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Worldwide polystyrene (PS) production in 2020 was approximately 27 million metric tons, distributed among many nations, making it one of the most heavily imported and exported chemicals. Commercially produced PS usually possesses a broad molar mass distribution, often with a substantial oligomeric component. The latter can significantly affect processing and end-use, in addition to having potentially hazardous health effects and to impacting the polymer's export classification by regulatory agencies. Quantitation of the oligomeric region of polymers by size-exclusion chromatography with concentration-sensitive and/or static light scattering detection is complicated by the non-constancy of the specific refractive index increment (∂n/∂c) in this region, which affects the calculated amount (mass fraction) of oligomer in a polymer, molar mass averages, and related conclusions regarding macromolecular properties. Here, a multi-detector SEC approach including differential refractometry, multi-angle static light scattering, and differential viscometry has been applied to determining the ∂n/∂c of n-butyl terminated styrene oligomers at each degree of polymerization from monomer to hexamer, and also of a hexadecamer. Large changes in this parameter from one degree of polymerization to the next are observed, including but not restricted to the fact that the (∂n/∂c) of the monomer is less than half that of PS polymer at identical experimental conditions. As part of this study, the individual effects of injection volume, flow rate, and temperature on chromatographic resolution were examined. Incorporation of the on-line viscometer allowed for accurate determination of the intrinsic viscosity and viscometric radius of the monomer and oligomers.

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Styrene oligomers (SOs) are ubiquitous contaminants that appear in the environment, sometimes to significant extent (see section 3.1). Despite the ongoing international debate on the human health risks posed by SOs, to the best of my knowledge, there are no studies on the aquatic toxicity and environmental fates (biodegradation and atmospheric degradation) of SOs in the environment. This study is to predict the aquatic toxicity and environmental fate of SOs by using the US EPA EPI suite program as an in-silico method. For better understanding, the risks and fates of SOs are compared with those of the well-known bisphenol A (BPA) and styrene monomer (SM or styrene). As a result of this study, SOs are predicted to be relatively more toxic than BPA and SM to aquatic and terrestrial organisms in the freshwater, marine, and terrestrial environments. In particular, the biodegradability of SOs is predicted to be relatively very slow in the environment, and most SOs are more likely to be effectively decomposed by hydroxyl radicals than by ozone in the atmosphere. As a result, this study can contribute to motivating understanding of the aquatic toxicity and fate of ubiquitous SOs in the environment.

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Styrene oligomers (SO) are well-known side products formed during styrene polymerization. They consist mainly of dimers (SD) and trimers (ST) that have been shown to be still residual in polystyrene (PS) materials. In this study migration of SO from PS into sunflower oil at temperatures between 5 and 70 °C and contact times between 0.5 h and 10 days was investigated. In addition, the contents of SD and ST in the fatty foodstuffs créme fraiche and coffee cream, which are typically enwrapped in PS, were measured and the amounts detected (of up to 0.123 mg/kg food) were compared to literature data. From this comparison, it became evident, that the levels of SO migrating from PS packaging into real food call for a comprehensive risk assessment. As a first step towards this direction, possible genotoxicity has to be addressed. Due to technical and experimental limitations, however, the few existing in vitro tests available are unsuited to provide a clear picture. In order to reduce uncertainty of these in vitro tests, four different knowledge and statistics-based in silico tools were applied to such SO that are known to migrate into food. Except for SD4 all evaluated SD and ST showed no alert for genotoxicity. For SD4, either the predictions were inconclusive or the substance was assigned as being out of the chemical space (out of domain) of the respective in silico tool. Therefore, the absence of genotoxicity of SD4 requires additional experimental proof. Apart from SD4, in silico studies supported the limited in vitro data that indicated the absence of genotoxicity of SO. In conclusion, the overall migration of all SO together into food of up to 50 µg/kg does not raise any health concerns, given the currently available in silico and in vitro data.

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While the coastal pollution of persistent toxic substances (PTSs) has been widely documented, information on offshore environments remains limited. Here, we investigated the spatial distribution and sources of PTSs in the offshore sediments (n = 34) of South Korea. Sediment samples collected from the Yellow Sea (n = 18), the South Sea (n = 10), and the East Sea (n = 6), in 2017-18 were analyzed for a total of 71 PTSs. Target compounds include 31 PCBs, 15 PAHs, 9 emerging PAHs (e-PAHs), 10 styrene oligomers (SOs), and 6 alkylphenols (APs). Sedimentary PCBs showed relatively low concentrations with no significant difference across the three seas (0.16-6.9 ng g-1 normalized organic carbon, OC). Low-chlorinated PCBs (tri- and tetra Cl-CBs) were predominant (mean: 77%), primarily indicating atmospheric inputs. PAHs widely accumulated in the three seas with low to moderate level (22-250 ng g-1 OC), and dominated by high molecular weight PAHs (4-6 rings). PMF analysis revealed coast-specific PAHs sources; i.e., originated from mainly coke production (77%) in the Yellow Sea, vehicle emissions (68%) in the South Sea, and fossil fuel combustion (49%) in the East Sea. SOs showed significant contamination than other PTSs, with elevated concentrations in the Yellow Sea (mean: 350 ng g-1 OC). APs showed a similar regional distribution to SOs, but concentrations were much lower (mean: 17 ng g-1 OC). SOs and APs seemed to be introduced from rivers and estuaries on the west coast of Korea, where industrial and municipal activities are concentrated, then might be transported to offshore through tide or currents. Overall, the novel data presented for various PTSs in offshore Korean sediments warrant the necessity of a long-term monitoring effort and urgent management practice to protect marine ecosystem.

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Plastic pollution is one of the major issues impacting on the marine environment. Plastic polymers are known to leach industrial chemicals and associated contaminants. In this review, we focused on assessing the global distribution and concentration of two polystyrene-derived contaminants, hexabromocyclododecanes (HBCDs) and styrene oligomers (SOs), in marine sediments and seawater. Overall, most of the studies were carried out in Asia, North America, and Europe. Relatively high concentrations of these contaminants are generally attributed to the proximity of urban cities, plastic industries, polystyrene pollution, and aquaculture. Moreover, the concentrations in sediments are many times higher than in seawater. HBCDs were found to be a negligible risk to marine biota when compared to the ecotoxicological endpoints. However, realistic concentrations of SOs could compromise the wellbeing of certain species in highly polluted sites. The future perspectives and research were discussed.

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Bisphenol A (BPA) poses a serious environmental threat and health concern. This study presents the global monitoring of BPA on oceanic sandy beaches. According to monitoring results, many beach sands contain a harmful concentrations of BPA. Likewise, styrene oligomers (SOs), anthropogenic chemicals derived from polystyrene plastics, show similar concentrations as BPA. This study shows a strong, positive correlation between BPA and SOs. The results indicate that probably BPA-containing materials including micro- and nano-plastics can be an important source of BPA to the sand beaches. Therefore, BPA presents potential health risks to people spending considerable time on the beach.

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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.

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Despite growing concerns regarding plastic additives, their environmental fate coupled with leaching from source materials are not well known. Styrene oligomers (SOs), which are unintended additives in expanded polystyrene (EPS), are estrogenic micropollutants. Here, we identified the effects of their potential sources (i.e., EPS buoy and its leachate) and environmental dilution on SO distribution within coastal sediments. SO content in fresh EPS particles was 0.1% (w/w), dominated by 2,4,6-triphenyl-hexene (ST-1), while 2,4-diphenyl-1-butene (SD-2) accounted for most of the SOs in EPS leachate, indicating its faster leachability. In lake and offshore environments, the SO composition profiles from their terrestrial inputs and inner sites were similar to those of EPS leachate; meanwhile, the exponentially decreasing SO concentration and increasing styrene trimers (STs) fraction with distance from the inner to outer sites were evident. These profiles indicated continuous SO leaching from their potential sources in the inland, followed by a change in SOs due to environmental dilution. SOs in beach sediment implied the presence of micro-sized EPS particles. We suggest the ST-1 to SD-2 ratio as an index to differentiate among freshly leached SOs (∼0.02), environmentally diluted SOs after leaching (∼0.1), SOs in fresh EPS (∼1.2), and SOs in aged EPS (> 2).

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The Yellow and Bohai seas comprise one of the most rapidly developing regions in the world, but efforts to assess coastal pollution by persistent toxic substances (PTSs) on wide spatial scale are lacking. The present study aimed to (1) measure the concentrations of PTSs, such as polycyclic aromatic hydrocarbons (PAHs), alkylphenols (APs), and styrene oligomers (SOs) via large-scale sediment monitoring (total of 125 locations), (2) assess potential ecological risk of PTSs in sediments to coastal ecosystems, (3) estimate various sources and fresh inputs of PTSs, (4) determine distribution patterns of PTSs by human activities and land-use type, and (5) address decadal (2008-2018) changes in distributions of PTSs. The high concentrations of PAHs [> 7000 ng g-1 dry weight (dw)] in sediments were detected in Nantong in the Yellow Sea of China (YSC) and Huludao and Qinhuangdao in the Bohai Sea (BS), whereas lesser concentrations (< 200 ng g-1 dw) were detected in the Yellow Sea of Korea (YSK). We found relatively high concentrations of sedimentary APs and SOs in Nantong, Huludao, and Qinhuangdao from the YSC and BS regions, but corresponding concentrations were generally below < 100 ng g-1 dw in other locations. Concentrations of PAHs at 38 locations (30% of YSC and BS) posed a potential risk to aquatic ecosystems, whereas relatively low risk concentrations occurred in all locations of YSK. The main source of PAHs (concentrated in YSC and BS) were by-products of diesel and gasoline combustion (42% of total concentration), whereas biomass combustion (24%) dominated in YSK. Fresh inputs of PTSs indicated that the generation and use of PTSs continue across all regions and locations. Among PTSs, concentrations of PAHs were significantly associated with location (p < 0.05) relative to land-use within a given region, whereas concentrations of APs and SOs showed no significant relationships (p > 0.05) among or within regions. Over time, concentrations of PAHs have generally declined, but sediment contamination has increased at some locations in China, with sources shifting from a mixture of PAHs types to those linked to diesel and gasoline combustion. Additional studies are needed on the fate and potential ecological risk posed by certain PTSs in hotspots. This is one of the first efforts providing backgrounds on PTS pollution in the large marine ecosystem of the Yellow and Bohai seas.

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For decades, in response to industrialization and urbanization, environmental qualities of estuarine and coastal areas of the west coast of Korea have been deteriorating. Long-term changes in concentrations of persistent toxic substances (PTSs) in sediments, including PAHs, styrene oligomers, nonylphenols, and metals and their potential toxicities via AhR- and ER-mediated potencies, and bioluminescent bacterial inhibition, were investigated. Long-term monitoring in five estuarine and coastal areas (2010-2018; 10 sites) showed that concentrations of PAHs and nonylphenols in sediments have declined while concentrations of some metals, Cd, Cr, and Hg have increased. Similarly, AhR-mediated potencies in sediments have declined, but inhibitions of bioluminescent bacteria have increased. Concentrations of sedimentary PAHs and AhR-mediated potencies were significantly (p < 0.01) and positively correlated. Sources of PAHs from combustion have been gradually declining while inputs from vehicle exhaust by-products have been increasing. Overall, this study brought our attention a balanced regulation in chemical-specific manner.

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The risk of marine organisms ingesting plastics has become a growing concern due to hazard chemicals in plastics. To identify compounds to which seabirds potentially have substantial exposure, 194 plastics fragments and pellets ingested by seabirds, i.e., northern fulmars from the Faroe Islands, and laysan albatross and black-footed albatross from Mukojima Island, were analyzed piece by piece. Four kinds of UV stabilizers, 2 brominated flame retardants, and styrene oligomers were detected at detection frequencies of 4.6%, 2.1%, and 2.1%, respectively. Concentrations ranging from not detected (n.d.) - 1700 µg/g were measured for UV stabilizers, n.d. - 1100 µg/g for flame retardants, and n.d. - 3200 µg/g for styrene oligomers. We found that these chemicals could be retained in plastics during drifting and fragmentation in the ocean and transported to seabirds. This type of transport via plastics can be direct pathway that introduces hazardous compounds to marine organisms.

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Sources of organic matter in a polluted coastal embayment (Lake Sihwa) indicated that δ13C and δ15N of suspended particulate matter (SPM) and sediments could be distinguished by land-use type and surrounding activities. Specifically, low δ15N occurred in inland creeks near industrial complex, where severe contamination by persistent toxic substances (PTSs) is evidenced. To identify the sources of 15N-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 δ15N 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.

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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 Kow 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.

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Currently, styrene oligomers (SOs) are persistent contaminants that are present in the environment globally. SOs are artificial substances originating from styrene-based polymer materials, mainly including PS plastic, resin, and rubber. However, the behavior of SOs in the environment is not well-understood yet due to the scarcity of experimental data. The objective of this study was to use in-silico tool to estimate key physicochemical properties of these SOs. The US EPA EPI suite program was used to predict SOs' physicochemical properties including solubility, vapor pressure, LogKow, Henry's constant, LogKoc, and fugacity-based multimedia mass balance. Although styrene monomer (SM) and SOs have structural similarity, the physicochemical properties of SOs are significantly different from those of SM, a precursor of SOs. In particular, it is estimated that as much as the heavy molecular weight, most SOs persist for comparable periods of time in a sandy environment. Although there is uncertainty, this preliminary in-silico study provides a sufficient reason to assure an experimental study to better determine properties of SOs.

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The objective of this study is to investigate the qualitative contribution of internal and external factors of the area contaminated by polystyrene (PS) in coastal marine environments. This study is based on the extensive results of monitoring the styrene oligomers (SOs) present in sand and seawater samples along various coastlines of the Pacific Ocean. Here, anthropogenic SOs is derived from PS during manufacture and use, and can provide clues about the origin of SOs by PS pollution. The monitoring results showed that, if the concentration of SOs in water is higher than those concentrations in beach sand, this area could be affected by PS plastic caused by an external factor. On the other hand, if the concentration of SOs is higher in the beach sand, the region can be mainly influenced by PS plastic derived from its own area. Unlike the case of an external factor, in this case (internal influence), it is possible to take policy measures of the area itself for the PS plastic problem. Thus, this study is motivated by the need of policy measures to establish a specific alternative to the problems of PS plastic pollution in ocean environments.

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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.

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Styrene oligomers (SOs) as global contaminants are an environmental concern. However, little is known on the distribution of SOs in the ocean. Here, we show the distribution of anthropogenic SOs generated from discarded polystyrene (PS) plastic monitored from the coastal ocean surface waters (horizontal distribution) and deep seawaters (vertical distribution) in the North-West Pacific Ocean. SOs concentrations in surface seawater and deep seawater ranged from 0.17 to 4.26 µg L-1 (total mean: 1.48 ± 1.23 µg L-1) and from 0.31 to 4.31 µg L-1 (total mean: 1.32 ± 0.87 µg L-1), respectively. Since there is no significant difference in the mean concentrations, SOs seems to be spread across marine environment selected in this study. Nevertheless, regional SOs appears to persist to varying degrees with their broad horizontal and vertical distribution in the ocean. Each horizontal and vertical distribution of SOs differs by approximately 1.95-2.57 times, probably depending on the events of weather and global ocean circulation. These results provide the distribution pattern of SOs for assessing environmental pollution arising from PS plastic.

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Polystyrene (PS) plastic marine pollution is an environmental concern. However, a reliable and objective assessment of the scope of this problem, which can lead to persistent organic contaminants, has yet to be performed. Here, we show that anthropogenic styrene oligomers (SOs), a possible indicator of PS pollution in the ocean, are found globally at concentrations that are higher than those expected based on the stability of PS. SOs appear to persist to varying degrees in the seawater and sand samples collected from beaches around the world. The most persistent forms are styrene monomer, styrene dimer, and styrene trimer. Sand samples from beaches, which are commonly recreation sites, are particularly polluted with these high SOs concentrations. This finding is of interest from both scientific and public perspectives because SOs may pose potential long-term risks to the environment in combination with other endocrine disrupting chemicals. From SOs monitoring results, this study proposes a flow diagram for SOs leaching from PS cycle. Using this flow diagram, we conclude that SOs are global contaminants in sandy beaches around the world due to their broad spatial distribution.

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Beach sand and seawater taken from the coastlines of the North-East Pacific Ocean and Hawaii State were investigated to determine the causes of global chemical contamination from polystyrene (PS). All samples were found to contain styrene monomer (SM), styrene dimers (SD), and styrene trimers (ST) with a concentration distribution of styrene analogues in the order of ST > SD > SM. The contamination by styrene analogues along the West Coast proved more severe than in Alaska and other regions. The Western Coastlines of the USA seem be affected by both land- and ocean-based pollution sources, which might result from it being a heavily populated area as the data suggest a possible proportional relationship between PS pollution and population. Our results suggest the presence of new global chemical contaminants derived from PS in the ocean, and along coasts.

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Here, we conducted in vitro genotoxicity tests to evaluate the genotoxicity of styrene oligomers extracted from polystyrene intended for use in contact with food. Styrene oligomers were extracted with acetone and the extract was subjected to the Ames test (OECD test guideline No. 471) and the in vitro chromosomal aberration test (OECD test guideline No. 473) under good laboratory practice conditions. The concentrations of styrene dimers and trimers in the concentrated extract were 540 and 13,431 ppm, respectively. Extraction with acetone provided markedly higher concentrations of styrene oligomers compared with extraction with 50% ethanol aqueous solution, which is the food simulant currently recommended for use in safety assessments of polystyrene by both the United States Food and Drug Administration and the European Food Safety Authority. And these high concentrations of styrene dimers and trimers were utilized for the evaluation of genotoxicity in vitro. Ames tests using five bacterial tester strains were negative both in the presence or absence of metabolic activation. The in vitro chromosomal aberration test using Chinese hamster lung cells (CHL/IU) was also negative. Together, these results suggest that the risk of the genotoxicity of styrene oligomers that migrate from polystyrene food packaging into food is very low.