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A simultaneous monitoring study on organotins (butyltins and phenyltins) and most frequently used alternative antifouling biocides (Irgarol 1051, Diuron, Sea-Nine 211 and M1) in water and sediments (n=44) collected from three Special Management Sea Areas operated by Korean government. The lower concentration of butyltins (BTs) than that of new antifouling biocides (NEW) was found in water but the significant greater concentration of BTs than that of NEW was still found in sediments. The tributyltin (TBT) levels in water exceeded the chronic criterion to protect seawater aquatic life at several sites. Even ten years after the ban of the use of TBT-based antifouling paint, the concentrations of TBT, Diuron and Irgarol 1051 in sediments from shipyards exceeded global sediment quality guidelines and potentially poses adverse risks on marine organisms and extremely high concentration of TBT up to 2304ng/g was found for a sediment collected at a shipyard.

To examine how tributyltin (TBT), a model obesogen, affects the lipid metabolism in the marine rotifer Brachionus koreanus, we carried out life-cycle studies and determined the in vitro and in silico interactions of retinoid X receptor (RXR) with TBT, the transcriptional levels of RXR and lipid metabolic genes, and the fatty acid content. The lethal concentration 10% (LC10) was determined to be 5.12 μg/L TBT, and negative effects on ecologically relevant end points (e.g., decreased lifespan and fecundity) were detected at 5 μg/L TBT. On the basis of these findings, subsequent experiments were conducted below 1 μg/L TBT, which did not show any negative effects on ecologically relevant end points in B. koreanus. Nile red staining analysis showed that after exposure to 1 μg/L TBT, B. koreanus stored neutral lipids and had significantly increased transcriptional levels of RXR and lipid metabolism-related genes compared to the control. However, the content of total fatty acids did not significantly change at any exposure level. In the single fatty acids profile, a significant increase in saturated fatty acids (SFAs) 14:0 and 20:0 was observed, but the contents of omega-3 and omega-6 fatty acids were significantly decreased. Also, a transactivation assay of TBT with RXR showed that TBT is an agonist of Bk-RXR with a similar fold-induction to the positive control. Taken together, these results demonstrate that TBT-modulated RXR signaling leads to increase in transcriptional levels of lipid metabolism-related genes and the synthesis of SFAs but decreases the content of polyunsaturated fatty acids (PUFAs). Our findings support a wider taxonomic scope of lipid perturbation due to xenobiotic exposure that occurs via NRs in aquatic animals.

Perfluoroalkyl substances (PFASs) have been found in water environment globally. However, the difference on occurrence profiles between PFASs in water from coastal areas and inland rivers or/and agricultural areas is still limited. In this study, the presence of thirteen PFASs in sixty-five surface water samples collected from coastal areas of three southeastern industrialized bays, four major rivers, and six rice field areas in Korea were analyzed. Total PFAS concentrations (ng/L) range from 0.22-73.9 (mean=22.1) for the major rivers, 0.54-3.19 (mean=1.77) for the rice field areas, and

The concentrations, distributions, and bioaccumulation of nine organophosphate flame retardants (OPFRs) were investigated in both abiotic and biotic media, comprising river water, sediment, and crucian carp. The highest concentrations were observed in liver (6.22–18.1 ng/g ww), and the levels in muscle (4.23–7.75 ng/g ww) and gonad (3.08–7.70 ng/g ww) were similar. In whole blood, tris(2-butoxyethyl) phosphate (TBOEP; 31.1–256 ng/mL) accounted for 90% of the total OPFR concentration. Distributions of OPFRs differed between biotic and abiotic media, as tris(2-chloroethyl) phosphate (TCEP), tris(1-chloro-2-propyl) phosphate (TCIPP), and TBOEP were dominant in abiotic media, whereas triethyl phosphate (TEP), tri-n-butyl phosphate (TNBP), TCEP, and TBOEP dominated in crucian carp. The TNBP had remarkable accumulation potential among nine OPFRs, which the TNBP concentrations in muscle increased with increased total length and body weight. The higher perfusion rate of TNBP to female eggs were observed rather than to male gonads as the concentrations were higher in males than in females, while the opposite results were observed in gonad. Moreover, the concentration of TNBP in female muscle began to decrease near maximum growth as a sexually dimorphic difference in crucian carp. This is the first study to simultaneously investigate the fate of OPFRs in biotic and abiotic media and to show sex differences.

Water, sediment, plankton, and blood and liver tissues of crucian carp (Carassius auratus) and mandarin fish (Siniperca scherzeri) were collected from six major rivers and lakes in South Korea (including Namhan River, Bukhan River, Nakdong River, Nam River, Yeongsan River and Sangsa Lake) and analyzed for perfluorinated alkyl substances (PFASs). Perfluorooctane sulfonate (PFOS) was consistently detected at the greatest concentrations in all media surveyed with the maximum concentration in water of 15 ng L(-1) and in biota of 234 ng mL(-1) (fish blood). A general ascending order of PFAS concentration of watersedimentplanktoncrucian carp tissuesmandarin fish tissues was found. Except for the Nakdong River and Yeongsan River, the sum PFAS concentrations in water samples were below 10 ng L(-1). The PFOS and perfluorooctanoic acid (PFOA) concentrations in water did not exceed levels for acute and/or chronic effects in aquatic organisms. High concentrations of long chain perfluorocarboxylates (LCPFCAs) were found in sediment samples. PFOS, perfluoroundecanoic acid (PFUnA), perfluorododecanoic acid (PFDoA) and perfluorodecanoic acid (PFDA) accounted for 94-99% of the total PFASs concentration in fish tissues. The mean ratios of PFAS concentration between fish blood and fish liver were above 2 suggesting higher levels in blood than in liver. Significant positive correlations (r0.80, p0.001) were observed between PFOS concentration in blood and liver tissues of both crucian carp and mandarin fish. This result suggests that blood can be used for nonlethal monitoring of PFOS in fish. Overall, the rank order of mean bioconcentration factors (BCFs) of PFOS in biota was; phytoplankton (196 L/kg)zooplankton (3,233 L/kg)crucian carp liver (4,567 L/kg)crucian carp blood (11,167 L/kg)mandarin liver (24,718 L/kg)mandarin blood (73,612 L/kg).

Six organotins including monobutyltin, debutyltin, tributyltin (TBT), monophenyltin, dephenyltin (DBT), triphenyltin were analyzed to investigate a status and effects of a shipyard to organotins pollution in seawater and sediment from 31 sampling sites, in total, in Jinhae Bay. TBT (mean concentration=2.24 ng/L as Cl) and DBT (mean concentration=3.69 ng/L as Cl) were found as two dominant organotins in water samples. In sediment samples, TBT, which has mean concentration of 53.4 ng/g wet weight as Cl and accounted for 74% in total organotins concentration, in average, was consistently found as the predominant organotin. Phenyltins were not found or found as low concentrations comparing with butyltins. Remarkable geographic distribution of TBT and butyltin compounds showed lower concentrations of those compounds in sampling sites located far from the shipyard.

This study investigated the bioaccumulation effects of endocrine disruption chemicals (EDCs) such as Tributyltin (TBT), Nonylphenol (NP) and Bisphenol-A (BPA) on flounder,Paralichthys olivaceus. The exposure experiment with the flow through system was performed to examine the effects of bioconcentration for single or multi-chemicals. In the muscle of flounder exposed to TBT, the concentrations of TBT were significantly increased compared with the control tank after two months. It is markedly more accumulated in the liver of the flounder than in the muscle. TBT in muscle of the low level of EDCs were highly accumulated in single exposures of TBT compared to multi-chemical exposure with NP and/or BPA. The concentrations of TBT in muscle were increased in the multi-chemical exposure system. The concentration of TBT in the liver of flounder showed a slight decrease in the multi-chemical exposure system. The metabolites of TBT, DBT and MBT were also concentrated in the muscle and liver. NP and BPA in the muscle of flounder were accumulated with high concentration of EDCs. NP and BPA in muscle were significantly decreased compared with TBT after the depuration period.

The rock shell (Thais clavigera) has attracted interest due to high frequency of imposex induced by endocrine disrupting chemicals (EDCs) in its natural populations. Oxidative stress is one of the mechanisms of action of EDCs. Glutathione S-transferases (GSTs) play an important role in antioxidant defense protecting the cells from oxidative stress. So far, there is no information on antioxidant defense or detoxification genes from T. clavigera. We cloned the full length cDNA sequence for a Mu-class of GST gene from T. clavigera (Tc-GSTM) and purified recombinant Tc-GSTM protein by bacterial expression. The deduced amino acid sequence of Tc-GSTM exhibited 45 to 66% identity with other Mu-class GSTs. Real-time RT-PCR analysis showed highest expression of Tc-GSTM in gill, while reproductive organs showed low expression. The biochemical characteristics of purified recombinant Tc-GSTM were typical, and thus Tc-GSTM showed highest specific activity for the universal GST substrate, 1-chloro-2,4-dinitrobenzene (CDNB). After exposure to prooxidant H(2)O(2), transformed Escherichia coli containing Tc-GSTM showed higher survival rate compared to control bacteria without expressed Tc-GSTM. The present study reveals a conserved antioxidant role for GSTM in rock shells, and the tissue-specific differences in Tc-GSTM transcripts would partly reflect vulnerability of reproductive organs to chemically induced oxidative stress.

Phytoestrogens and organochlorine pesticides in the diet of laboratory animals are a possible source of interference in bioassays that assess estrogenic activity. In the present study, we investigated the levels of dietary phytoestrogens, organochlorine pesticides and the estrogenic activity of various diets for an experimental fish and discuss the potential contribution of these substances to estrogenic activity, in comparison with those used in previous studies. After hydrolysis with β-glucuronidase, genistein and daidzein were detected in all of the diets, and there were no significant differences in the contents of these substances among present and previous investigations. In addition, organochlorine pesticides, such as hexachlorobenzene (HCB), β-benzene hexachloride (β-BHC), γ-BHC, trans-nonachlor, and/or endrin, were detected in most fish diets. All of these diets exhibited higher levels of activation of β estrogen receptors than with α estrogen receptors in an in vitro yeast-based bioassay. These results indicate that phytoestrogens, such as genistein and daidzein, were the main substances contributing to the estrogenic activity of the diet. Moreover, some diets may exert estrogenic activity in in vivo tests, indicating the necessity for more careful selection of the feeding diet and measurement of estrogenic substances when performing routine screening assays for endocrine-disrupting chemicals., Journal of Health Science v.51(2) p.212-219, 2005

Toxicity and persistence of perfluorinated alkyl substances (PFASs) in human have raised considerable concern and several biomonitoring studies throughout the world reported the widespread occurrence of these compounds in human tissues. However, information regarding influence of geographic, lifestyle and demographic factor on PFAS levels in human blood tissues is limited. In this study, whole blood samples collected in 2006–2007 from 319 donors from suburban Seoul (Suwon and Yongin), Busan and Yeosu in Korea were analyzed for perfluorooctane sulfonate (PFOS), perfluorooctanoate (PFOA), perfluorononanoate (PFNA), perfluorohexane sulfonate (PFHxS) and perfluorooctane sulfonamide (PFOSA). Blood donors classified into seven age groups with ages ranging from 8 to 82 years, and different lifestyles and socio-economic status. PFOS (median = 4.15 ng/mL) was found at the highest concentration with a maximum concentration of 59.1 ng/mL. The concentrations of other PFASs were in the decreasing order of; PFOA (median = 1.30 ng/mL) > PFNA (median = 0.85 ng/mL) > PFHxS (median = 0.47 ng/mL) > PFOSA (median = 0.12 ng/mL). Geographical differences in the concentrations of five target PFASs were found. Significant positive relationships between PFAS concentrations and the age of the donors were found. Gender-related differences were found in the concentrations of PFOA, PFNA, PFHxS and PFOSA. No association was found between PFAS levels and several lifestyle factors and socio-economic status which included drinking habit, furniture/carpet in an indoor environment and monthly income. Occupation was an important determinant for PFNA and PFHxS concentrations in the whole blood. Except for PFOSA, significant associations were noted between PFASs concentrations and smoking habit. The results of this study provide information for further public health monitoring and safety management for PFASs in Korea.

Acute toxicity tests of tributyltin (TBT) and triphenyltin (TPT) were conducted on hte larvae of the rock shell, Thais clavigera, the disk abalone, Haliotis discus discus and the giant abalone, Haliotis madaka. For the rock shell larvae, the LC50 values (based on the nominal concentrations) were 8.4 μg (24 h) and 5.6 μg (48 h) TBT/IL; 8.6 μg (24 h) and 4.6 μg (48 h) TPT/L. For the disk abalone larvae, the 48 h LC50 values were 5.4 μg TBT/L and 1.4 μg TPT/L. For the giant abalone larvae, the LC50 values were 3.9 μg (24 h) and 1.2 μg (48 h) TBT/L; 2.4 μg (24 h) and 1.5 μg (48 h) TPT/L. Some effects on swimming behavior (e.g. unusual swimming behavior or low swimming activity) and irregular movement of cilia due to atrophy of velum compared to that in the control, as well as stripping out of the larvae from the shell, were observed even at lower concentrations than the LC50 values. From these experimental results and actual organotin concentrations in Japanese inshore waters, TBT pollution may have adversely affected the recruitment of the rock shell, the disk abalone and the giant abalone in heavily polluted areas.

Bisphenol A (BPA) is an industrial chemical used in the manufacture of polycarbonate plastics and epoxy resins. Due to the potential of this compound to disrupt normal endocrinal functions, concerns over human exposure to BPA have been raised. Although several studies have reported human exposure to BPA in Western nations, little is known about exposure in Asian countries. In this study, we determined total urinary BPA concentrations (free plus conjugated) in 296 urine samples (male/female: 153/143) collected from the general population in seven Asian countries, China, India, Japan, Korea, Kuwait, Malaysia, and Vietnam, using high-performance liquid chromatography (HPLC) tandem mass spectrometry (MS/MS). On the basis of urinary BPA concentrations, we estimated the total daily intake. The results indicated that BPA was detected in 94.3% of the samples analyzed, at concentrations ranging from0.1 to 30.1 ng/mL. The geometric mean concentration of BPA for the entire sample set from seven countries was 1.20 ng/mL. The highest concentration of BPA was found in samples from Kuwait (median: 3.05 ng/mL, 2.45 μg/g creatinine), followed by Korea (2.17 ng/mL, 2.40 μg/g), India (1.71 ng/mL, 2.09 μg/g), Vietnam (1.18 ng/mL, 1.15 μg/g), China (1.10 ng/mL, 1.38 μg/g), Malaysia (1.06 ng/mL, 2.31 μg/g), and Japan (0.95 ng/mL, 0.58 μg/g). Among the five age groups studied (≤ 19, 20-29, 30-39, 40-49, and ≥ 50 years), the highest median concentration of BPA was found in urine samples from the age group of ≤ 19 years. There was no significant difference in BPA concentrations between genders (male and female) or domicile of residence (rural and urban). The estimated median daily intakes of BPA for the populations in Kuwait, Korea, India, China, Vietnam, Malaysia, and Japan were 5.19, 3.69, 2.90, 2.13, 2.01, 1.80, and 1.61 μg/day, respectively. The estimated daily intake of BPA in the seven Asian countries was significantly lower than the tolerable daily intake recommended by the U.S. Environmental Protection Agency. This is the first study to document the occurrence of and human exposure to BPA in several Asian countries.

Tributyltin (TBT) is the most common pesticide in marine and freshwater environments. To evaluate the potential ecological risk posed by TBT, we measured biological responses such as growth rate, gonad index, sex ratio, the percentage of intersex gonads, filtration rate, and gill abnormalities in the equilateral venus clam (Gomphina veneriformis). Additionally, the biochemical and molecular responses were evaluated in G. veneriformis exposed to various concentrations of TBT. The growth of G. veneriformis was significantly delayed in a dose-dependent manner after exposure to all tested TBT concentrations. After TBT was administered to G. veneriformis, the gonad index decreased and the sex balance was altered. The percentage of intersex gonads also increased significantly in treated females, whereas no intersex gonads were detected in the solvent control group. Additionally, intersex gonads were detected in male G. veneriformis specimens exposed to relatively high TBT concentrations (20 μg L⁻¹). The filtration rate was also reduced in a dose-dependent manner in TBT-exposed G. veneriformis. We also noted abnormal gill morphology in TBT-exposed G. veneriformis. Furthermore, increases in antioxidant enzyme activities were observed in TBT-exposed G. veneriformis clams, regardless of dosage. Vitellogenin gene expression also increased significantly in a dose-dependent manner in G. veneriformis exposed to TBT. These results provide valuable information regarding our understanding of the toxicology of TBT in G. veneriformis. Moreover, the responses of biological and molecular factors could be utilized as information for risk assessments and marine monitoring of TBT toxicity.

The occurrence of 14 phthalate metabolites was found in human urine samples collected from seven Asian countries: China, India, Japan, Korea, Kuwait, Malaysia, and Vietnam. Phthalate metabolites were found in all samples, indicating widespread exposure of humans to phthalates in these Asian countries. The highest total (the sum of 14 phthalates) phthalate metabolite concentrations were found in samples collected from Kuwait (median: 1050 ng/mL), followed in decreasing order by samples from India (389 ng/mL), China (234 ng/mL), Vietnam (133 ng/mL), Japan (120 ng/mL), Korea (117 ng/mL), and Malaysia (94.9 ng/mL). The creatinine-adjusted median concentrations of total phthalates for urine samples from Kuwait, India, China, Vietnam, Japan, Korea, and Malaysia were 692, 506, 289, 119, 103, 104, and 169 μg/g creatinine, respectively. Monomethyl phthalate (mMP), monoethyl phthalate (mEP), mono (2-isobutyl phthalate) (miBP), mono-n-butyl phthalate (mBP), and metabolites of di-(2-ethylhexyl) phthalate (DEHP) were the dominant compounds, collectively accounting for95% of the total concentrations in the samples from the seven countries. The profiles of urinary phthalate metabolite concentrations varied among the samples collected from the seven countries. Urine samples from Kuwait contained the highest concentrations of mEP (median: 391 ng/mL), mBP (94.1 ng/mL), and the metabolites of DEHP (202 ng/mL), whereas samples from China and Japan contained the highest concentrations of miBP (50.8 ng/mL) and mMP (17.5 ng/mL), respectively. mEP was the predominant metabolite in urine samples from India and Kuwait (accounting for 49% of the total), mBP and miBP were the predominant compounds in samples from China (52%), and DEHP metabolites were the predominant compounds in samples from Korea (46%) and Vietnam (52%). Based on the urinary concentrations of mEP, mBP, miBP, and DEHP metabolites of the samples from the seven Asian countries, we estimated daily intake rates of diethyl phthalate (DEP), dibutyl phthalate (DBP), and DEHP. The results indicated that people in the seven Asian countries are exposed to DEP, DBP, and DEHP at levels well below the reference doses (RfD) suggested as unsafe by the U.S. Environmental Protection Agency (EPA). The estimated exposure doses to DEHP in Kuwait, however, were above the RfD recommended by the EPA.

The PCDD/DFs and coplanar PCBs (co-PCBs) in sediment samples from Gwangyang Bay in South Korea was investigated. The total concentration of dioxins and their toxic equivalent quantity (TEQ; calculated with the WHO 2005 Toxic Equivalency Factors) value in the surface sediment of the outer site (261 pg g −1 TOC, 4.4 pg-TEQ g −1 ) were 3-fold higher than the inner site (90 pg g −1 TOC, 1.1 pg-TEQ g −1 ) in the Bay. The dioxin in the sediment samples was found to come from a mixture of the impurities of pentachlorophenol (PCP), chloronitrofen (CNP) and combustion based on the result of hierarchical cluster analysis (HCA). These dioxin sources have been influenced by the characterization associated with this region which was both an agricultural-centered and industrial-centered area. According to principal component analysis (PCA) related to the K ow values for the congener-specific composition of co-PCBs in the sediment core, the Kanechlor (KC)-500 and the atmospheric deposition were identified as the possible sources. The maximum burden in the sediment core was 1.3 kg for 1967–1974 and the total burdens of PCDD/DFs and co-PCBs in the sediment core were estimated to be 6.6 kg during the past 50 years. The cumulative burdens of dioxin are still increasing in Gwangyang Bay.

Perfluorinated compounds (PFCs), such as perfluorooctane sulfonate (PFOS), perfluorooctanoate (PFOA), perfluorononanoate (PFNA), perfluorohexane sulfonate (PFHS), and perfluorooctane sulfonamide (PFOSA) are widely distributed in aquatic ecosystems. Despite studies reporting the occurrence of PFCs in aquatic organisms, the fate of PFCs in tidal flat and marine coastal ecosystems is not known. In this study, we determined concentrations of PFOS, PFOA, PFNA, PFHS, and PFOSA in sediments; benthic organisms, including lugworm, mussel, crab, clam, oyster, and mudskipper fish from tidal flat; and shallow water species, such as filefish, bream, flounder, shark, finless porpoise, gull, and mallard collected from the Ariake Sea, Japan. PFOS and PFOA were detected in most of the samples analyzed, followed by PFNA, PFOSA, and PFHS. In shallow water species, PFOS was the dominant contaminant, and elevated concentrations were found in higher trophic level species, such as marine mammals and omnivorous birds. These results suggest biomagnification of PFOS through the coastal food chain. In contrast, PFOA was the most abundant compound in tidal flat organisms and sediments. PFOA concentrations in sediments, lugworms, and omnivorous mudskippers in tidal flat were approximately 1 order of magnitude greater than the levels of PFOS. This indicates differences in exposure pattern and bioavailability of PFOS and PFOA between shallow water and tidal flat organisms. The accumulation profiles of PFCs were compared with those of organochlorines (polychlorinated biphenyls, PCB), organotin (tributyltin,TBT), and polycyclic aromatic hydrocarbons (PAHs) in tidal flat and shallow water samples collected from the Ariake Sea. Concentrations of PFCs in sediments and in tidal flat organisms were significantly lower than that found for PCBs, TBT, and PAHs. Nevertheless, PFOS concentrations in shallow water species were comparable to and/or significantly greater than those of other classes of contaminants. This implies that the aqueous phase is a major sink for PFCs, which is different from what was observed for nonpolar organic pollutants.