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This is the first report to evaluate the potential effects of microplastics (MPs) on wild wharf roaches (Ligia exotica) in a shoreline habitant. L. exotica is an important plastic detritus consumer in coastal area. A survey was conducted from May to June in the years 2019 and 2020 in two South Korean nearshore sites: Nae-do (as MPs-uncontaminated) and Maemul-do (as MPs-contaminated). MPs (>20 μm in size) were detected highly in gastrointestinal tracts of the L. exotica from Maemul-do, at an average level of 50.56 particles/individual. They were detected in much lower levels in the L. exotica from Nae-do. at an average rate of 1.00 particles/individual. The polymer type and shape were dominated by expanded polystyrene (EPS, 93%) and fragment (99.9%) in L. exotica from Maemul-do. Especially, Hexabromocyclododecanes, brominated flame retardants added to EPS, have been detected highly in L. exotica from Maemul-do (630.86 ± 587.21 ng/g l. w.) than those of Nae-do (detection limit: 10.5 ng/g l. w). Genome-wide transcriptome profiling revealed altered expression of genes associated with fatty acid metabolic processes, the innate-immune response-activating system and vesicle cytoskeletal trafficking in L. exotica from Maemul-do. The activation of the p53 signaling pathway (which is related to proteasome, ER regulation and cell morphogenesis) is likely to be involved in the EPS-uptake of wild L. exotica. Four neurosteroids were also detected in head tissue, and cortisol and progesterone concentrations differed significantly in L. exotica from Maemul-do. Our findings also suggest that resident plastic detritus consumer might be a useful indicator organism for evaluating pollution and potential effects of environmental microplastics., 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 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Expanded polystyrene (EPS) is a major component of marine debris globally. Recently, hazardous hexabromocyclododecanes (HBCDDs) were detected in EPS buoys used for aquaculture farming. Subsequently, enrichment of HBCDDs was found in nearby marine sediments and mussels growing on EPS buoys. It was suspected that EPS buoys and their debris might be sources of HBCDDs. To confirm this, the release of HBCDDs from EPS spherules detached from a buoy to seawater was investigated under field (open sea surface and closed outdoor chambers with sun exposure and in the dark) and laboratory (particle-size) conditions. In all exposure groups, initial rapid leaching of HBCDDs was followed by slow desorption over time. Abundant release of HBCDDs was observed from EPS spherules exposed to the open sea surface (natural) and on exposure to sunlight irradiation or in the dark in controlled saline water. Water leaching and UV-light/temperature along with possibly biodegradation were responsible for about 37% and 12% of HBCDDs flux, respectively. Crumbled EPS particles (≤1 mm) in samples deployed on the sea surface for 6 months showed a high degree of weathering. This implies that surface erosion and further fragmentation of EPS via environmental weathering could enhance the leaching of HBCDDs from the surface of EPS. Overall, in the marine environment, HBCDDs could be released to a great extent from EPS products and their debris due to the cumulative effects of the movement of large volumes of water (dilution), biodegradation, UV-light/temperature, wave action (shaking), salinity and further fragmentation of EPS spherules., (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.)

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.)

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.)

Polycyclic aromatic hydrocarbons (PAHs) and their alkylated forms are important components of crude oil. Both groups of PAHs have been reported to cause dioxin-like responses, mediated by aryl hydrocarbon receptor (AhR). Thus, characterization of binding affinity to the AhR of unsubstituted or alkylated PAHs is important to understand the toxicological consequences of oil contamination on ecosystems. We investigated the potencies of major PAHs of crude oil, e.g., chrysene, phenanthrene and dibenzothiophene, and their alkylated forms (n=17) to upregulate expression of AhR-mediated processes by use of the H4IIE-luc transactivation bioassay. In addition, molecular descriptors of different AhR activation potencies among PAHs were investigated by use of computational molecular docking models. Based on responses of the H4IIE-luc in vitro assay, it was shown that potencies of PAHs were determined by alkylation in addition to the number and conformation of rings. Potencies of AhR-mediated processes were generally greater when a chrysene group was substituted, especially in 1-methyl-chrysene. Significant negative correlations were observed between the in vitro dioxin-like potency measured in H4IIE-luc cells and the binding distance estimated from the in silico modeling. The difference in relative potency for AhR activation observed among PAHs and their alkylated forms could be explained by differences among binding distances in the ligand binding domain of the AhR caused by alkylation. The docking model developed in the present study may have utility in predicting risks of environmental contaminants of which toxicities are mediated by AhR binding., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Polystyrene (PS) is made flame retardant by combining with hexabromocyclododecane (HBCD). HBCD can release from consumer products during their production, use or disposal. As a result, it has become a ubiquitous contaminant in the environment with a high potential for bioaccumulation. Therefore, to evaluate the extent of exposure to HBCD from PS, we determined the concentration of HBCD in a variety of products (n=34) made from three types of commonly used PS: expanded PS (EPS), extruded PS foam (XPS), and extruded PS. The concentration of HBCD was highest in EPS, with a mean value and range of 475643±16710ngg(-1) and 106-960000ngg(-1), respectively. PS related to building construction and laboratory uses had a significantly higher concentration of HBCD (3300-905000ngg(-1)), except XPS styroboard (191±100ngg(-1)). Lower concentrations were measured in most food-related products (24.3-199ngg(-1)). However, a relatively high concentration of HBCD was detected in an ice box (960000±29000ngg(-1)), aquaculture buoy (53500±2100ngg(-1)), and disposable tray (8430±730ngg(-1)) used in fish market, raising concern for public health. Our data demonstrate a wide variation in the concentration of HBCD, suggesting a lack of proper controls for the addition of HBCD to PS products. Other brominated flame retardants (BFRs) were also detected in a majority of the XPS products (TBBPA=3.83-545ngg(-1), BTBPE=44-216ngg(-1) and DBDPE=215-4200ngg(-1)). Thus, HBCD is being added to PS along with other BFRs that cannot be ignored., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

We determined the toxicity of the water accommodated hydrocarbon fraction (WAF), two chemically enhanced WAFs (CEWAFs; CEWAF-C, Crude oil+Corexit 9500 and CEWAF-H, Crude oil+Hiclean) of crude oil and two dispersants (Corexit 9500 and Hiclean) to the rock pool copepod Tigriopus japonicus. In the acute toxicity test, Corexit 9500 was the most toxic of all the chemicals studied. The nauplius stage of T. japonicus was more susceptible to the toxic chemicals studied than the adult female. The toxicity data using the nauplius stage was then considered as baseline to determine the spiking concentration of chemicals for chronic toxicity tests on the copepod. As the endpoints in the chronic toxicity test, survival, sex ratio, developmental time and fecundity of the copepod were used. All chemicals used in this study resulted in increased toxicity in the F1 generation. The lowest-observed-adverse-effect (LOAE) concentrations of WAF, CEWAF-H, CEWAF-C, Hiclean and Corexit 9500 were observed to be 50%, 10%, 0.1%, 1% and 1%, respectively. The results in present study imply that copepods in marine may be negatively influenced by spilled oil and dispersant., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Crude oils from different geological formations vary in composition, yet most crude oils contain a polycyclic aromatic hydrocarbon (PAH) fraction that would be expected to produce cardiotoxic effects in developing fish. To determine whether different crude oils or PAH compositions produce common or distinct effects, we used zebrafish embryos to directly compare two crude oils at different states of weathering. Iranian heavy crude oil (IHCO) spilled in the Yellow Sea following the 2007 Hebei Spirit accident was compared to the intensively studied Alaska North Slope crude oil (ANSCO) using two different exposure methods, water-accommodated fractions containing dispersed oil microdroplets and oiled gravel effluent. Overall, both crude oils produced a largely overlapping suite of defects, marked by the well-known effects of PAH exposure on cardiac function. Specific cardiotoxicity phenotypes were nearly identical between the two oils, including impacts on ventricular contractility and looping of the cardiac chambers. However, with increased weathering, tissue-specific patterns of aryl hydrocarbon receptor (AHR) activation in the heart changed, with myocardial AHR activation evident when alkyl-PAHs dominated the mixture. Our findings suggest that mechanisms of cardiotoxicity may shift from a predominantly AHR-independent mode during early weathering to a multiple pathway or synergistic mode with prolonged weathering and increased proportions of dissolved alkyl-PAHs. Despite continued need for comparisons of crude oils from different sources, the results here indicate that the body of knowledge already acquired from studies of ANSCO is directly relevant to understanding the impacts of other crude oil spills on the early life history stages of fish., (Published by Elsevier Ltd.)

Chemical contamination of the coastal marine environment by polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) was assessed along with emerging contaminants such as polybrominated diphenyl ethers (PBDEs) in an industrially well-developed country (France) and a fast-developing country (Korea). Other chemicals, i.e. nonylphenol (NP) and 5 beta(H)-cholestan-3beta-ol (coprostanol) were determined to trace industrial waste and/or domestic inputs. These compounds were analyzed in coastal sediments and mussels in two enclosed coastal water bodies: Masan Bay (South Korea) and Thau lagoon (France). The overall levels of target organic contaminants were higher in Masan Bay than in Thau lagoon. The mean concentrations of 17 PCDD/Fs, 13 PBDEs, NP and coprostanol in Masan Bay sediments were, respectively, 1.3, 11, 248 and 291 ng g(-1) dry weight (d.w.); in Thau lagoon sediments they were, respectively, 0.39, not detectable (nd), 23 and 395 ng g(-1)d.w. Mean concentrations in mussels (coprostanol and cholestanol were not measured) were 0.0093, 13, 140 ng g(-1)d.w. in Masan Bay and 0.016, 0.94, 38 ng g(-1)d.w. in Thau lagoon. Principal component analysis of the contaminants and chemical tracers indicates possible point sources of pollution for Masan Bay and Thau lagoon. This study highlights a growing pollution problem in Asia and in particular a tremendous uptrend in Korea, in comparison to more controlled discharges and releases in Western Europe.

The contamination status of twelve persistent organic pollutants (POPs) on the Stockholm convention in the surface sediments of Han river, which is one of the largest river in the South Korea were investigated. Five organochlorine pesticides (OCPs) such as aldrin, dieldrin, endrin, mirex, and SigmaCHLs (alpha-chlordane, gamma-chlordane, cis-nonachlor, trans-nonachlor, and heptachlor) were not detected in all sediment samples. The overall concentrations of DDTs, HCB, dioxin-like PCBs (DL-PCBs) and PCDD/Fs were in the range of 1.05-8.94microgkg(-1) (average value: 3.93microgkg(-1)), 0.485-3.73microgkg(-1) (1.48microgkg(-1)), 41.5-4,530ngkg(-1) (548ngkg(-1)), and 23.1-368ngkg(-1) (131ngkg(-1)), respectively. The principal source of HCB, DL-PCBs and PCDD/Fs was identified as a deposition in this study. For the DL-PCBs, it was also shown that commercial PCBs product (Kanechlor 500 and/or Aroclor 1254) plays a role as a source in sediment.

To understand the distribution characteristics of nonylphenolics and sterols, samples such as in creek water, sea surface water, waste water treatment plant (WWTP) effluent water, sediment and mussel were collected and analyzed. The principal analytes are nonylphenol (NP), nonylphenol monoethoxylate (NP1EO), nonylphenol diethoxylate (NP2EO), coprostanol (5beta) and cholestanol (5alpha). All these target pollutants showed 100% detection frequency in all of the samples analyzed. Total concentration of nonylphenolic compounds ranged from 334 to 3628ngl(-1) (average: 1331ngl(-1)) in creek water, from 15 to 36400ngl(-1) (average: 1013ngl(-1)) in sea surface water, from 131 to 2811ngg(-1) dry weight (average: 581ngg(-1) dry weight) in sediment and from 50.5 to 289ngg(-1) dry weight (average: 139ngg(-1) dry weight) in mussel. For water samples, levels of nonylphenolics determined in summer season were higher than those in spring season. Among them, nonylphenol and NP1EO was dominant in creek water and seawater, respectively. The highest concentration was recorded in sediment near a WWTP effluent outlet. And high levels of nonylphenolics and sterols were found in about 3km area surrounding WWTP effluent outlet. Coefficient of linear regression (R(2)) for NP in mussel and in sediment was 0.90. Similarly good correlation (R(2)=0.98) was obtained between concentration in water and in mussel indicating that a steady state has been reached in this bay. The calculated bio concentration factor (BCF=2990) for NP in Masan Bay agrees well with reported values in the literature.

A congener-specific determination of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in 21 surface sediments from Masan Bay, Korea revealed that the most toxic 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) was detected in 76% of the samples and 2,3,7,8-tetrachlorodibenzofuran (2,3,7,8-TCDF) in 100% of the samples analyzed. The concentration range of SigmaPCDDs and SigmaPCDFs are: 230-6900; 120-16700pgg(-1) dry mass respectively. WHO Toxic Equivalents (WHO-TEQ) in Masan Bay sediment ranged from 0.53 to 99ng TEQkg(-1)d.m. for PCDDs; 4 to 1300ngTEQkg(-1)d.m. for PCDFs. In comparison with an earlier survey, the concentrations of dioxins and furans have more than doubled and the SigmaWHO-TEQ values have increased 15 times within a decade. Both point and non-point sources of pollution are suspected, especially, local sewage treatment plants are found to contribute.

In order to understand the behavior of nonylphenol (NP) in Han River, water, suspended particle and sediment samples were analyzed during summer, autumn and winter. Concentrations of nonylphenol in water ranged from 23.2 to 187.6 ng/l, in suspended particle from 6.8 to 190.8 ng/l and in sediment from 25.4 to 932.0 ng/gdrywt. An increasing trend in the concentration is noticed in all matrices along down the river. In case of water and suspended particle, concentrations were higher in warmer season than in colder season. Percentage of nonylphenol in the suspended particle phase decreased from 67% to 28% with decreasing temperature in water. A reasonable correlation (R2 = 0.63) was obtained for water and suspended particle. The partition coefficient Log Kp is 4.8. No seasonal variation of the concentration in sediment is noticed in this study., (Copyright 2004 Elsevier Ltd.)