Discrimination of metal contaminant sources in river sediments influenced by mining and smelting activities using stable Pb and Zn isotopes.

To determine the sources and pathways of lead (Pb) and zinc (Zn) in river sediments contaminated with metals from mining and smelting activities, metal concentrations and Pb and Zn isotope ratios were measured in river water and sediment, and potential metal contaminant samples (imported Zn concentrates, smelting wastes, soils around the smelter, mine ores, and riverside tailings). Zn and cadmium (Cd) concentrations in river water and sediment samples were 30- and 11-25-fold higher, respectively, near the smelter than upstream, while a 6-fold increase in sediment Pb concentrations was detected over the same region. Sediment samples near the smelter (207Pb/206Pb = 0.8638 and 208Pb/206Pb = 2.0960) were observed to have a different Pb isotopic composition from upstream of the smelter (207Pb/206Pb = 0.8322 and 208Pb/206Pb = 2.0502), with δ66Zn values increasing from -0.01 to 0.82‰. Analysis of Pb and Zn isotopes and concentrations revealed that dust-contaminated soils were a major Pb source, and baseline sediments were found to be contaminated by regional mining tailings. For Zn in sediments, the main Zn sources were groundwater-derived Zn (δ66Zn = 1.02 ± 0.43‰, n = 4), dust-contaminated soils (δ66Zn = -0.18 ± 0.08‰, n = 3), and tailings-contaminated sediments (δ66Zn = 0.01 ± 0.07‰, n = 10). Endmember mixing model results showed that dust-contaminated soils contributed 78% and 64% of sediment Pb and Zn, respectively, within 2 km of the Zn smelter, decreasing to negligible levels after 47.1 km downstream. Downstream of the smelter, groundwater-derived Zn contributed 54% of sediment Zn, whereas tailings contaminated sediments contributed 70% and 25% of Pb and Zn, respectively.

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.

Importance of hydraulic residence time for methylmercury accumulation in sediment and fish from artificial reservoirs.

Excessive methylmercury (MeHg) accumulation in dietary fish is a global concern due to its harmful effects on human health, however, environmental factors affecting MeHg accumulation in reservoir ecosystems are not clearly known. In this study, we aim to identify the main sources of MeHg in the water column and the critical factors related to MeHg concentration and methylation rate constant (km) in sediment and total Hg concentration in fish using five-year (2016-2020) monitoring data of the five artificial reservoirs. The preliminary mass budgets constructed using the measurement and online data showed that sediment transport dominated over runoff in the long residence time reservoirs (400-475 days), while runoff dominated over sediment transport in the short residence time reservoirs (10 days). Whereas the sediment km showed a comparable variation with the algal biomass, the sediment MeHg concentration and the length-normalized Hg concentration in the barbel steed and bluegill increased in the longer residence time reservoirs with lower algal biomass. As MeHg accumulation in sediment and fish tends to increase in the slowly overturning reservoirs, the hydraulic residence time should be carefully managed to meet the best protection of human health from chronic Hg exposure by fish consumption.

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.

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.

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.

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.