounds in water. Greater concentrations of PFCs were found in waters from the inner regions of sea dikes in three artificial lakes, Shihwa, Asan, and Sapgyo, than outer regions. Concentrations were also comparable in two estuarine areas, which indicated that most PFCs in coastal areas originated from industrial and local regions and river water flowing through estuaries. Concentrations of PFCs in soils and sediments were generally less than limits of quantification and were generally less than those measured in biota. Compound-specific bioaccumulation of PFBS and PFOS had the greatest BCF values in crab, while in fish it was PFOS and PFDA, and in gastropods and bivalves it was PFHxS. Distributions of BCFs for PFOS in body-parts of crab showed the greatest values in soft tissues followed by shells and then legs. Distribution among tissues and organs of fishes was more variable than those observed for crab. When compared to a similar study conducted by our group in 2008, concentrations of PFCs in water samples were significantly less in 2009. However, there was little change in bioconcentration from sediments into benthic organisms. Finally, we conducted the assessment of potential adverse effects for PFCs on aquatic life by use of current and previous reported data.

Perfluorinated compounds in estuarine and coastal areas of north Bohai Sea, China

Perfluorinated compounds (PFCs) in water, sediment, soil, and biota collected from estuarine and coastal areas of the north Bohai Sea, China, were determined by use of HPLC-MS/MS. Significant concentrations of PFCs were found in water (mean: 18.4 ng/l) and biologic samples (fish: 265 ng/g dw), while concentrations of PFCs in soils and sediments were less. The predominately detected compound was perfluorooctanesulfonate (PFOS), with a maximum concentration of 30.9 ng/l in water and 791 ng/g dw in fish. Concentrations of PFCs were significantly greater in the Liaohe River system than other locations, which suggests point sources in this urbanized and industrialized region. PFOS concentrations in water and biota were both less than the reported threshold concentrations. Detection of PFCs at relatively great concentrations in various environmental matrices from this region suggested that further studies characterizing concentrations of PFCs, their sources and potential risk to both humans and wildlife are needed.

AhR-mediated potency of sediments and soils in estuarine and coastal areas of the Yellow Sea region: a comparison between Korea and China.

Extracts of sediments (n = 45) and soils (n = 37) collected from the coast of the Yellow Sea, in Korea and China, were screened for their ability to induce dioxin-like gene expression in vitro using the H4IIE-luc, transactivation bioassay. Significant dioxin-like potency was observed except for a few soils from Korea. Concentrations of TCDD-EQ (2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents) in sediments were comparable between Korea and China, but concentrations of TCDD-EQ in soil were 2-fold greater from Korea. Mass balance analysis indicated that concentrations of TCDD-EQ were to some degree chemical- and/or matrix-dependent, but were much more site-specific. For example, the proportion of the TCDD-EQ that could be identified varied among locations, which suggests different sources. Unidentified AhR-active compounds represented a greater proportion of the TCDD-EQ in samples from Korea, which suggests that sources in Korea were more complex than those in China. Potential sources of TCDD-EQ were investigated by considering land-uses and local activities.

Sources and distribution of polychlorinated-dibenzo-p-dioxins and -dibenzofurans in soil and sediment from the Yellow Sea region of China and Korea

Polychlorinated-dibenzo-p-dioxins and -dibenzofurans (PCDD/Fs) were measured in soils and sediments from the Yellow Sea region. Korean soils and sediments mostly contained detectable PCDD/Fs and showed a widespread distribution among locations. Soil and sedimentary PCDD/Fs from China were comparable to or less than those in Korea. The patterns of relative concentrations of individual congeners in soils were different between the two countries, but similar in sediments. Sources of PCDD/Fs in China and Korea were found to be independent of each other and their distributions reflected matrix-dependent accumulation. Spatial distribution indicated some point sources in Korea while Chinese sources were more widespread and diffuse. PCDD/Fs measured in the coastal areas of the Yellow Sea were comparable to or less than those previously reported in for eastern Asia. However, ∑TEQs in soils and sediments were near to or, in some cases exceeded environmental quality guidelines.

Species- and tissue-specific bioaccumulation of arsenicals in various aquatic organisms from a highly industrialized area in the Pohang City, Korea.

Contamination of water and sediment with arsenic (As) in a highly industrialized area of Pohang City, Korea was investigated, with emphasis on in situ bioaccumulation of arsenicals by various aquatic organisms. Species- and tissue-specific concentrations of arsenicals were determined by use of HPLC-ICP/MS and μ-X-ray absorption near-edge structure (μ-XANES). Concentrations of arsenic in aquatic organisms were strongly associated with corresponding water concentrations, which indicates point sources associated with land use and activities. Arsenobetaine was the most dominant form of arsenic found in fishes, bivalves, crabs, and shrimps, while As(III) was predominant in freshwater snails. The μ-XANES analysis provided additional information about the unidentified arsenicals such as As-thiol. Arsenicals were mainly localized in intestine of mullet and marsh clam. Distribution and bioaccumulation of arsenic were strongly correlated with salinity, which indicates that natural processes controlling biogeochemistry of arsenic would be important in estuarine lotic system.

Bioaccumulation characteristics of perfluoroalkyl acids (PFAAs) in coastal organisms from the west coast of South Korea

Year-round monitoring for perfluoroalkyl acids (PFAAs) along the west coast of South Korea targeting long-term changes in water and coastal organisms has been conducted since 2008. In this study, we present the most recent 5-years of accumulated data and scrutinize the relationship between concentrations in water and biota highlighting bioaccumulation characteristics. Twelve individual PFAAs in samples of water (n=43) and biota (n=59) were quantified by use of HPLC-MS/MS after solid phase extraction. In recent years, concentrations of PFAAs in water have been generally decreasing, but profiles of relative concentrations of individual PFAAs vary among location and year. Bioaccumulation of PFAAs in various organisms including fishes, bivalves, crabs, gastropods, shrimps, starfish, and polychaetes varied among species. However, overall bioaccumulation of PFAAs was dependent on corresponding concentrations of PFAAs in water within an area. In organ-specific distributions of PFAAs, greater concentrations of PFAAs were found in intestine of fish (green eel goby). This result suggests that PFAAs are mainly accumulated via dietary exposure, while greater concentrations were found in gill and intestine of bivalve (oyster) which suggests both waterborne and dietary exposures to these organisms. Concentrations of PFAAs in biota did not decrease over time (2008-2010), indicating that continuing bioaccumulation followed by slow degradation or excretion of PFAAs accumulated in biota. Overall, spatio-temporal distributions of PFAAs in water and bioaccumulation characteristics seemed to be associated with recent restrictions of PFOS-based products and uses of PFBS-based substitutes.

In vitro and in vivo toxicities of sediment and surface water in an area near a major steel industry of Korea: Endocrine disruption, reproduction, or survival effects combined with instrumental analysis

The influence of industrial and/or municipal contaminant inputs on the aquatic environment of Pohang, Korea was investigated, with a focus on bioassay combined with instrumental analysis. Pohang is the most heavily populated city in Gyeongsangbuk-do province of Korea, with more than half a million residents, and also hosts the nations biggest steel manufacturer and related industries. Sediment (n=15) and surface water samples (n=17) were collected from Hyeongsan River which runs across the Pohang city, in two separate events, i.e., June 2010 and February 2011. Sediment samples were first Soxhlet-extracted (raw extract) and were measured for estrogenicity using H295R cell line, and also analyzed for alkylphenols (APs), bisphenol A (BPA), PAHs, and PCBs. For sediment samples which exhibited greatest effects in the cell line, further fractionation was performed into non-polar, mid-polar, and polar portions. In surface water samples, heavy metals were also analyzed. Among 15 sediment samples, station S2 near the steel industry complex and station M3 near the municipal area showed the greatest sex hormone changes, and these changes were generally explained by the fractions which contained APs and BPA. Principal component analysis (PCA) however suggests that chemicals that were not analyzed in the present study would better explain endocrine disruption capacity of sediments. In water samples, adverse effects on hatchability and growth of Japanese medaka fish, and on Daphnia reproduction were noted following exposure to six water samples collected from stations near industrial and municipal areas. Several heavy metals and nonylphenol (NP) concentrations exceeded surface water quality guidelines, suggesting adverse effects of contamination inputs from both industrial and municipal activities. Observed estrogenicities in stations such as S2 and M3 warrant further investigations on longer term ecosystem impacts near industrial and municipal areas. The levels of major organic chemicals in sediments are quite comparable to those reported in ~10 years ago, emphasizing a need for source control.

Instrumental and bioanalytical measures of dioxin-like compounds and activities in sediments of the Pohang Area, Korea

Pohang is a mid-sized city in which Koreas largest manufacturer of steel is located. The Hyeongsan River, which runs through Pohang and empties into Yeongil Bay, is therefore expected to be affected by various municipal and industrial inputs. In order to characterize aryl hydrocarbon receptor (AhR)-mediated activities in sediments from the Pohang area, a total of eight locations along the Hyeongsan River were chosen and 16 sediment samples were collected during two sampling campaigns in 2010. Organic extracts of sediments were characterized by both quantitative chemical analyses of dioxin-like chemicals and the in vitro H4IIE-luc bioassay. Significant dioxin-like activities were observed in sediments from industrial and municipal areas, which indicates that most of the dioxin-like chemicals were associated with surrounding anthropogenic sources. In general, responses of the H4IIE-luc assay were significantly correlated with concentrations of target compounds including dioxins, furans, co-planar PCBs, and dioxin-like PAHs. A potency balance analysis indicated that instrumentally derived TCDD equivalents (TEQs) explained about 77% of the bioassay-derived TCDD equivalents (TCDD-EQs). Among the target chemicals measured, certain penta-chlorinated dioxin and furan compounds accounted for the majority of dioxin-like activities associated with sediments. Compositional analysis of target chemicals the sources of such dioxin-like activities were mainly derived from the local activities such as the iron and steel industries. Concentrations and activities of AhR agonists were similar to what was measured approximately 10 years ago. Thus, while AhR agonists seem to be persistent in sediments there seem to have been no large increases in these chemicals in the Pohang area.