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Microalgal bioassays were conducted to evaluate the ecotoxicological effects of suspended sediments (SS) collected from coastal environments. Growth inhibition was assessed for six microalgal species, and multiple endpoints were measured using flow cytometry (FCM) and pulse-amplitude modulation (PAM) fluorometry for three species (Dunaliella tertiolecta, Isochrysis galbana, and Phaeodactylum tricornutum). Among these, the EC50 for growth inhibition of D. tertiolecta (6700 mg L -1 ) was notably lower compared to the other species, and among several endpoints, esterase activity was the most inhibited. Species-specific responses to SS exposure were identified, with D. tertiolecta exhibiting greater susceptibility across most endpoints. Meanwhile, measurements of Fo', Fm', and Y(NPQ) in P. tricornutum using PAM fluorometry revealed greater sensitivity. Based on the results of this study and review, the tentative predicted no-effect concentration was calculated as 12.1 mg L -1 . Overall, this study provides novel insights into SS ecotoxicity, establishing a crucial baseline for future investigations., 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 The Authors. Published by Elsevier Ltd.. All rights reserved.)

This study investigated the large-scale distributions of persistent toxic substances (PTSs) and heavy metals in sediments of the Yellow Sea, collected from six transects between latitudes 32 and 37 degrees north (n = 35). Elevated concentrations of polychlorinated biphenyls (PCBs) were detected near the mainland, with a predominance of low-chlorinated congeners (di to tetra, ∼60%), indicative of atmospheric deposition. Analysis of traditional and emerging polycyclic aromatic hydrocarbons (t-PAHs and e-PAHs) revealed notable enrichment in the Central Yellow Sea Mud Zone (CYSM), attributing fossil fuel combustion as the significant source. Styrene oligomers and alkylphenols exhibited notable accumulation near the Han River Estuary in South Korea and the Yangtze River Estuary in China, respectively. The accumulation of heavy metals was predominantly observed in the CYSM, with element-specific distribution patterns. Cluster analysis revealed distinct distribution patterns for PTSs and metals, highlighting their source-dependent and grain size-dependent behaviors. In addition, the distribution and accumulation of PTSs tended to depend on their partitioning coefficients, such as the octanol-air partition coefficient (log K OA ) and octanol-water partition coefficient (log K OW ). This study offers valuable insights into the sources, transport, and fate of hazardous substances in the Yellow Sea, emphasizing the necessity for targeted environmental management strategies., 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 B.V. All rights reserved.)

The environmental DNA (eDNA) metabarcoding was applied to assess benthic ecological health in the west coast of South Korea by investigating a long-term microbial community change (2015-17). The ecological interaction among microorganisms, from phylum to family level, and their associations to environmental variables across the five regions were highlighted. As part of the study, the available chemistry and toxicological data in the regions during the monitoring periods were incorporated into an integrated sediment triad assessment. The bacterial communities were dominated by Proteobacteria (34.2%), Bacteroidetes (13.8%), and Firmicutes (10.8%). Proteobacteria and Bacteroidetes dominated consistently across regions and years, while Firmicutes and Cyanobacteria significantly varied by region and years (p < 0.05). The abundance of this phylum declined over time with the increasing abundance of Cyanobacteria, indicating their independent interactions to certain environmental changes. Planctomycetes and Gemmatimonadetes linked to some contaminants (ΣPAHs and Cu), implying indicator taxa. Overall, eDNA-based microbial community analysis combined with exposures of contaminants and responses of microorganisms is a promising strategy for the assessment of benthic ecological health in contaminated sediments from coastal waters., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

An enhanced, multiple lines of evidence approach was applied to assess potential toxicological effects associated with polluted sediments. Two in vitro bioassays (H4IIE- luc and Vibrio fischeri ) and three in vivo bioassays (microalgae: Isochrysis galbana and Phaeodactylum tricornutum ; zebrafish embryo: Danio rerio ) were applied. To identify causative chemicals in samples, targeted analyses (polycyclic aromatic hydrocarbons (PAHs), styrene oligomers (SOs), and alkylphenols) and nontargeted full-scan screening analyses (FSA; GC- and LC-QTOFMS) were performed. First, great AhR-mediated potencies were observed in midpolar and polar fractions of sediment extracts, but known and previously characterized AhR agonists, including PAHs and SOs could not fully explain the total potencies of samples. Enoxolone was identified as a novel AhR agonist in a highly potent sediment fraction by use of FSA. Enoxolone has a relative potency of 0.13 compared to benzo[ a ]pyrene (1.0) in the H4IIE- luc bioassay. Nonylphenols associated with membrane damage that influenced the viability of the microalgae were also observed. Finally, inhibitions of bioluminescence of V. fischeri and lethality of D. rerio embryos were strongly related to nonpolar compounds. Overall, the present work addressed assay- and end point-specific variations and sensitivities for potential toxicities of mixture samples, warranting a significant utility of the "multiple lines of evidence" approach in ecological risk assessment.

During the past few decades, contamination of sediments by persistent toxic substances (PTSs) has been observed in estuarine and coastal areas on the west coast of South Korea. The contaminants are suspected to cause toxicities in aquatic biota, but little is known about their ecological effects, particularly on benthic microbial communities. In this study, an eDNA-based assessment was applied along with classic assessments of exposure, such as chemistry and in vitro bioassays, to evaluate condition of benthic bacterial communities subjected to PTSs. Two strategies were adopted for the study. One was to conduct a comprehensive assessment in space (by comparing seawater and freshwater sites at five coastal regions) and in time (by following change over a 5-y period). Although we found that bacterial composition varied among and within years, some phyla, such as Proteobacteria (28.7%), Actinobacteria (13.1%), Firmicutes (12.7%), and Chloroflexi (12.5%) were consistently dominated across the study regions. Certain bacterial groups, such as Firmicutes and Verrucomicrobia have been linked to contamination at some sites in the study area and at specific points in time. Bacterial communities were not significantly correlated with salinity or AhR- and ER-mediated potencies, whereas concentrations of PAHs, APs, and certain metals (Cd and Hg) exhibited significant associations to the structure of bacterial communities at the phylum level. In fact, the relative abundance of microbes in the phylum Planctomycetes was significantly and negatively correlated with concentrations of PAHs and metals. Thus, the relative abundance of Planctomycetes could be used as an indicator of sedimentary contamination by PAHs and/or metals. Based on our correlation analyses, Cd and ER-mediated potencies were associated more with bacterial abundances at the class taxonomic level than were other PTSs and metals. Overall, the eDNA-based assessment was useful by augmenting more traditional measures of exposure and responses in a sediment triad approach and has potential as a more rapid screening tool., (Copyright © 2020 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Sedimentary organic matters in the typical intertidal areas were investigated to address year-round monthly distributions and site-specific sources. Target areas included four natural tidal flats (Ganghwa, Garolim, Sinan, and Suncheon) and one artificially closed estuary (Nakdong River), South Korea (in 2018). Among the parameters monitored, mud content was a key factor controlling organic matter contents, across varying habitats, with significant positive correlations to total organic carbon (TOC, r = 0.66, p < 0.001) and total nitrogen (TN, r = 0.44, p < 0.001). The elevated TOC and TN contents and heavier carbon stable isotope ratios (δ 13 C) in sediments of Garolim and Suncheon from February to April reflected the winter microphytobenthos blooms, receiving prevailed marine sources. Whilst, the depleted δ 13 C and δ 15 N values in sediments of Nakdong River estuary were observed during flood season (September-October), indicating direct influence of terrestrial organic input through freshwater discharge. Overall, distributions and sources of sedimentary organic matters in the Korean coastal waters suggested variabilities in season and space, with anthropogenic alteration. The data accumulated in this study would provide baseline information for sediment organic carbon stocks in the Korean coastal waters and elsewhere., (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.)

After the Gulf War Oil Spill, there have been many investigations about distributions of oil-derived pollutants nearby areas, but lacking in ecotoxicological assessment. We evaluated the potential toxicity of asphalt mats, sediments, and biota (polychaetes, chitons, snapping shrimps, and crabs) by combining two bioassays (H4IIE-luc and Vibrio fischeri) and in situ microbial community (eDNA). Samples were collected from Abu Ali Island, and organic extracts were bioassayed and further fractionated according to the chemical polarity using silica gel column. Great aryl hydrocarbon receptor (AhR)-mediated potencies and inhibition of bioluminescence were mainly found in aromatics (F2) and saturates (F1) fractions of asphalt mat and sediments, respectively, while great toxicological responses in biota samples were found in resins and polar (F3) fraction. We also confirmed that potential toxicities of biota were species-specific; great AhR-mediated potencies were found in polychaetes and great bioluminescence inhibitions were found in crabs. In microbial communities, most genera (up to 90%) were associated with polycyclic aromatic hydrocarbons (PAHs)-degrading bacteria, supporting that PAHs are the primary stressors of the benthic community around Abu Ali Island. The present study provides useful information on the contamination status, risk assessment of environmental matrices and benthic organisms in Abu Ali Island., (Copyright © 2019 Elsevier Inc. All rights reserved.)

North Abu Ali Island is contaminated by crude oil from exogenous sources with a variety of persistent toxic substances (PTSs) being input into intertidal sediments. We detected an array of PTSs in sediments and benthic biota off north Abu Ali Island (Arabian Gulf), including 35 polycyclic aromatic hydrocarbons (PAHs), 6 alkylphenols (APEOs), 10 styrene oligomers (SOs), and tributyltin. The PTS concentrations were generally greater than those reported in other areas of Arabian Gulf. PAHs mainly originated from petrogenic sources, and APEOs and SOs seem to be of recent origin. Field-based biota-sediment accumulation factors (BSAF) varied by taxa and compounds, but clearly depended on the log K ow values of individual compounds. Some PTSs exceeded the established guidelines for sediments and biota; we found particularly great BSAFs for alkyl-naphthalenes (C1- and C2-), nonylphenol monoethoxylates, and 2,4,6-triphenyl-1-hexene. Remediation will require on-site clean-up of toxic chemicals together with immediate efforts on preventing input of current pollution sources in the given area., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Oil spills offshore can cause long-term ecological effects on coastal marine ecosystems. Despite their important ecological roles in the cycling of energy and nutrients in food webs, effects on bacteria, protists or arthropods are often neglected. Environmental DNA (eDNA) metabarcoding was applied to characterize changes in the structure of micro- and macro-biota communities of surface sediments over a 7-year period since the occurrence of Hebei Spirit oil spill on December 7, 2007. Alterations in diversities and structures of micro- and macro-biota were observed in the contaminated area where concentrations of polycyclic aromatic hydrocarbons were greater. Successions of bacterial, protists and metazoan communities revealed long-term ecological effects of residual oil. Residual oil dominated the largest cluster of the community-environment association network. Presence of bacterial families (Aerococcaceae and Carnobacteriaceae) and the protozoan family (Platyophryidae) might have conferred sensitivity of communities to oil pollution. Hydrocarbon-degrading bacterial families (Anaerolinaceae, Desulfobacteraceae, Helicobacteraceae and Piscirickettsiaceae) and algal family (Araphid pennate) were resistant to adverse effects of spilt oil. The protistan family (Subulatomonas) and arthropod families (Folsomia, Sarcophagidae Opomyzoidea, and Anomura) appeared to be positively associated with residual oil pollution. eDNA metabarcoding can provide a powerful tool for assessing effects of anthropogenic pollution, such as oil spills on sediment communities and its long-term trends in coastal marine environments., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Complexity of anthropogenic influences on coastal ecosystems necessitates use of an integrated assessment strategy for effective interpretation and subsequent management. In this study a multiple lines of evidence (LOE) approach for sediment assessment, that combined use of chemistry, toxicity, and benthic community structure in the sediment quality triad was used to assess spatiotemporal changes and potential risks of persistent toxic substances (PTSs) in sediments of Masan Bay highlighting "long-term changes" between 1998 and 2014. Specific target objectives encompassed sedimentary PTSs (PAHs, alkylphenols (APs), and styrene oligomers), potential aryl hydrocarbon receptor (AhR; H4IIE-luc assay)- and estrogen receptor (ER; MVLN assay)-mediated activities, and finally several ecological quality (EcoQ) indices of benthic community structure. Concentrations of target PTSs in Masan Bay sediments were generally less by half in 2014 compared to those measured in 1998. Second, AhR-mediated potencies in sediments also decreased during this time interval, whereas ER-mediated potencies increased (+3790%), indicating that there has been substantial ongoing, input of ER agonists over the past 16 years. Potency balance analysis revealed that only 3% and 22% of the AhR- and ER-mediated potencies could be explained by identified known chemicals, such as PAHs and APs, respectively. This result indicated that non-targeted AhR and ER agonists had a considerable presence in the sediments over time. Third, EcoQ indices tended to reflect PTSs contamination in the region. Finally, ratio-to-mean values obtained from the aforementioned three LOEs indicated that quality of sediments from the outer region of the bay had recovery more during the period of 16-years than did the inner region. Overall, the results showed that even with the progress supported by recent efforts from the Korean governmental pollution control, PTSs remain a threat to local ecosystem, especially in the inner region of Masan Bay., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

In the late 1990s, severe pollution by persistent organic contaminants (POCs) was observed in Lake Sihwa by use of a combination of instrumental analyses and in vitro bioassays. To determine long-term changes (>15-year gaps) in distributions of POCs and their potential toxic potencies in the given region, sediment assessments were reconducted. Target chemicals include polycyclic aromatic hydrocarbons (PAHs), alkylphenols (APs), and recently reported emerging chemicals, styrene oligomers (SOs). We employed in vitro bioassays (such as H4IIE-luc and MVLN) to determine potential sediment toxicities. The reduction rates of mean concentrations of APs and SOs in sediments between the two sampling years (1998 vs. 2015) were estimated to be 99% and 67%, respectively. Although APs and SOs significantly declined over the 15-year period, concentrations of PAHs were consistent. Results of the bioassays were consistent with the instrumental data, with relatively great concentrations of all target compounds being detected, particularly in inland creeks. Compositions of all target compounds exhibited changes in homologue patterns over the 15 years considered. This result indicated varying and/or continuing sources in this region. In particular, PAHs were dominated by higher-molecular-weight PAHs (e.g., benzo[g,h,i]perylene and benzo[b]fluoranthene) in recent years. This result might indicate consumption of oil-related fuels. Quantitative potency balance analysis revealed that concentrations of instrumentally-derived equivalents accounted for as little as 18.5% of bioassay-derived equivalents, which indicated significant amounts of unknown and/or unmeasured compounds were present. The present study documented the continuing severe pollution by selected POCs in the Lake Sihwa region over the last 15 years, indicating a lack of management in the area studied., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Benthic communities in the aquatic ecosystem are influenced by both natural and anthropogenic stressors. To understand the ecogenomic responses of sediment communities to the multiple stressors of polluted environments, the bacteria, protistan and metazoan communities in sediments from marine and adjacent riverine areas of North Bohai Sea were characterized by environmental DNA meta-systematics, and their associations with environmental variables were assessed by multiple statistical approaches. The bacterial communities were dominated by Firmicutes (mean 22.4%), Proteobacteria (mean 21.6%) and Actinobacteria (mean 21.5%). The protistan communities were dominated by Ochrophyta (33.7%), Cercozoa (18.9%) and Ciliophora (17.9%). Arthropoda (71.1%) dominated the metazoan communities in sediments. The structures of communities in sediments were shaped by both natural variables (spatial variability and/or salinity (presented as Na and Ca)) and anthropogenic contaminants, including DDTs, PAHs or metals (Cu, Al, Co, Cr, Cu, Fe, K, Mg, Mn, Ni and Zn). Particularly, the correlation network of multiple communities was modulated by the concentrations of Na and DDTs at the family level. Overall, environmental DNA meta-systematics can provide a powerful tool for biomonitoring, sediment quality assessment, and key stressors identification., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Over the last 30 years, the Geum River Estuary and Saemangeum Coast have been subject to major environmental changes, including dike construction, reclamation, and development of industrial complexes. This study aimed to: 1) investigate the occurrence of polycyclic aromatic hydrocarbons (PAHs), alkylphenols (APs), and styrene oligomers (SOs), 2) identify the sources of sedimentary organic matter, and 3) determine key environmental factors controlling the macrozoobenthos community structure. A total of 58 surface sediments were collected from the estuary and coastal area in 2014. Specific persistent organic contaminants (POCs), including 24 PAHs, 6 APs, and 10 SOs were measured. PAHs, APs, and SOs were detected in the sediments at all sites, with concentrations varying among sites. Although POCs concentrations were generally below the Canadian sediment quality guidelines, relatively greater concentrations of POCs were found at some sites adjacent to industrial complexes and the estuarine area. Sediment organic carbon, total nitrogen, and the stable carbon isotope ratio (δ 13 C) were determined. Some sites near watergate had about 2-3‰ lighter δ 13 C values compared to other areas, indicating that these sites are affected by terrestrial organic matter. The number of species in the macrofaunal community was significantly correlated with δ 13 C values (p < 0.001), positively, suggesting that the origin of sedimentary organic matter is important for controlling the macrozoobenthos distribution. Overall, this research provides information about the level and sources of sediment pollution, the origins of organic matter, and the relationships with the macrofaunal community., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Oil spills near the coastlines may damage marine and intertidal ecosystem. Constituents of the oil have been reported to cause toxic consequences mediated by aryl hydrocarbon receptor (AhR), and estrogen receptor (ER). In the present study, AhR- and ER-mediated toxicities of coastal sediments of Taean were investigated seven years after Hebei Spirit oil spill (HSOS). Sediment samples were collected on June and October 2014 from seven locations along the Taean coastline, where signs of oil spill were detected. Sediment samples were extracted in Soxhlet extractors and further processed through activated silica gels to separate into four fractions; F1 (saturate hydrocarbons), F2 (aromatic hydrocarbons), F3 (resins and polar compounds), and F4 (residues). ER-mediated and AhR-mediated potencies (% E2 max and % TCDD max ) of each fraction were determined using MVLN cells and H4IIE-luc cells, respectively. F2 and F3 fractions of Sinduri 1, Sinduri 2, and Sogeunri 1 samples showed greater AhR-mediated potencies (up to 107% TCDD max ). Chemical analysis revealed that PAH components are correlated with AhR-binding activities. The % E2 max results varied by sample: While there was no noticeable induction of ER-dependent responses (<45%), some aromatics fractions (F2) exhibited the highest ER-mediated responses. Compared with previous reports from the same sites, both AhR-mediated and ER-mediated potencies have decreased over time. Nevertheless, AhR-mediated potencies could be identified in the environmental samples even after 7 years of the incident. Therefore, possible ecosystem implications of these findings should be further investigated., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Rapid economic growth during the past two decades in the region surrounding the Bohai and Yellow Seas has resulted in severe pollution. Large amounts of monitoring data on persistent organic pollutants (POPs) in various environmental media have been accumulated, which allows us to conduct a fairly comprehensive assessment of the region around the Bohai and Yellow Seas to elucidate spatial patterns of pollution on a regional scale. This review summarized distributions of traditional and new POPs, including organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs), and perfluoroalkyl substances (PFASs), in various environmental media. In general, due to their physico-chemical properties (poor solubility in water), OCPs and PCBs were mainly detected in sediments, PBDEs and HBCDs were mainly detected in sediments and soils. PFASs, which have greater solubility, were mainly detected in the hydrosphere. For conventional POPs, such as OCPs and PCBs, Bohai Bay and Haihe River in China, Gyeonggi Bay and Lake Sihwa in South Korea were found to be most polluted areas. While for new POPs, such as PBDEs, HBCDs and PFASs, some areas were heavily polluted due to local production and applications. Estuarine and coastal areas of the Bohai Sea were more severely contaminated by POPs than coastal regions of the Yellow Sea. Overall, the present review will guide identification of key areas for strengthening risk assessment of POPs and management practices., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Oil is a complex mixture of numerous compounds. Therefore, oil spills near shore can cause various adverse effects on coastal ecosystems. However, most toxicological assessments conducted on oil spill sites have focused on limited modes of toxic actions. In the present study, we utilized the Escherichia coli (E. coli) live cell array system (LCA) to identify novel modes of toxicities of the oil spill-affected sediments. For this purpose, sediment samples were collected from an area heavily polluted by Hebei Spirit oil spill (HSOS) incident of 2007. A total of 93 E. coli reporter genes were used to study responses to the chemicals in the mixture. E. coli K12 strains were exposed to extracts of oil or the sediment, and changes in gene expression were measured. Exposure to extracts of crude and weathered oil resulted in decreased expression in ∼30% of tested genes. However, changes in expression observed after exposure to sediment extracts varied. Sediment extracts containing large concentrations of polycyclic aromatic hydrocarbons (PAH) caused down-regulation of >70% of the genes, while extracts containing lesser total concentrations of PAHs exhibited different trends: genes involved in drug resistance were generally up-regulated, while genes responsive to DNA damage were up-regulated in only two extracts. Results suggest that oil pollution can modulate several toxic response pathways related to DNA repair and antibiotic responses. Results from LCA obtained from the sediment and oil samples were different from those observed in the H4IIE-luc assay. Toxicological implications of such observations deserve further examination. Overall, LCA is a promising tool for screening samples and identifying potential modes of toxicities of environmental samples associated with oil spills., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The west coast of Korea has experienced environmental deterioration for more than half a century. In the present study, we specifically aimed to: i) evaluate potential toxicities of contaminants in sediments that cause effects mediated through the aryl hydrocarbon receptor (AhR) and estrogen receptor (ER); ii) determine spatio-temporal distributions of polycyclic aromatic hydrocarbons (PAHs) and alkylphenols (APs); and iii) identify causes of greater potencies of samples. From 2010 to 2014, sediments were collected from 12 major estuarine and coastal regions along the west coast of South Korea. In vitro cell bioassays were performed to determine AhR- and ER-mediated potencies using H4IIE-luc and MVLN cells, respectively. Fifteen PAHs and six APs in sediments were identified by GC/MSD. Results of bioassays generally showed a low-to-moderate degree of contamination, however, greater AhR- and ER-mediated potencies were measured at some locations. Concentrations of PAHs and APs varied among locations, which indicated that sources were independently affected by the surrounding environment (e.g., industrial complex and cities). Results of bioassays were generally well correlated with concentrations of putative causative chemicals. Benzo[k]fluoranthene, dibenz[a,h]anthracene, and benzo[b]fluoranthene were the major AhR agonists, explaining approximately 30% of the bioassay-derived benzo[a]pyrene equivalent concentration (BaP-EQ). Unknown AhR and ER agonists and potential mixture effects remain in question. Overall, the present study provides baseline information on chemical contaminations and potential toxicity of sediments in a fairly wide geographical region of the west coast of South Korea., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Effect-directed analysis (EDA) was performed to identify the major aryl hydrocarbon receptor (AhR) agonists in sediments collected from a highly industrialized area (Lake Shihwa, Korea). Great AhR-mediated potencies were found in fractions containing aromatic compounds with log Kow values of 5-8, and relatively great concentrations of styrene oligomers (SOs) and polycyclic aromatic hydrocarbons (PAHs) were detected in those fractions. Until now, there was little information on occurrences and toxic relative potencies (RePs) of SOs in coastal environments. In the present study; i) distributions and compositions, ii) AhR binding affinities, and iii) contributions of SOs to total AhR-mediated potencies were determined in coastal sediments. Elevated concentrations of 10 SOs were detected in sediments of inland creeks ranging from 61 to 740 ng g(-1) dry mass (dm), while lesser concentrations were found in inner (mean = 33 ng g(-1) dm) and outer regions (mean = 25 ng g(-1) dm) of the lake. Concentrations of PAHs in sediments were comparable to those of SOs. 2,4-diphenyl-1-butene (SD3) was the predominant SO analogue in sediments. SOs and PAHs were accumulated in sediments near sources, and could not be transported to remote regions due to their hydrophobicity. RePs of 3 SOs could be derived, which were 1000- to 10,000-fold less than that of one representative potent AhR active PAH, benzo[a]pyrene. Although concentrations of SOs in sediments were comparable to those of PAHs, the collective contribution of SOs to total AhR-mediated potencies were rather small (<1%), primarily due to their smaller RePs. Overall, the present study provides information on distributions and AhR binding affinities for SOs as baseline data for degradation products of polystyrene plastic in the coastal environment., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Bioaccessibility of toxic substances in sedimentary residual oil is a crucial factor that needs to be considered for accurate risk assessments posed by oil spills. However, information on oil weathering processes and bioaccessibility of residual oil is often not sufficient and clear. In the present study, bioaccessibility of aryl hydrocarbon receptor (AhR)-active polycyclic aromatic hydrocarbons (PAHs) in coastal sediments near the site of the Hebei Spirit oil spill (Korea, 2007) was assessed by Tenax extraction in effect-directed analysis (EDA). Sediment samples collected 6 years after the oil spill were extracted using Soxhlet or Tenax, and EDA was performed using a battery of H4IIE-luc bioassay and GC/MSD analysis. Concentrations of PAHs and alkyl-PAHs in Soxhlet extracts ranged from 210 to 53,000 μg kg(-1) dry mass. However, concentrations of PAHs and alkyl-PAHs in Tenax extracts were approximately 20-fold less compared to those in Soxhlet extracts. In Soxhlet and Tenax extracts, the major AhR-active PAHs were identified as C1-chrysene, C3-chrysene, and C4-phenanthrene. Concentrations of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) equivalents (TEQ(PAHs)) explained 31% and 60% of the bioassay-derived TCDD-EQ concentrations in Soxhlet and Tenax extracts, respectively. Overall, bioaccessibility of PAHs and alkyl-PAHs in sedimentary residual oils depended on hydrophobicity (log K(ow)) and degree of weathering of crude oil. The results of the present study provide further evidence in support of the biological and ecological recoveries of oil spill sites., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

We examined the degree of DNA damage caused by three fractions (F1, aliphatic hydrocarbons; F2, aromatic hydrocarbons; and F3, polar compounds) of the organic extract of sediments taken from Taean, Korea, following the Hebei Spirit oil spill. DNA damage was measured using the comet assay with blood cells of the striped beakfish (Oplegnathus fasciatus). DNA damage was also examined for fractions of crude oil (Iranian Heavy Crude Oil, IHC), weathered oil and six subfractions (F2.1-F2.6). The greatest DNA damage was found from the Sinduri dune region and DNA damage decreased to 40% weathered oil in F2 fraction compared with crude oil. The DNA damage of the sum of fractions was found higher than the organic extracts of sediments, suggesting antagonistic interactions between the genotoxic compounds. This study confirmed the persistence of potential genotoxicity in sediments of the severely affected regions as long as 5 years after the oil spill., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

The major AhR-active PAHs were identified in crude oil and oil-contaminated sediments by use of effect-directed analysis. As part of the study, an enhanced potency balance analysis was conducted by establishing the novel relative potency values of (alkyl)-PAHs from the H4IIE-luc bioassay. Silica gel column fractionation of crude oil resulted in greater AhR-mediated potencies in fractions of aromatics (F2) and resins (F3), and such trend was also observed for field collected sediment samples. AhR-mediated potencies of six F2 sub-fractions from HPLC indicated that the majority of F2 responses were attributable to 3-4 ring aromatics. Target PAHs including C4-phenanthrene, C1-chrysene, and C3-chrysene in sediments explained ∼ 18% of the bioassay-derived TCDD-EQs, however, the unknown AhR agonists and potential mixture effects remain in question. Overall, the AhR-potency and antagonistic potential of residual oil in sediment tended to decrease over time, thus monitoring of weathering process would be key for the post management of oil-contaminated sites., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Naphthenic acids (NAs) as toxic components in most petroleum sources are suspected to be one of the major pollutants in the aquatic environment following oil spills, and the polarity and persistence of NAs make it a potential indicator for oil contamination. However, the contamination and potential effects of pollutants in oil spill affected areas remain unknown. To investigate NAs in oil spill affected areas, a sensitive method was first established for analysis of NAs, together with oxy-NAs in sediment samples by UPLC-QTOF-MS. Then the method was applied to determine the NA mixtures in crude oil, weathered oil, and sediments from the spilled sites after the Hebei Spirit oil spill, Taean, South Korea (Dec. 2007). Concentrations of NAs, O3-NAs, and O4-NAs were found to be 7.8-130, 3.6-44, and 0.8-20 mg kg(-1) dw in sediments from the Taean area, respectively, which were much greater than those measured in the reference sites of Manlipo and Anmyundo beaches. Concentrations of NAs were 50-100 times greater than those (0.077-2.5 mg kg(-1) dw) of PAHs in the same sediment samples, thus the ecological risk of NAs in oil spill affected areas deserves more attention. The sedimentary profiles of oil-derived NAs and background NAs centered around compounds with 21-35 and 12-21 carbons, respectively, indicating that the crude-derived NA mixtures originating from the 2007 oil spill were persistent. Acyclic NAsn=5-20 were easily degraded compared to cyclic NAsn=21-41 during the oil weathering processes, and the ratio of oxy-NAsn=21-41 relative to NAsn=21-41 could be a novel index to estimate the degree of oil weathering in sediments. Altogether, the persistent oil-derived NAsn=21-41 could be used as a potential indicator for oil-specific contamination, as such compounds would not be much affected by the properties of coastal sediments possibly due to the high sorption of the negatively charged compounds (NAs) in sediment.

The influence of industrial and/or municipal contaminant inputs on the aquatic environment of Pohang, Korea was investigated, with a focus on bioassay combined with instrumental analysis. Pohang is the most heavily populated city in Gyeongsangbuk-do province of Korea, with more than half a million residents, and also hosts the nation's biggest steel manufacturer and related industries. Sediment (n=15) and surface water samples (n=17) were collected from Hyeongsan River which runs across the Pohang city, in two separate events, i.e., June 2010 and February 2011. Sediment samples were first Soxhlet-extracted (raw extract) and were measured for estrogenicity using H295R cell line, and also analyzed for alkylphenols (APs), bisphenol A (BPA), PAHs, and PCBs. For sediment samples which exhibited greatest effects in the cell line, further fractionation was performed into non-polar, mid-polar, and polar portions. In surface water samples, heavy metals were also analyzed. Among 15 sediment samples, station S2 near the steel industry complex and station M3 near the municipal area showed the greatest sex hormone changes, and these changes were generally explained by the fractions which contained APs and BPA. Principal component analysis (PCA) however suggests that chemicals that were not analyzed in the present study would better explain endocrine disruption capacity of sediments. In water samples, adverse effects on hatchability and growth of Japanese medaka fish, and on Daphnia reproduction were noted following exposure to six water samples collected from stations near industrial and municipal areas. Several heavy metals and nonylphenol (NP) concentrations exceeded surface water quality guidelines, suggesting adverse effects of contamination inputs from both industrial and municipal activities. Observed estrogenicities in stations such as S2 and M3 warrant further investigations on longer term ecosystem impacts near industrial and municipal areas. The levels of major organic chemicals in sediments are quite comparable to those reported in ~10 years ago, emphasizing a need for source control., (© 2013 Elsevier B.V. All rights reserved.)

Pohang is a mid-sized city in which Korea's largest manufacturer of steel is located. The Hyeongsan River, which runs through Pohang and empties into Yeongil Bay, is therefore expected to be affected by various municipal and industrial inputs. In order to characterize aryl hydrocarbon receptor (AhR)-mediated activities in sediments from the Pohang area, a total of eight locations along the Hyeongsan River were chosen and 16 sediment samples were collected during two sampling campaigns in 2010. Organic extracts of sediments were characterized by both quantitative chemical analyses of dioxin-like chemicals and the in vitro H4IIE-luc bioassay. Significant dioxin-like activities were observed in sediments from industrial and municipal areas, which indicates that most of the dioxin-like chemicals were associated with surrounding anthropogenic sources. In general, responses of the H4IIE-luc assay were significantly correlated with concentrations of target compounds including dioxins, furans, co-planar PCBs, and dioxin-like PAHs. A potency balance analysis indicated that instrumentally derived TCDD equivalents (TEQs) explained about 77% of the bioassay-derived TCDD equivalents (TCDD-EQs). Among the target chemicals measured, certain penta-chlorinated dioxin and furan compounds accounted for the majority of dioxin-like activities associated with sediments. Compositional analysis of target chemicals the sources of such dioxin-like activities were mainly derived from the local activities such as the iron and steel industries. Concentrations and activities of AhR agonists were similar to what was measured approximately 10 years ago. Thus, while AhR agonists seem to be persistent in sediments there seem to have been no large increases in these chemicals in the Pohang area., (© 2013. Published by Elsevier B.V. All rights reserved.)

Here we summarize and review the previous efforts on sediment assessment together with major scientific findings that were conducted in the Korean coastal waters since late 1990s. Towards integrated triad analysis, sediment data (>1700 samples) reported from the Korean coasts were collected and reviewed of which data collectively includes three components of chemical, toxicological, and ecological measures. First, the chemistry data suggested widespread and historic distribution of sedimentary pollutants along the Korean coasts. Spatial distributions suggested that their sources were independent of each other, while some localized areas (highlighted for Lake Shihwa, Masan Bay, and Ulsan Bay) and zones with extremely high pressures of certain pollutants were also identified. The mass balance analyses and/or direct correlations linking triad components reflected a general agreement between endpoints. The benthic community responses given by species occurrence and diversity also reflected the type and degree of sediment contamination, however, could not be fully explained by the known target chemicals. Overall, the triad assessment of trace pollutants in Korean coastal sediments seemed to be useful and much powerful when all the components are fully addressed., (© 2013. Published by Elsevier B.V. All rights reserved.)

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.

The Hebei Spirit oil spill episode (December 7, 2007) has affected the western coastal area of South Korea; however, there is limited information on the potential toxicity of the oil spill to the ecosystem or humans. The potential toxicity of sediments collected from the affected area (n = 22) 2 years after the spill was evaluated. Acute lethal toxicity tests using Vibrio fischeri and Moina macrocopa and tests for genotoxicity and alteration of steroidogenesis using chicken DT40 cells and H295R cells, respectively, were conducted. Both crude and weathered oil extracts were evaluated in order to link the observed toxicity in the sediment extracts to the oil spill. Whereas toxicity to bacteria and daphnids was observed in only two elutriate samples, 10 of the 22 sediment extracts showed genotoxic potential in DT40 cells. The mechanisms of genotoxicity involved nucleotide excision repair (XPA(-/)), homologous recombination (RAD54(-/-)), and translesion synthesis pathways (REV3(-/-)). In addition, nine sediment extracts caused significantly greater production of E2 in H295R cells, and significant up-regulation of CYP19, CYP11B2, and 3βHSD2 by sediment extracts was observed. The pattern of toxicities observed in both crude and weathered oil samples was similar to that observed in the sediment extracts. The genotoxicicity and endocrine-disruption potential of the sediment extracts suggest a need for long-term followup for such toxicity in humans and wildlife in this area.

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.