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This study investigated the nitrate dual isotopic compositions (δ 15 N NO3 and δ 18 O NO3 ) of water samples to trace nitrate sources in Lake Sihwa, which encompasses various land-use types (e.g., urban, industry, wetland, and agriculture). The biogeochemical interactions of anthropogenic nitrogen sources (e.g., soil, road dust, and septic water) were also evaluated through multiple pathways from terrestrial boundaries to the water column. Based on increased concentrations of dissolved total nitrogen (DTN; 3.1 ± 1.6 mg/L) after typhoon, the variation of element stoichiometry (N:P:Si) in this system shifted to the relatively N-rich conditions (DIN/DIP; 14.1 ± 8.1, DIN/DSi; 1.4 ± 1.8), potentially triggering the occurrence of harmful algal blooms. Furthermore, discriminative isotopic compositions (δ 15 N NO3 ; 4.0 ± 2.1 ‰, δ 18 O NO3 ; 6.1 ± 4.3 ‰) after the typhoon suggested the increased DTN input of anthropogenic origins within Lake Sihwa would be mainly transported from urban sources (76 ± 9 %). Consequently, the isotopic-based approach may be useful for effective water quality management under increased anthropogenic activities near aquatic systems., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

This study utilized both conventional molecular analysis and compound-specific isotopic techniques to identify the sources of polycyclic aromatic hydrocarbons (PAHs) in sediments of Ulsan Bay, South Korea. The concentrations of 15 traditional and 11 emerging PAHs were determined in sediments from 21 source sites and 26 bay sites. The concentrations and compositions of traditional and emerging PAHs varied significantly, even at sites close to the source areas. The results obtained from diagnostic ratios and the positive matrix factorization model for source identification were inconsistent in adjacent source areas. The δ 13 C profiles of PAHs, such as phenanthrene (Phe), fluoranthene (Fl), pyrene (Py), and benz[a]anthracene (BaA) in the sediments showed distinct features depending on the surrounding sources. In urban sediments, lighter δ 13 C Phe values were observed (mean: -25.1‰), whereas relatively heavier values of δ 13 C Py were found in petroleum industry areas (mean: -23.4‰). The Bayesian isotope mixing model indicates that the predominant source of PAHs in Ulsan Bay sediments was the petroleum industry (45%), followed by the non-ferrous metals industry (30%), automobile industry (18%), and urban areas (6.3%). These results demonstrated the utility of stable isotopes in assessing the sources and contributions of PAHs in small-scale regions. However, there are still limitations in compound-specific isotope analysis of PAHs, including insufficient end-members for each source, difficulty in analysis, and the influence of non-point sources; thus, further study is needed to expand its application., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Although many attempts have been carried out to elaborate trophic magnification factor (TMF) and biomagnification factor (BMF), such as normalizing the concentration of pollutants and averaging diet sources, the uncertainty of the indexes still need to be improved to assess the bioaccumulation of pollutants. This study first suggests an improved BMF (i.e., BMF') applied to mercury bioaccumulation in freshwater fish from four sites before and after rainfall. The diet source and TP of each fish were identified using nitrogen stable isotope of amino acids (δ 15 N AAs ) combined with bulk carbon stable isotope (δ 13 C). The BMF' was calculated normalizing with TP and diet contributions derived from MixSIAR. The BMF' values (1.3-27.2 and 1.2-27.8), which are representative of the entire food web, were generally higher than TMF (1.5-13.9 and 1.5-14.5) for both total mercury and methyl mercury, respectively. The BMF' implying actual mercury transfer pathway is more reliable index than relatively underestimated TMF for risk assessment. The ecological approach for BMF calculations provides novel insight into the behavior and trophic transfer of pollutants like mercury., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Quantitative estimation for tracking the transport of various nitrate sources is required to effectively manage nitrate loading in complex river systems. In this study, we validated an integrated framework using field isotopic data (δ 15 N NO3 and δ 18 O NO3 ) of nitrates and hydrological modeling (hydrological simulation program FORTRAN; HSPF) to determine anthropogenic nitrate flux among different land-use types within a watershed. Nitrate isotopic compositions showed different ranges among four land-use types (4.9 to 15.5‰ for δ 15 N NO3 , -4.9 to 12.1‰ for δ 18 O NO3 ), reflecting the different nitrate sources (sewage, synthetic fertilizer, effluent and soil) within watersheds. Based on the integration of HSPF modeling, we also found that total nitrate loads might be partially controlled by hydrological conditions such as water discharge (12,040.3-22,793.2 L/s) from upstream to downstream. Among the nitrate sources, the sewage transport showed unique enhancement near urban boundaries, along with an increase in total nitrate load (>193.5 NO 3 -N g/s km 2 ) in downstream areas. In addition, the isotopic- and model-based nitrate fluxes showed good correlation for urban sources (R 2 =0.73, p < 0.05) but poor correlations for agriculture-dominated land use (R 2 =0.13, p > 0.05), reflecting the potential influence of surface runoff and ground infiltration into the watershed. Consequently, this research provided useful information to establish nitrogen management policy controlling point and non-point nitrate source loads in various land-use types for the restoration of water quality and aquatic ecosystem in the complex river system. Considering the recent increase in human activities near aquatic environments, this framework would be effective for individually estimating the quantitative contributions of anthropogenic nitrate sources transported along river-coastal systems., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier Ltd.)

The freshwater water flea Daphnia magna is a planktonic animal belonging to the Cladocera. To evaluate differences between two D. magna strains (KIT and NIES) in terms of life parameters and fatty acid profiles, we examined several endpoints. In the D. magna KIT strain, the numbers of total and cumulative offspring were lower at 23 °C and higher at 14 °C than in the D. magna NIES strain. However, at 14 °C, the D. magna KIT strain showed an increased lifespan. Although the n-3/n-6 polyunsaturated fatty acids (PUFA) ratio was always decreased at a low temperature, the PUFA ratio in the KIT strain had a higher value on day 3 than the NIES strain, which gave it higher adaptability to low temperature. In addition, we identified the elongation of very long chain fatty acids (elovl) and fatty acid desaturase (fad) genes, which are involved in fatty acid biosynthesis pathways, in the genomes of both D. magna KIT and NIES. The Elovl and Fad genes in both D. magna strains were highly conserved, including tandem duplicated Elovl 1/7 genes. This study provides new information about the molecular basis for the difference in temperature sensitivity between two strains of D. magna., (Copyright © 2022. Published by Elsevier Inc.)

We coupled compound-specific isotopic analyses of nitrogen (N) in amino acids (δ 15 N Glu , δ 15 N Phe ) and mercury stable isotopes (δ 202 Hg, Δ 199 Hg) to quantify ecological traits governing the concentration, variability, and source of Hg in largemouth bass (LB) and pike gudgeon (PG) across four rivers, South Korea. PG displayed uniform Hg concentration (56-137 ng/g), trophic position (TP corrected ; 2.6-3.0, n = 9), and N isotopes in the source amino acid (δ 15 N Phe ; 7-13‰), consistent with their specialist feeding on benthic insects. LB showed wide ranges in Hg concentration (45-693 ng/g), TP corrected (2.8-3.8, n = 14), and δ 15 N Phe (1.3-16‰), reflecting their opportunistic feeding behavior. Hg sources assessed using Hg isotopes reveal low and uniform Δ 199 Hg in PG (0.20-0.49‰), similar to Δ 199 Hg reported in sediments. LB displayed site-specific δ 202 Hg (-0.61 to -0.04‰) and Δ 199 Hg (0.53-1.09‰). At the Yeongsan River, LB displayed elevated Δ 199 Hg and low δ 15 N Phe , consistent with Hg and N sourced from the atmosphere. LB at the Geum River displayed low Δ 199 Hg and high δ 15 N Phe , both similar to the isotope values of anthropogenic sources. Our results suggest that a specialist fish (PG) with consistent ecological traits and Hg concentration is an effective bioindicator species for Hg. When accounting for Hg sources, however, LB better captures site-specific Hg sources.

Despite the extensive usage of synthetic musk compounds (SMCs) and siloxanes in various personal care products (PCPs), trophic magnification of such chemicals in aquatic environments remains unexplored. In June and September 2020, eleven SMCs and nineteen siloxanes were measured in water, sediments, and biota. Samples were collected from two sites where levels were expected to be influenced by the distance from the wastewater treatment plant (WWTP) in the Geum River, Republic of Korea, were expected. High concentrations of SMCs and siloxanes entered through WWTP were measured in water, sediment, and biota at the both sites and both seasons. The δ 15 N of amino acids provided a high-resolution food web and accurate trophic position (TP), which is an important factor for determining the trophic magnification factor (TMF). Among 24 TMFs, 19 of them were <1, ranging 0.7-0.8 for 1,3,4,6,7,8‑hexahydro‑4,6,6,7,8,8‑hexamethyl‑cyclopenta‑γ‑2‑benzopyran (HHCB), 0.6-0.8 for 6-Acetyl-1,1,2,4,4,7-hexamethyltetralin (AHTN), 0.7-0.8 for 4-tert-Butyl-3,5-dinitro-2,6-dimethylacetophenone (MK), 0.7-0.9 for octamethylcyclotetrasiloxane (D4), 0.1-0.4 for decamethylcyclopentasiloxane (D5), and 0.04-0.8 for dodecamethylcyclohexasiloxane (D6), and the remaining ones including HHCB, AHTN, MK, and D4 showed values close to 1 or slightly higher (TMF range: 1.0-2.3) indicating no or a little trophic magnification. The TMFs of these compounds were constant across sites and seasons. The TMF values of PCPs might be affected by species specificity and food web structure rather than by chemical properties such as log K ow , which describes a wide range of TMF values in various environments. This study presents valuable implications for assessing risk and managing environmental fate and trophic transfer of SMCs and siloxanes in freshwater environments., (Copyright © 2022 The Authors. Published by Elsevier Ltd.. All rights reserved.)

The increased use of disinfectants due to the spread of the novel coronavirus infection (e.g. COVID-19) has caused burden in the environment but knowledge on its ecotoxicological impact on the estuary environment is limited. Here we report in vivo and molecular endpoints that we used to assess the effects of chloroxylenol (PCMX) and benzalkonium chloride (BAC), which are ingredients in liquid handwash, dish soap products, and sanitizers used by consumers and healthcare workers on the estuarine rotifer Brachionus koreanus. PCMX and BAC significantly affected the life table parameters of B. koreanus. These chemicals modulated the activities of antioxidant enzymes such as superoxide dismutase and catalase and increased reactive oxygen species even at low concentrations. Also, PCMX and BAC caused alterations in the swimming speed and rotation rate of B. koreanus. Furthermore, an RNA-seq-based ingenuity pathway analysis showed that PCMX affected several signaling pathways, allowing us to predict that a low concentration of PCMX will have deleterious effects on B. koreanus. The neurotoxic and mitochondrial dysfunction event scenario induced by PCMX reflects the underlying molecular mechanisms by which PCMX produces outcomes deleterious to aquatic organisms., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Here, we investigated the characteristics of the environmental multimedia distribution of microcystins (MCs) introduced from freshwater discharge through the estuary dam of the Geum River. In addition, the applicability of a passive sampling device (polar organic chemical integrative sampler, POCIS) for monitoring MCs was evaluated. Surface water, suspended solids (SS), sediments, and oysters were collected from the inner and outer estuary dam. Seven MC variants were analyzed using HPLC-MS/MS. POCIS was deployed at three sites over one week, and MCs were monitored for four weeks from August to September 2019. Before POCIS was deployed in the field, compounds-specific sampling rates of MCs were determined as functions of water temperature (10, 20, and 30 °C), flow rate (0, 0.38, and 0.76 m s -1 ), and salinity (0, 15, and 30 psu) in the laboratory. The sampling rates of MCs in POCIS increased significantly with increasing water temperature and flow rate, whereas salinity did not significantly affect the sampling rates between freshwater and saltwater. The MCs in the Geum River Estuary mainly existed as particulate forms (mean: 78%), with relatively low proportions of dissolved forms (mean: 22%), indicating that MCs were mainly contained in cyanobacterial cells. There was no significant correlation among the concentrations of MCs in water, SS, sediments, and oysters. Time-weighted average concentrations of MCs from POCIS were not significantly correlated with the concentrations of MCs in water and oysters. The metabolites of MCs, including MC-LR-GSH, MC-LR-Cys, MC-RR-GSH, and MC-RR-Cys, were detected in oysters (no metabolites were detected in POCIS). Overall, POCIS can be useful for monitoring dissolved MCs in the aquatic ecosystem, particularly in calculating time-weighted average concentrations, but it seems to have limitations in evaluating the contamination status of total MCs, mainly in particulate form., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Contamination status of traditional and emerging persistent toxic substances (PTSs) in sediments and their major sources were investigated in Ulsan Bay, Korea. A total of 47 PTSs, including 15 traditional PAHs, ten styrene oligomers (SOs), six alkylphenols (APs), and 16 emerging PAHs (E-PAHs) were analyzed. Concentrations of traditional PAHs, SOs, and APs ranged from 35 to 1300 ng g -1 dry weight (dw), 30 to 3800 ng g -1 dw, and 30 to 430 ng g -1 dw, respectively. For the last 20 years, PTSs contamination in the bay area has been improved. However, 12 E-PAHs were widely detected in sediments, with a maximum of 240 ng g -1 dw (for benzo[e]pyrene) at the creek site. These E-PAHs seemed to originate from surrounding activities, such as biomass combustion, mobile sources, and diesel combustion. Due to environmental concerns for E-PAHs, further research on the potential toxicity, distribution, and behavior of these compounds should be implemented., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Trophic magnification factor (TMF) of persistent toxic substances (PTSs: Hg, PCBs, PAHs, and styrene oligomers (SOs)) in a coastal food web (12 fish and four invertebrates) was determined in Ulsan Bay, South Korea. The nitrogen stable isotope ratios (δ 15 N) of amino acids [δ 15 N Glu-Phe based on glutamic acid (δ 15 N Glu ) and phenylalanine (δ 15 N Phe )] were used to estimate the trophic position (TP Glu-Phe ) of organisms. The TP Glu-Phe of organisms ranged from 1.64 to 3.69, which was lower than TP estimated by δ 15 N of bulk particulate organic matter (TP Bulk : 2.46-4.21). Mercury and CB 138, 153, 187, and 180 were biomagnified through the whole food web (TMF > 1), while other PTSs, such as PAHs and SOs were not (biodilution of SOs firstly reported). In particular, the trophic transfer of PTSs was pronounced in the resident fish (e.g., rock bream, sea perch, Korean rockfish). Of note, CB 99, 101, 118, and 183 were additionally found to be biomagnifying PTSs in these species. Thus, fish residency appears to represent an important factor in determining the TMF of PTSs in the coastal environment. Overall, δ 15 N Glu-Phe provided accurate TPs of organisms and could be applied to determine the trophic transfer of PTSs in coastal food webs., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

In this study, surface water samples were collected at sites located in the lowest reaches of closed (Geum) (i.e. with an estuary dam at the river mouth) and open (Seomjin) estuary systems between May 2016 and May 2018. We analyzed concentrations and stable isotopes of particulate organic carbon (POC) and dissolved organic carbon (DOC) to assess OC sources, to estimate fluxes of riverine OC, and to assess some of the factors driving OC exports in these two contrasting Korean estuary systems. Our geochemical results suggest that the contribution of the phytoplankton-derived POC to the total POC pool was larger in the Geum River than in the Seomjin River. Notably, a heavy riverine algae bloom occurred in the Geum River in August 2016, resulting in a high carbon isotopic composition (-19.4‰) together with low POC/PN ratio (<10) and POC/Chl-a ratio (<100). In contrast, potential DOC sources in both the Geum River and the Seomjin River were a mixture of C 3 -derived forest soils and cropland organic matter. During the study period, the catchment area-normalized fluxes of POC and DOC were 0.40 × 10 -3  tC/km 2 /yr and 6.5 × 10 -2  tC/km 2 /yr in the Geum River and 5.2 × 10 -4  tC/km 2 /yr and 8.6 × 10 -4  tC/km 2 /yr in the Seomjin River, respectively. It appears that the POC flux was more weakly associated with the water discharge in the Geum River than in the Seomjin River, but the DOC fluxes were in general controlled by the water discharges in both rivers. Accordingly, the estuary dam of the Geum River might be one of the most strongly influencing factors on seasonal patterns in POC fluxes into the adjacent coastal seas, strongly modifying water residence times and thus biogeochemical processes., (Copyright © 2019 The Authors. Published by Elsevier Ltd.. All rights reserved.)

This study utilized effect-directed analysis (EDA) combined with full-scan screening analysis (FSA) to identify aryl hydrocarbon receptor (AhR)-active compounds in sediments of inland creeks flowing into Lake Sihwa, South Korea. The specific objectives were to (i) investigate the major AhR-active fractions of organic extracts of sediments by using H4IIE-luc in vitro bioassay (4 h and 72 h exposures), (ii) quantify known AhR agonists, such as polycyclic aromatic hydrocarbons (PAHs) and styrene oligomers (SOs), (iii) identify unknown AhR agonists by use of gas chromatography-quadrupole time-of-flight mass spectrometry (GC-QTOFMS), and (iv) determine contributions of AhR agonists to total potencies measured by use of the bioassay. FSA was conducted on fractions F2.6 and F2.7 (aromatics with log K ow 5-7) in extracts of sediment from Siheung Creek (industrial area). Those fractions exhibited significant AhR-mediated potency as well as relatively great concentrations of PAHs and SOs. FSA detected 461 and 449 compounds in F2.6 and F2.7, respectively. Of these, five tentative candidates of AhR agonist were selected based on NIST library matching, aromatic structures and numbers of rings, and available standards. Benz[b]anthracene, 11H-benzo[a]fluorene, and 4,5-methanochrysene exhibited significant AhR-mediated potency in the H4IIE-luc bioassay, and relative potencies of these compounds were determined. Potency balance analysis demonstrated that these three newly identified AhR agonists explained 1.1% to 67% of total induced AhR-mediated potencies of samples, which were particularly great for industrial sediments. Follow-up studies on sources and ecotoxicological effects of these compounds in coastal environments would be required., (Copyright © 2019 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Sources of organic matter in a polluted coastal embayment (Lake Sihwa) indicated that δ 13 C and δ 15 N of suspended particulate matter (SPM) and sediments could be distinguished by land-use type and surrounding activities. Specifically, low δ 15 N occurred in inland creeks near industrial complex, where severe contamination by persistent toxic substances (PTSs) is evidenced. To identify the sources of 15 N-depleted organic matter and PTSs, the SPM and/or sediments were collected along ~8 km of the Singil Creek and in stormwater drainage pipes that carried pollutants to the creeks from upland areas. Results indicated that stormwater originating in industrial areas was the main source of low δ 15 N and elevated PTSs, which appeared to flow into stormwater drains with rainwater and eventually into the creeks at stormwater outfalls. To improve the water quality of inland creeks, it will be necessary to reduce the amount of untreated stormwater entering stormwater drainage system from industrial complex., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

In this study, ideal mixing behaviors of the three commonly-used source tracking tools, which include fluorescence spectroscopy, stable isotope ratios, and lipid biomarkers, were evaluated in controlled particular organic matter (POM) mixtures of two contrasting end members e.g., soil and algae. In parallel, three different extraction methods based on water (WEOM) and two alkaline solutions were compared to identify the preferential pre-treatment option that leads to a good performance of the spectroscopic source tracking indices on the dissolved organic matter (DOM) extracted from the POM. Based on three evaluation criteria concerning the linearity of the relationships, the discrimination sensitivity, and the conservative mixing behavior of fourteen tested indices, the fluorescence proxies such as the relative distribution of the fluorescence components and the modified fluorescence index YFI of the WEOM were found to be reliable and robust indices for POM source tracking. The carbon stable isotope ratios of the POM samples exhibited an ideal mixing behavior even after the DOM extraction, while the biomarkers of sterols/stanols did not present a good linear and conservative behavior at similar conditions. In addition, the WEOM was identified as the preferred extraction method for the application of spectroscopic indices for POM source discrimination. This study provides a guideline to select the optimum indices for the POM source discrimination via the end member mixing analysis., (Copyright © 2019 Elsevier B.V. All rights reserved.)

The main sources of nutrients fueling coastal green tides off a volcanic island surrounded by an oligotrophic ocean are obscure, although they result in many societal and ecosystem problems. In this study, we attempted to trace the source inputs of nutrients in coastal waters off a volcanic island, Jeju, Korea, where the formation of green tides is perennial, using a radioisotope ( 222 Rn) and stable isotopes (δ 15 N and δ 18 O) as tracers. Sampling of groundwater, seawater, fish-farm water, and Ulva spp. was performed during April and July 2015. The contribution of submarine fresh groundwater discharge (SFGD) to the dissolved inorganic nitrogen input was >70%, with additional inputs from aqua-cultural activities and bottom sediments. The δ 15 N-NO 3 and δ 18 O-NO 3 values in the coastal seawater and groundwater indicate that the main source of NO 3 - is fertilizer, rather than other potential sources, such as aquacultural wastewater, sewage/manure contamination, or precipitation, in this region. The δ 15 N value (+7.3-+7.7‰) in Ulva spp. also indicates the same source. Thus, our results suggest that the rapid infiltration of land N-fertilizer and subsequent leakage into the coastal ocean through submarine groundwater discharge (SGD) results in green tide massive occurrence in coastal waters off a high-permeability volcanic island., (Copyright © 2019 Elsevier B.V. All rights reserved.)

The Mekong River Delta (Vietnam) is a flat, low-lying area formed by a dense network of main tributaries of the Tien and Hau Rivers, providing a nourishing habitat for aquatic organisms. A sediment survey of the total mercury (Hg), monomethylmercury (MMHg), and geochemical variables was carried out from the coast to 131 km upriver to establish an overview of the environmental factors affecting the bioaccumulation of Hg and MMHg in delta fish. The survey results revealed that the total Hg (12-90 ng g -1 ) and MMHg (0.014-1.5 ng g -1 ) concentrations were in the range of uncontaminated sediment. Statistical analysis using various geochemical factors demonstrated that sediment MMHg concentrations and fractions of MMHg over total Hg in sediment were higher at sites with higher total organic carbon (TOC) and total nitrogen sites. The current levels of TOC in Mekong Delta sediment are relatively low (0.2-1.5%); however, expanding dam constructions and aquacultures related to salinity intrusion are reinforcing the carbon burial rate by increasing the fine fractions. Based on the positive relationship found between MMHg and TOC in sediment, proper management efforts are necessary to reduce MMHg production in the Mekong River Delta sediment. Environ Toxicol Chem 2019;38:503-510. © 2018 SETAC., (© 2018 SETAC.)

We investigate historical environmental changes in an artificial lake, Lake Shihwa in South Korea, based on bulk (TOC, TN, C/N ratio, δ 13 C TOC , and δ 15 N TN ) and molecular (concentrations and δ 13 C of n-alkanes) parameters, by analyzing riverbank sediments (n = 12), lake surface sediments (n = 9), and lake core sediments (n = 108). Although the bulk organic parameters showed similar characteristics for all lake surface sediment samples, the distribution pattern and δ 13 C of n-alkanes revealed distinct differences between 2009 samples and 2012/2016 samples. This change of sedimentary organic matter characteristics can be attributed to operation of the tidal power plant that began in 2011, which improved lake water circulation and thus changed the lake sedimentary environment from anoxic to more oxic conditions. The vertical profiles of bulk and molecular lake sediment core records collected in 2009, especially at the site closest to the dike, showed a drastic shift around 1987, indicating that stronger anoxic sedimentary conditions prevailed after 1987. This is linked to sea dike construction in 1987, which prohibited sea-lake water exchange and thus deteriorated water quality in Lake Shihwa. We conclude that Lake Shihwa has experienced severe environmental changes due to human activities., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Laboratory-scale sediment exposure was conducted as a preliminary study to assess the long-term effects of sediment contaminated with crude oil. For this purpose, indirect exposure using a glass filter crucible was tested and compared with direct exposure by observing several parameters (e.g., mortality, growth, reproduction, hatching, and uptake) in the benthic copepod Tigriopus japonicus. In direct exposure, short-term exposure caused significant damages to the eggs of ovigerous females, and there were difficulties in observing small oil droplets. However, indirect exposure did not induce any mortality during a 96-h exposure in adults. A 10-day exposure was also possible in an indirect exposure method and caused a decrease in reproduction and consequently a reduction in the hatching rate. In fact, the water phase collected from indirect exposure indicated significant polycyclic aromatic hydrocarbon (PAH) concentrations, although only a few components were present. The components of PAHs were similar to water-accommodated fractions (WAFs) of crude oil that are associated with the water-soluble part, but the relative portion of high-molecular-weight of PAHs was higher than WAF. In this approach, exposure tests caused reduction in the uptake rate in copepods even in the 24-h exposure. In conclusion, the biological effects of oil droplets from direct exposure were excluded by using a glass filter in indirect exposures, and several parameters could be derived in the long-term exposure. These results indicate that the indirect method could likely assess the chronic effects of oil-contaminated sediments on individual level parameters for deriving the ultimate effects on the population and community., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The temporal changes in the frequency and degree of imposex and tributyltin (TBT) levels in gastropod (Reishia clavigera) were evaluated in Jinhae Bay, 5 and 10 years after the total ban on TBT usage in South Korea. The frequency and degree of imposex decreased significantly after the ban, accompanied by an increase in the female-to-male ratio. The TBT concentrations in R. clavigera also decreased significantly after the ban. There were good correlations between the TBT concentration in rock shell and both the degree of imposex and the female-to-male ratio. The total TBT ban effectively reduced the TBT levels and the frequency and degree of imposex in R. clavigera. However, the current low exposure level in the study area is still sufficient to cause imposex in R. clavigera. More time is needed to reduce the TBT levels to levels that do not have adverse biological effects on R. clavigera.

Coastal areas are subjected to significant allochthonous organic matter deposits from surrounding areas; however, limited information is available on the source and delivery of this organic matter. In this study, to assess seasonal changes in the sources of organic matter in Lake Sihwa (Korea), biodegradability, fluorescence property, and stable isotopic compositions (carbon, nitrogen, and sulfur) of the organic matter were determined. Water samples were collected from the inner lake (n = 9) and inland creeks (n = 10) in five separate events, from November 2012 to October 2013. Organic matter originating from rural, urban, and industrial areas was examined as the potential sources. The organic matter contents and biodegradability in the industrial area were the highest, whereas low concentrations and poor biodegradability of organic matter were found in the rural area, and moderate properties were observed in the urban area. In Lake Sihwa, a large concentration of total organic matter and enhanced biodegradability were observed during March and August. However, main source of organic matter differed between the sampling events. The largest contribution of organic matter, deriving from marine phytoplankton, was found in March. On the other hand, in August, the organic matter originating from the industrial area, which is characterized by high levels of heavy metals and persistent organic pollutants, was significantly increased. Our results could be useful to enhance the management of water bodies aimed at reducing the organic matter concentrations and improving the water quality of Lake Sihwa, and even that of the Yellow Sea., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Temporal trend studies are useful to evaluate the effectiveness of regulations on local pollutants. The emission of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (PCBs) has been regulated by the Korean government in accordance with the Stockholm Convention. The accumulation and temporal trends of PCDD/Fs and dioxin-like PCBs were investigated in finless porpoises (Neophocaena asiaeorientalis) collected in Korean waters. Median concentrations of PCDDs, PCDFs, non-ortho PCBs, and mono-ortho PCBs were 1.0, 1.1, 0.1, and 1.8pgTEQ/g lipid weight, respectively, which were lower than threshold values for marine mammals. Age- and sex-dependent accumulation patterns were found for PCDFs and DL-PCBs. Temporal trends in finless porpoises collected between 2003 and 2010 showed significant reduction rates of 57%, 54%, 69%, and 60% for PCDDs, PCDFs, non-ortho PCBs, and mono-ortho PCBs, respectively. Our results suggest that the regulations on dioxin-like contaminants have been effective for marine mammals in Korea., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The occurrence and distribution of tributyltin (TBT) and alternative biocides were investigated in sediment from semi-enclosed bays, fishing ports, and large commercial harbors in Korea. Extremely high concentration of TBT (55,264ngSn/g) was detected near a large shipyard, even after a total ban on its use in Korea. Diuron was the biocide with the highest detection frequency and concentration levels, followed by Irgarol 1051. Sea-Nine 211 was detected at 3 of 32 stations surveyed. Dichlofluanid, zinc and copper pyrithiones levels were below the detection limits at all the stations surveyed. The relatively high levels of Diuron (9-62.3ng/g) and Irgarol 1051 (1.5-11.5ng/g) were detected in harbor and shipyard areas. Diuron and Irgarol 1051 levels including TBT in sediments from hot spots in Korea exceeded global sediment quality guidelines., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Superoxide dismutases (SODs) are important antioxidant enzymes whose expression levels are often used as biomarkers for oxidative stress. To investigate the biomarker potential of the monogonont rotifer Brachionus koreanus SOD genes, the full-length Cu/Zn-SOD (Bk-Cu/Zn-SOD) and Mn-SOD (Bk-Mn-SOD) genes were cloned from genomic DNA and characterized. All amino acid residues involved in the formation of tertiary structure and metal binding in Bk-Cu/Zn-SOD and Bk-Mn-SOD were highly conserved across species. Phylogenetic analysis revealed that Bk-Mn-SOD, in particular, was closely clustered with mitochondrial Mn-SOD. Transcript analysis after exposure to six different biocides (alachlor, chlorpyrifos, dimethoate, endosulfan, lindane, and molinate) revealed that the transcriptional level of Bk-Cu/Zn-SOD was significantly increased in a dose-dependent manner. In contrast, the level of Bk-Mn-SOD transcript was significantly increased compared with control cells in response to chlorpyrifos, endosulfan, and molinate at their no observed effect concentrations (NOECs). However, exposure to alachlor, chlorpyrifos, and molinate significantly reduced the enzymatic activity of total SOD protein, while a decreased pattern was observed in all biocide treatments. Taken together, these results indicate that exposure to waterborne environmental biocides induces the transcription of Bk-Cu/Zn-SOD and Bk-Mn-SOD, but inhibits the enzymatic activity of Bk-SODs. These results contribute to our understanding of the modes of action of oxidative stress-mediating biocides on rotifer., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

The intertidal copepod Tigriopus japonicus has been widely used in aquatic toxicity testing for diverse environmental pollutants including metals. Despite relatively well-characterized in vivo physiological modulations in response to aquatic pollutants, the molecular mechanisms due to toxicity and detoxification are still unclear. To better understand the mechanisms of metal transport and further detoxification, T. japonicus P-glycoprotein (TJ-P-gp) with conserved motifs/domains was cloned and measured for protein activity against the transcript and protein expression profiles in response to metal exposure. Specifically, we characterized the preliminary efflux activity and membrane topology of TJ-P-gp protein that supports a transport function for chemicals. To uncover whether the efflux activity of TJ-P-gp protein would be modulated by metal treatment, copepods were exposed to three metals (Cd, Cu, and Zn), and were observed for both dose- and time-dependency on the efflux activity of TJ-P-gp protein with or without 10μM of P-gp-specific inhibitors verapamil and zosuquidar (LY335979) for 24h over a wide range of metal concentrations. In particular, treatment with zosuquidar induced metal accumulation in the inner body of T. japonicus. In addition, three metals significantly induced the transporting activity of TJ-P-gp in a concentration-dependent manner in both transcript and protein levels within 24h. Together these data indicate that T. japonicus has a conserved P-gp-mediated metal defense system through the induction of transcriptional up-regulation of TJ-P-gp gene and TJ-P-gp protein activity. This finding provides further understanding of the molecular defense mechanisms involved in P-glycoprotein-mediated metal detoxification in copepods., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Temporal change in tributyltin (TBT) levels in Jinhae Bay, which has various TBT sources, was investigated in water, sediments, and oysters from 2003 to 2013 after its total ban in South Korea. The seawater TBT levels decreased over 500-fold from 1995/97 to 2008/09. The oyster TBT levels were about fourfold lower in 2012/13 than in 1995/97. However, the sediment TBT levels did not significantly change, even 10 years after the partial TBT ban on small ships and 7 years after the total TBT ban on all oceangoing vessels in Korea. The total ban of TBT use effectively reduced water and oyster TBT levels in Jinhae Bay, but TBT levels in water, oysters, and sediment remained above the global environmental quality standards established to protect marine organisms., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

In this study, selected spectroscopic characteristics of sediment organic matter (SOM) were compared and discussed with respect to their different isolation methods, the source discrimination capabilities, and the association with the extent of phenanthrene binding. A total of 16 sediments were collected from three categorized locations including a costal lake, industrial areas, and upper streams, each of which is likely influenced by the organic sources of algal production, industrial effluent, and terrestrial input, respectively. The spectroscopic properties related to aromatic structures and terrestrial humic acids were more pronounced for alkaline extractable organic matter (AEOM) isolates than for the SOM isolates based on water soluble extracts and pore water. The three categorized sampling locations were the most differentiated in the AEOM isolates, suggesting AEOM may be the most representative SOM isolates in terms of describing the chemical properties and the organic sources of SOM. Parallel factor analysis (PARAFAC) based on fluorescence excitation-emission matrix (EEM) showed that a combination of three fluorescent groups could represent all the fluorescence features of SOM. The three categorized sampling locations were well discriminated by the percent distributions of humic-like fluorescent groups of the AEOM isolates. The relative distribution of terrestrial humic-like fluorophores was well correlated with the extent of phenanthrene binding (r=0.571; p<0.05), suggesting that the presence of humic acids in SOM may contribute to the enhancement of binding with hydrophobic organic contaminants in sediments. Principal component analysis (PCA) further demonstrated that the extent of SOM's binding affinity might be affected by the degree of biogeochemical transformation in SOM., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

The distribution and bioaccumulation features of PCBs, DDTs, and HCHs were investigated in the sediments and Manila clams collected from along the Mid-Western coast of Korea. The measured concentrations of ΣPCBs, ΣDDTs and ΣHCHs were 1.08-3.5, 0.12-0.35 and 0.090-0.30 ng g(-1) dw in sediment, and 33-390, 7.4-46 and 6.3-27 ng g(-1) lipid in Manila clam, respectively. Their levels were found to be relatively lower than those of other contaminated areas and the consumption of Manila clam from these areas seems to be safe for human health according to calculated lifetime cancer risk and hazard indices. The ΣPCBs and ΣDDTs concentrations in sediments showed a significant relationship to those in clams. The significant correlation was observed between BSAF in clams and Kow for each PCB congeners and DDT metabolites. These findings support that the PCBs and DDTs levels, which are highly hydrophobic chemicals, in clam reflect the sediment pollution through bioaccumulation., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

The characteristics and sources of organic matter in water of the Lake Shihwa, which receives inputs from rural, urban, and industrial areas, were evaluated by examining the biodegradable organic carbon concentration, fluorescence spectra, and carbon and nitrogen isotope ratios, especially during rainy season and dry season. The organic matter transported from rural areas was of refractory nature, while that of industrial origin decomposed rapidly. As compared to the dry season, the organic matter in the rainy season was characterized by a reduced labile fraction. During the dry season, the autochthonous organic matter dominated in the lake, however, the contributions of allochthonous organic sources by industrial and rural areas significantly increased at rainy season. This investigation revealed that the transport of organic matter of anthropogenic origin to the Lake Shihwa was mainly influenced by heavy rainfall. Moreover, each anthropogenic source could differently influence the occurrence of organic matter in water of the Lake Shihwa., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

In this study, we investigated the effects of the water-accommodated fraction (WAF) of crude oil on the development and reproduction of the intertidal copepod Tigriopus japonicus through life-cycle experiments. Furthermore, we investigated the mechanisms underlying the toxic effects of WAF on this benthic organism by studying expression patterns of cytochrome P450 (CYP) genes. Development of T. japonicus was delayed and molting was interrupted in response to WAF exposure. Hatching rate was also significantly reduced in response to WAF exposure. Activities of antioxidant enzymes such as glutathione S-transferase (GST), glutathione reductase (GR), and catalase (CAT) were increased by WAF exposure in a concentration-dependent manner. These results indicated that WAF exposure resulted in oxidative stress, which in turn was associated with dysfunctional development and reproduction. To evaluate the involvement of cytochrome P450 (CYP) genes, we cloned the entire repertoire of CYP genes in T. japonicus (n=52) and found that the CYP genes belonged to five different clans (i.e., Clans 2, 3, 4, mitochondrial, and 20). We then examined expression patterns of these 52 CYP genes in response to WAF exposure. Three TJ-CYP genes (CYP3024A2, CYP3024A3, and CYP3027C2) belonging to CYP clan 3 were significantly induced by WAF exposure in a time- and concentration-dependent manner. We identified aryl hydrocarbon responsive elements (AhRE), xenobiotic responsive elements (XREs), and metal response elements (MRE) in the promoter regions of these three CYP genes, suggesting that these genes are involved in detoxification of toxicants. Overall, our results indicate that WAF can trigger oxidative stress and thus induce dysfunctional development and reproduction in the copepod T. japonicus. Furthermore, we identified three TJ-CYP genes that represent potential biomarkers of oil pollution., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Seawater samples from major enclosed bays, fishing ports, and harbors of Korea were analyzed to determine levels of tributyltin (TBT) and booster biocides, which are antifouling agents used as alternatives to TBT. TBT levels were in the range of not detected (nd) to 23.9 ng Sn/L. Diuron and Irgarol 1051, at concentration ranges of 35-1360 ng/L and nd to 14 ng/L, respectively, were the most common alternative biocides present in seawater, with the highest concentrations detected in fishing ports. Hot spots were identified where TBT levels exceeded environmental quality targets even 6 years after a total ban on its use in Korea. Diuron exceeded the UK environmental quality standard (EQS) value in 73% of the fishing port samples, 64% of the major bays, and 42% of the harbors. Irgarol 1051 levels were marginally below the Dutch and UK EQS values at all sites., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

To report a novel CYP genes and to evaluate its potency as a biomarker for oil pollution, we cloned three CYP genes and measured their expression profiles under controlled lab conditions using real-time reverse transcription PCR (real-time RT-PCR) after exposure of the water accommodated fraction (WAF) of Iranian crude oil and benzo[α]pyrene (B[α]P) as a positive control. Of these, CYP432A1 (CYP3 clan) gene was significantly induced by B[α]P exposure, indicating that the CYP3 clan gene would play an important role in polycyclic aromatic hydrocarbon (PAH) metabolisms, particularly for B[α]P in this species. However, the Perinereis nuntia CYP431A1 mRNA, a CYP2 clan gene, was sensitively expressed to WAF exposure with other two CYP genes. As one of Phase II detoxification enzymes, the glutathione S-transferase (GST) genes also upregulated with other antioxidant genes (SOD and CAT), indicating that WAF-exposed P. nuntia was properly responding to this kind of chemical stress. Thus, three CYP genes from the polychaete, P. nuntia have a potential as a biomarker in monitoring of the marine sediment after an oil spill accident., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

The polychaete, Perinereis nuntia, has been used as an indicator species to assess the environmental condition of benthic communities in coastal marine environments. Recently, high-throughput sequencing technology has been proven to be a useful method for analyzing expressed sequence tags (ESTs) in non-model species. Thus, we have obtained extensive cDNA information by the pyrosequencing method, to utilize the polychaete species as a test organism for sediment quality monitoring studies. From the total RNA of P. nuntia, cDNA was reversely synthesized and randomly sequenced using a GS-FLX sequencer. In the assembly stage 1, 40,379 transcripts (13,666 contigs and 26,713 singletons) were acquired and showed 47% hitting rate compared with the GenBank non-redundant (NR) amino acid sequence database using BLASTX. After the stage-2 assembly, 21,657 transcripts were identified and showed 28% hitting rate. Finally, we obtained 6 064 unigenes that corresponded to the GenBank NR amino acid sequence database using BLASTX. Of the transcripts obtained in this species, we found a number of stress- and cell defense-related genes (e.g. heat shock protein family, antioxidant-related genes, cytochrome P450 genes) that are potentially useful for sediment monitoring at the molecular level, indicating that the pyrosequencing method is an effective approach to uncover gene families of potential biomarker genes simultaneously, and thus make transcriptomic studies possible. To confirm the usefulness of those potential biomarker genes, we analyzed the comparative profiling of P. nuntia mRNA transcripts between the samples collected from the polychaete aquaculture farm and the southern coast field of South Korea. In this paper, we summarize the expressed cDNA information of P. nuntia and discussed its potential use in environmental genomics and ecotoxicological studies for uncovering the potential molecular mechanisms of environmental stresses and chemical toxicity to the indicator species, P. nuntia in marine sediments., (Copyright © 2011 Elsevier Inc. All rights reserved.)

An assessment was made to monitor the short-term impact of heavily polluted sediments that may move out from the brackish man-made Lake Shihwa outside of the sea dike due to operations of a tidal power plant. Here, we exposed the Manila clam Ruditapes philippinarum collected from the western coast of Korea to natural sediment under lab condition for 96 h. Sediments were collected from Lake Shihwa and outside of the sea dike representing polluted and reference conditions, respectively. The results of chemical analysis revealed that the concentrations of nonylphenol and heavy metals in water and sediment from the inner region of Lake Shihwa were significantly higher than those of reference sediments. After 48 and 96 h of exposure, 30 specimens of clams were sampled from each experimental condition, and concentrations of nonylphenol and metals were measured in clams, water, and sediments. Several biomarkers, including concentrations of metallothionein-like proteins, and activities of the antioxidant enzymes glutathione S-transferase and catalase were determined in clams to characterize the effects of polluted sediments to clams. After 96 h of exposure, R. philippinarum assimilated nonylphenol up to 71 times compared to initial concentrations. However, there was no apparent uptake of heavy metals into the clams. Additionally, antioxidant enzymes exhibited higher activities in clams exposed to the polluted sediment. The results of the present study with physiological responses in R. philippinarum suggest that sediment transportation caused by the operation of a tidal power plant in Lake Shihwa will have striking effects on benthic organisms in the adjacent coastal area.

Glutathione S-transferase (GST) is a phase II enzyme that functions as a detoxicant by catalyzing the conjugation of reduced glutathione with a variety of xenobiotics via cysteine thiol. Molecular genetic approaches using gene biomarkers show substantial relevance as sensitive biomarkers for the indication of pollution levels. In order to use GSTs as molecular biomarkers for marine pollution monitoring, we cloned and sequenced the full-length cDNA of seven GST genes from the marine polychaete Perinereis nuntia. The deduced amino acid sequence of Pn-GSTs showed a high similarity to those of other species that clustered into the same clades in a phylogenetic analysis. In addition, to evaluate Pn-GSTs as useful biomarkers on effects after cadmium (Cd) exposure, we exposed sublethal concentrations of Cd (5, 50, and 500 μg/L) to P. nuntia, and they showed relatively different but significantly increases, depending on exposure time and Cd concentrations. Particularly, Pn-GST-omega and Pn-GST-sigma genes were highly sensitive with a clear dose-dependent manner on mRNA expression. The total GST activities also have significantly increased levels at higher concentrations of Cd exposure. These results indicate that Pn-GSTs play important roles in Cd-induced oxidative stress in terms of the physiological changes relating to metabolism and cell protection, and those genes would have great potential as molecular biomarkers to monitor marine environmental health., (Copyright © 2011 Elsevier Inc. All rights reserved.)

To evaluate the superoxide dismutase (SOD) genes as a potential indicator of environmental stress, we cloned and sequenced the full-length cDNA of a Cu/Zn-SOD and Mn-SOD genes from the marine polychaete, Neanthes succinea. Ns-Cu/Zn- and Mn-SOD expression was measured using quantitative real-time RT-PCR in response to the oxidative stress induced by copper in the form of CuCl2. Ns-Cu/Zn-SOD expression increased in a dose dependent manner but the increase of Mn-SOD expression was evident only at a high concentration of copper. Particularly, Ns-Mn-SOD dramatically increased in the 72 μg/L CuCl2-exposed groups, indicating that both Ns-SOD genes were induced by copper exposure. These results suggest that Ns-Cu/Zn- and Ns-Mn-SOD would play important roles in the detoxification of cellular oxidative stresses in the polychaete, N. succinea. Furthermore, as part of field work, the marine polychaete, N. succineaCu/Zn-SOD mRNA collected from the polluted area was accordingly upregulated in expression but not for NS-Mn-SOD., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

Polychaetes are suitable organisms for evaluation of impact of sediment pollution. We evaluated toxicity of cadmium and copper and measured metallothionein-like proteins (MTLPs) in the polychaete Perinereis nuntia. At the same concentration ranges copper was unexpectedly more toxic than cadmium. Copper also caused no significant increase in MTLPs in the polychaetes. When P. nuntia and another polychaete species, Cirratulus cirratus were cultured in the contaminated sediments collected from Lake Sihwa (Korea), a high mortality of 80% was observed on day 6 in P. nuntia in the sediment with the highest metal concentration. However, no mortality was observed up to 35 days in C. cirratus in any sediment. MTLP contents between two species also varied. These findings suggest that MTLP induction response in the polychaetes varies with the metal type and species and it may be used as a biomarker of sediment pollution in the polychaetes after further validation and field trials.