Chan-Kook Kim

Distribution of perfluorochemicals between sera and milk from the same mothers and implications for prenatal and postnatal exposures

The levels of six perfluorocarboxylates (PFCAs), four perfloroalkylsulfonates (PFASs), and one sulfonamide were measured in paired samples of maternal serum, umbilical cord serum, and breast milk. The maternal and cord sera were strongly correlated with each other for all measured compounds (r>0.5 and p<0.01). Nevertheless, there was a significant difference in compound composition profile between the two sera matrices, with a more depletion of the longer chain compounds in cord serum. The transfer efficiency values from maternal to cord serum (TFCS/MS) decreased by 70% with each increasing unit of -CF2 chain within a PFCA group, and for perfluorooctanesulfonate (PFOS), by a half compared to perfluorooctanoate (PFOA). In contrast to the strong correlation in concentrations between the two sera matrices, the pattern of compounds in breast milk differed considerably with those in sera. Accordingly, compound- and matrix-specific transfer must be considered when assessing prenatal and postnatal exposure.

Two Years after the Hebei Spirit Oil Spill: Residual Crude-Derived Hydrocarbons and Potential AhR-Mediated Activities in Coastal Sediments

The Hebei Spirit oil spill occurred in December 2007 approximately 10 km off the coast of Taean, South Korea, on the Yellow Sea. However, the exposure and potential effects remain largely unknown. A total of 50 surface and subsurface sediment samples were collected from 22 sampling locations at the spill site in order to determine the concentration, distribution, composition of residual crudes, and to evaluate the potential ecological risk after two years of oil exposure. Samples were extracted and analyzed for 16 polycyclic aromatic hydrocarbons (PAHs), 20 alkyl-PAHs, 15 aliphatic hydrocarbons, and total petroleum hydrocarbons using GC-MSD. AhR-mediated activity associated with organic sediment extracts was screened using the H4IIE-luc cell bioassay. The response of the benthic invertebrate community was assessed by mapping the macrobenthic fauna. Elevated concentrations of residual crudes from the oil spill were primarily found in muddy bottoms, particularly in subsurface layers. In general, the bioassay results were consistent with the chemistry data in a dose-dependent manner, although the mass-balance was incomplete. More weathered samples containing greater fractions of alkylated PAHs exhibited greater AhR activity, due to the occurrence of recalcitrant AhR agonists present in residual oils. The macrobenthic population distribution exhibits signs of species-specific tolerances and/or recolonization of certain species such as Batillaria during weathering periods. Although the Hebei Spirit oil spill was a severe oil exposure, it appears the site is recovering two years later.

Childhood exposure to DEHP, DBP and BBP under existing chemical management systems: A comparative study of sources of childhood exposure in Korea and in Denmark

In this paper, the cumulative risks of Di(2-ethylhexyl) phthalate (DEHP), Di-n-butyl phthalate (DBP), and Benzyl-butyl phthalate (BBP) to 2-year-old children in two countries: one European (Denmark) and one Asian (South Korea) were compared. Denmark does not produce phthalates as a raw material, while Korea produces more than 0.4milliontons of the three above-mentioned phthalates each year. First, a comparative review of the existing phthalate regulations in the two countries was performed. Next, the level of childhood phthalate exposure from environmental and food sources was estimated using an exposure scenario approach. Then, the scenario based exposure level was compared with back-calculated exposure levels based on biomonitored urinary phthalate metabolite concentrations. The result verifies the existence of varying territorial human background exposure levels and the gap between exposure estimations based on exposure modeling and biomonitoring data. Cumulative childhood risk levels in Denmark were lower than in Korea. For both countries, risk levels from back calculation were higher than those from scenario estimation. The median cumulative risk levels from scenario estimation and back calculation respectively were 0.24 and up to 0.5 in Denmark while 0.52 and up to 0.95 in Korea. Food and indoor dust were the main exposure sources for all three phthalates. In order to protect human health from cumulative risks of these phthalates, the exposure scenarios in existing regulations such as the EU REACH need to be strengthened. Moreover, based on the contributions from different exposure sources, national specific risk management tools need to be developed and strengthened, applying a systemic approach to promote sustainable material flows.

Nationwide monitoring of mercury in wild and farmed fish from fresh and coastal waters of Korea

Mercury (Hg) concentrations were monitored in wild and cultured fish collected from fresh and coastal waters in the Korean peninsula from April 2006 to August 2008 nationwide. Total Hg concentrations were reported for 5043 fish samples, including 78 species from 133 locations. Significant interspecies variation was noted in the Hg levels. The average Hg concentration in each fish species ranged from 6.31 μg kg(-1) for mullet (Mugil cephalus) to 200 μg kg(-1) for mandarin fish (Siniperca scherzeri). Among the species collected, the maximum concentration of Hg, 1720 μg kg(-1), was measured in an Amur catfish (Silurus asotus). Only wild freshwater fish exceeded the WHO ingestion standard. Wild freshwater piscivorous fish samples from a large artificial upstream lake contained the highest Hg levels. Hg concentrations were compared between fish groups categorized as wild and farmed fish from freshwater and coastal waters. Although the wild freshwater fish had similar size ranges, their Hg concentrations were higher than those of the other groups. Compared to the feed of farmed marine and freshwater fishes, the prey of wild freshwater fish had a higher Hg concentration, and the total Hg concentrations in freshwater and associated sediment samples were higher than those in coastal water and associated sediment samples. In the freshwater environment, piscivorous fish bioaccumulated two times more Hg than carnivorous and omnivorous fish and four times more than planktivorous fish. The difference in Hg concentrations among trophic groups might have been due to differences in the size of fish, in addition to the variations among different trophic groups. These data will be useful for developing the fish consumption advisory as a management measure to reduce Hg exposure.

Application of indigenous benthic amphipods as sediment toxicity testing organisms

A series of experiments were conducted to develop standard test organisms and test protocols for measuring sediment toxicity using candidate amphipods such asMandibulophoxus mai, Monocorophium acherusicum, Haustorioides indivisus, andHaustorioides koreanus, which are indigenous to Korea. The relevant association of test species with sediment substrates was one of the important factors in sediment bioassay. The indigenous amphipodsM. mai andM. acherusicum were well associated with test sediments when they were exposed to various sediment substrates from sand to mud. The tolerant limits to various physico-chemical factors affecting bioassay results such as temperature, salinity and ammonia, as well as sensitivities to reference toxicant and contaminated sediments, were investigated usingM. mai andM. acherusicum in the present study. These amphipods were tolerant to relatively wide ranges of salinity (10~30 psu) and ammonia (<50 ppm), and displayed relevant sensitivity to temperature as well. They are more sensitive to Cd, the reference toxicant, when compared to the standard test species used in other countries. Field-sediment toxicity tests revealed thatM. mai would be more sensitive to sediment-associated pollutants thanM. acherusicum, while the sensitivity ofM. acherusicum was comparable to that ofLeptocheirus plumulosus, which has been used as a standard test species in the United States of America. Overall results of this first attempt to develop an amphipod sediment toxicity test protocol in Korea indicated thatM. mai andM. acherusicum would be applicable in the toxicity assessment of contaminated sediments, following the further evaluation encompassing various ecological and toxicological studies in addition to test method standardization.

Physicochemical factors affecting the spatial variance of monomethylmercury in artificial reservoirs

The aim of this study was to identify how hydrologic factors (e.g., rainfall, maximum depth, reservoir and catchment area, and water residence time) and water chemistry factors (e.g., conductivity, pH, suspended particulate matter, chlorophyll-a, dissolved organic carbon, and sulfate) interact to affect the spatial variance in monomethylmercury (MMHg) concentration in nine artificial reservoirs. We hypothesized that the MMHg concentration of reservoir water would be higher in eutrophic than in oligotrophic reservoirs because increased dissolved organic matter and sulfate in eutrophic reservoirs can promote in situ production of MMHg. Multiple tools, including Pearson correlation, a self-organizing map, and principal component analysis, were applied in the statistical modeling of Hg species. The results showed that rainfall amount and hydraulic residence time best explained the variance of dissolved Hg and dissolved MMHg in reservoir water. High precipitation events and residence time may mobilize Hg and MMHg in the catchment and reservoir sediment, respectively. On the contrary, algal biomass was a key predictor of the variance of the percentage fraction of unfiltered MMHg over unfiltered Hg (%MMHg). The creation of suboxic conditions and the supply of sulfate subsequent to the algal decomposition seemed to support enhanced %MMHg in the bloom reservoirs. Thus, the nutrient supply should be carefully managed to limit increases in the %MMHg/Hg of temperate reservoirs.

Assessing correlations between monomethylmercury accumulation in fish and trophic states of artificial temperate reservoirs

We investigated monomethylmercury (MMHg) concentrations in 448 samples of four common fish species (barbel steed, largemouth bass, leopard mandarin, and bluegill) and the trophic states of 14 artificial reservoirs in South Korea in order to understand how trophic states of reserviors affect MMHg concentrations in fish. The trophic state index (TSI) of each reservoir was determined using empirical equations based on the monthly chlorophyll-a, total phosphorus, and Secchi depth, collected over a three-year period. The length-normalized MMHg concentrations in fish showed a negative correlation with the TSI based on chlorophyll-a (r2=0.90) and total phosphorus (r2=0.75) that may be a result of particle dilution of MMHg in surface waters. This study revealed that MMHg accumulation in fish was better correlated with TSI than MMHg in water, therefore, we suggest that the measurement of TSI based on chlorophyll-a and total phosphorus is an effective way to predict MMHg bioaccumulation across diverse reservoirs.

Biomonitoring of trace metals using transplanted mussels, Mytilus galloprovincialis , in coastal areas around Ulsan and Onsan Bays, Korea

Mediterranean (blue) mussels (Mytilus galloprovincialis) collected from a reference site were transplanted to 15 stations in coastal areas around Ulsan and Onsan Bays, an extensively metal polluted area in Korean coastal waters, to assess metal contamination in the coastal oceans of Korea. During the biomonitoring periods (June 30 to July 20, 2003; 21 days), transplanted mussels, seawater, and particulate materials were collected for analysis of 15 metals (Ag, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sb, Se, Sn, and Zn). Transplanted mussels showed metal enrichment compared to initial concentrations and spatial gradients consistent with dissolved and/or particulate metal concentrations in seawaters. Based on Q mode factor analysis, stations were clustered into three groups. The first group, located on Onsan Bay, showed high Ag, Cd, Cu, Hg, Pb, Sb and Zn enrichment, presumably arising from non-ferrous metal refineries and chemical industries in this area. The second group was located near the mouth of the Oehwang River and was enriched in Co from petrochemical industries. The third group comprised a site intermediate between Group 1 and Group 2, an isolated station with independent metal sources located in Jangsaengpo harbor, where a number of ship repairing and building companies operate, and a less contaminated station near a small fishing village. Metal accumulation rates (%·day-1) in mussels were estimated to be between 8% (Cr) and 281% (Pb), based on accumulated metal concentrations over 21 days. The active biomonitoring technique using M. galloprovincialis demonstrated here is a useful monitoring method because it reflects the present status of seawaters; furthermore, physiological factors can be standardized, and bioavailable and time-integrated metal concentrations can be obtained. Furthermore, this method can be applied even in coastal seawaters so heavily contaminated that living organisms would not normally survive.

Monitoring trace metals in seawater using a diffusive gradient in thin film probe in Ulsan Bay, East Sea, Korea: Comparison with transplanted mussels

To evaluate the applicability of a diffusive gradient in thin film (DGT) probe for monitoring dissolved metals in coastal seawater, DGT-labile metal concentrations were compared with total dissolved metal concentrations using spiked and natural seawater samples in the laboratory and transplanted mussels (Mytilus galloprovincialis). This was achieved through the simultaneous deployment of DGT probes and transplanted mussels in Ulsan Bay during winter and summer. DGT-labile metal concentrations were 45% (Cu) ~ 90% (Zn) of total dissolved concentrations, and the order of non-labile concentrations was Cu > Pb > Co ~ Ni > Cd ~ Zn in both metal-contaminated and non-contaminated seawater samples, which was similar to the order of stability of metal complexes in the Irving–Williams series. The overall variability of the DGT probe results within and between tanks was less than 10% (relative standard deviation: RSD) for all the metals tested during a 48-h deployment. The accumulation of metals, as determined by DGT probes, represented the spatial gradients better than the transplanted mussels did for all of the metals tested, and the extent of metal accumulation in mussels differed depending on the metal. The comparison of results for the DGT probe and the transplanted mussels in two seasons (winter and summer) suggested that metal accumulation in mussels was controlled by the physiological factors of mussels and partly by their diet (particulate metal loadings). The DGT probe could be used as a monitoring tool for dissolved metals in coastal seawater because its results explained only labile species. When using the DGT probe, slightly more than half of the total dissolved concentration in seawater samples for all the metals investigated displayed timeintegrated properties and distinct spatial gradients from pristine to metal-contaminated seawater.