Rapid Production of Micro- and Nanoplastics by Fragmentation of Expanded Polystyrene Exposed to Sunlight.

Expanded polystyrene (EPS) is a common plastic marine debris found in oceans worldwide. The unique "foamed" structure of EPS, which is composed of thin layers, is more vulnerable to fragmentation than bulk plastics. However, the production rate of micro- and nanoplastics by the fragmentation of EPS following sunlight exposure remains largely unknown. Here, we determined the fragmentation rate and weight loss of EPS in an outdoor weathering experiment that ran for 24 months. It took only 1 month for the weight of an EPS box to decline by 5% due to photodegradation, and approximately 6.7 × 107 micro- and nanoparticles/cm2 could be produced at a latitude of 34 °N. These results indicate that macro EPS debris can continually produce a massive number of particles within a relatively short exposure duration. The findings provide useful information to inform policymakers how rapidly to remove "likely fragmented" plastic litter from the environment.

Horizontal and Vertical Distribution of Microplastics in Korean Coastal Waters.

This is the first survey to investigate the vertical distribution and composition of microplastics >20 µm at the surface (0-0.2 m; bulk sample) and in the water column (3-58 m depth; pump) of six semi-enclosed bays and two nearshore areas of South Korea. The average microplastic abundance of 41 stations at all sampling depths was 871 particles/m3, and the microplastic abundance near urban areas (1051 particles/m3) was significantly higher than that near rural areas (560 particles/m3). Although the average microplastic abundances in the midcolumn (423 particles/m3) and bottom water (394 particles/m3) were approximately 4 times lower than that of surface water (1736 particles/m3), microplastics prevailed throughout the water column in concentrations of 10-2000 particles/m3. The average sizes of fragment and fiber type microplastics were 197 and 752 µm, respectively. Although the polymer composition differed by depth depending on the particle size and density, polypropylene and polyethylene predominated throughout the water column regardless of their low density and particle size. Finally, the middle and bottom water samples contained higher abundances of microplastics than predicted by a model based on physical mixing, indicating that biological interactions also influence the downward movement of low-density microplastics.

Combined Effects of UV Exposure Duration and Mechanical Abrasion on Microplastic Fragmentation by Polymer Type.

It is important to understand the fragmentation processes and mechanisms of plastic litter to predict microplastic production in the marine environment. In this study, accelerated weathering experiments were performed in the laboratory, with ultraviolet (UV) exposure for up to 12 months followed by mechanical abrasion (MA) with sand for 2 months. Fragmentation of low-density polyethylene (PE), polypropylene (PP), and expanded polystyrene (EPS) was evaluated under conditions that simulated a beach environment. PE and PP were minimally fragmented by MA without photooxidation by UV (8.7 ± 2.5 and 10.7 ± 0.7 particles/pellet, respectively). The rate of fragmentation by UV exposure duration increased more for PP than PE. A 12-month UV exposure and 2-month MA of PP and PE produced 6084 ± 1061 and 20 ± 8.3 particles/pellet, respectively. EPS pellets were susceptible to MA alone (4220 ± 33 particles/pellet), while the combination of 6 months of UV exposure followed by 2 months of MA produced 12,152 ± 3276 particles/pellet. The number of fragmented polymer particles produced by UV exposure and mechanical abrasion increased with decreasing size in all polymer types. The size-normalized abundance of the fragmented PE, PP, and EPS particles according to particle size after UV exposure and MA was predictable. Up to 76.5% of the initial EPS volume was unaccounted for in the final volume of pellet produced particle fragments, indicating that a large proportion of the particles had fragmented into undetectable submicron particles.

Styrofoam Debris as a Source of Hazardous Additives for Marine Organisms.

There is growing concern over plastic debris and their fragments as a carrier for hazardous substances in marine ecosystem. The present study was conducted to provide field evidence for the transfer of plastic-associated chemicals to marine organisms. Hexabromocyclododecanes (HBCDs), brominated flame retardants, were recently detected in expanded polystyrene (styrofoam) marine debris. We hypothesized that if styrofoam debris acts as a source of the additives in the marine environment, organisms inhabiting such debris might be directly influenced by them. Here we investigated the characteristics of HBCD accumulation by mussels inhabiting styrofoam. For comparison, mussels inhabiting different substrates, such as high-density polyethylene (HDPE), metal, and rock, were also studied. The high HBCD levels up to 5160 ng/g lipid weight and the γ-HBCD dominated isomeric profiles in mussels inhabiting styrofoam strongly supports the transfer of HBCDs from styrofoam substrate to mussels. Furthermore, microsized styrofoam particles were identified inside mussels, probably originating from their substrates.

Occurrence and Distribution of Microplastics in the Sea Surface Microlayer in Jinhae Bay, South Korea.

Microplastic contamination of the marine environment is a worldwide concern. The abundance of microplastics was evaluated in the sea surface microlayer in Jinhae Bay, on the southern coast of Korea. The microplastics in this study are divided into paint resin particles and plastics by polymer type. The mean abundance of paint resin particles (94 ± 68 particles/L) was comparable to that of plastics (88 ± 68 particles/L). Fragmented microplastics, including paint resin particles, accounted for 75 % of total particles, followed by spherules (14 %), fibers (5.8 %), expanded polystyrene (4.6 %), and sheets (1.6 %). Alkyd (35 %) and poly(acrylate/styrene) (16 %) derived from ship paint resin were dominant, and the other microplastic samples consisted of polypropylene, polyethylene, phenoxy resin, polystyrene, polyester, synthetic rubber, and other polymers. The abundance of plastics was significantly (p < 0.05) higher in Jinhae Bay, which is surrounded by a coastal city, than along the east coast of Geoje, which is relatively open sea. The floating microplastic abundance in surface water was the highest reported worldwide.

Qualitative Analysis of Additives in Plastic Marine Debris and Its New Products.

Due to their formulation and/or processing, plastics contain additives and impurities that may leach out under conditions of use and accumulate in the environment. To evaluate their role as vectors of chemical contaminants in marine environment, plastic debris (n = 19) collected from coastal beaches along with new plastics (n = 25; same or same brand) bought from local markets were screened by gas chromatography-mass spectrometry in full scan mode. Detected peaks were identified using NIST library in different polymers (polypropylene (PP) > polyethylene (PE) > PP + PE > polyethyl terephthalate > poly(acylene:styrene) with different use (food, fishery, and general use). A database on the presence of 231 different chemicals were grouped into hydrocarbons, ultra-violet (UV)-stabilizers, antioxidants, plasticizers, lubricants, intermediates, compounds for dyes and inks, flame retardants, etc. The UV326, UV327, UV328, UV320, UvinualMC80, irganox 1076, DEHP, antioxidant no 33, di-n-octylisophthalate, diisooctyl phthalate, hexanoic acid 2-ethyl-hexadecyl ester, and hydrocarbons were most frequently detected. Finding of toxic phthalates and UV stabilizers in those products having moisture contact (like bottles with short use) raised concern to humans and indicated their irregular use. The comparison between new and debris plastics clearly indicated the leaching and absorption of chemicals and supports our assumption of plastic as media for transferring these additives in marine environment.

Distribution and Size Relationships of Plastic Marine Debris on Beaches in South Korea.

The characteristics of the distribution of plastic marine debris were determined on 12 beaches in South Korea in 2013 and 2014. The abundances of large micro- (1-5 mm), meso- (5-25 mm), and macroplastics (>25 mm) were 880.4, 37.7, and 1.0 particles/m(2), respectively. Styrofoam was the most abundant debris type for large microplastics and mesoplastics (99.1 and 90.9 %, respectively). Fiber (including fabric) was the most abundant of the macroplastics (54.7 %). There were no statistical differences in the mean numbers and weights of plastic debris among three beach groups from west, south, and east coasts. No significant differences were detected between the abundances of beached plastics in high strandline and backshore for all three size groups. Spearman's rank correlation was used to determine the relationships between the three debris size classes. The abundance of large microplastics was strongly correlated with that of mesoplastics for most material types, which suggests that the contamination level of large microplastics can be estimated from that of mesoplastics. As surveying of smaller particles is more labor intensive, the surveying of mesoplastics with a 5-mm sieve is an efficient and useful way to determine "hot-spots" on beaches contaminated with large microplastics.

Large accumulation of micro-sized synthetic polymer particles in the sea surface microlayer.

Determining the exact abundance of microplastics on the sea surface can be susceptible to the sampling method used. The sea surface microlayer (SML) can accumulate light plastic particles, but this has not yet been sampled. The abundance of microplastics in the SML was evaluated off the southern coast of Korea. The SML sampling method was then compared to bulk surface water filtering, a hand net (50 µm mesh), and a Manta trawl net (330 µm mesh). The mean abundances were in the order of SML water > hand net > bulk water > Manta trawl net. Fourier transform infrared spectroscopy (FTIR) identified that alkyds and poly(acrylate/styrene) accounted for 81 and 11%, respectively, of the total polymer content of the SML samples. These polymers originated from paints and the fiber-reinforced plastic (FRP) matrix used on ships. Synthetic polymers from ship coatings should be considered to be a source of microplastics. Selecting a suitable sampling method is crucial for evaluating microplastic pollution.

Microplastic emission characteristics of stormwater runoff in an urban area: Intra-event variability and influencing factors.

Stormwater runoff is considered a major pathway for land-based microplastic transportation to aquatic environments. By applying time-weighted stormwater sampling at stormwater outlets from industrial and residential catchments, we investigated the emission characteristics and loads (number- and mass-based) of microplastics to aquatic environments through urban stormwater runoff during rainfall events. Microplastics were detected in stormwater runoff from industrial and residential areas in the concentration range of 68-568 n/L and 54-639 n/L, respectively. Polypropylene and polyethylene were found as major polymers accounting for around 60 % of total microplastics. The fragment was the dominant shape of microplastics, and the most common size class was 20-100 µm or 100-200 µm. The microplastic load emitted from industrial and residential areas were estimated to be 1.54-46.1 × 108 and 0.63-28.5 × 108 particles, respectively. The discharge characteristics of microplastics inter- and intra-event were affected by the land-use pattern and rainfall characteristics. The concentration of microplastics did not significantly differ between industrial and residential catchments, but the composition of polymer types reflected the land-use pattern. The microplastics in stormwater were more concentrated when the number of antecedent dry days (ADDs) was higher; the concentration of microplastics was generally peaked in the early stage of runoff and varied according to rainfall intensity during a rainfall event. The contamination level and load of microplastics were heavily affected by the total rainfall depth. Most microplastics were transported in the early stage of runoff (19-37 % of total runoff time), but the proportion of larger and heavier particles increased in the later period of runoff. The microplastic emission via stormwater runoff was significantly higher than that through the discharge of wastewater treatment plant effluent in the same area, implying that stormwater runoff is the dominant pathway for transporting microplastics to aquatic environments.

Plastic debris as a mobile source of additive chemicals in marine environments: In-situ evidence.

Plastic debris can act as a source of hazardous chemicals in the ocean, but the significance of its role in the environment is not yet known. To address this question, a comprehensive field study of highly contaminated and non-contaminated islands was conducted. Comparison of the plastic additive hexabromocyclododecanes and ubiquitous contaminants polychlorinated biphenyls in marine invertebrates showed that the load of stranded plastics plays a significant role in the bioaccumulation of plastic additives in the marine debris-contaminated island. Fugacity analysis indicates that net flow of hexabromocyclododecanes occurred from plastics to environmental reservoirs. Additionally, significantly higher levels of antioxidants, 2,4-di-tert-butylphenol and butylated hydroxytoluene, was found in the marine invertebrates inhabiting the marine debris-contaminated island than those inhabiting the marine debris-noncontaminated island, but ultraviolet stabilizers did not show the regional difference. This study provides the first field evidence that the movement of plastic debris in the ocean drives the dispersal of plastic additives to pristine waters.

Intra-annual variation in microplastics in mussels (Mytilus galloprovincialis) inhabiting an urbanized bay of South Korea.

This study investigated the presence of microplastics (MPs) in mussels from an urbanized bay in Korea, focusing on intra-annual variation. The average MP concentration was 0.36 ± 0.14 n/g w.w. (1.24 ± 0.56 n/individual). MPs were detected throughout the year with minor monthly variation and no significant monthly changes. Although there was no correlation between MP concentration in mussel and seawater, a positive relationship was observed when normalizing MPs to mussel's condition index (except for July). Polypropylene, polyethylene and acrylate polymer were dominant MPs, with high-density polymers comprising 59 % of the total. Most MPs were fragments and particles <200 µm. This study indicates that strict time restrictions for mussel sampling may not be necessary to assess MP levels in this bay. Additionally, considering MPs in seawater, biological conditions of mussel may be essential for understanding variations in MP levels in mussels. Including small MPs (<200 µm) and high-density polymers in MP assessment is recommended.

Spatial distribution and historical trend of microplastic pollution in sediments from enclosed bays of South Korea.

Seafloor sediments are an important sink for microplastics (MPs), and the vertical profile of MP accumulation in a sediment core represents historical pollution trends. In this study, MP (20-5000 µm) pollution in surface sediments of urban, aquaculture, and environmental preservation sites in South Korea was evaluated, and the historical trend was investigated using age-dated core sediments from the urban and aquaculture sites. The abundance of MPs ranked in the order of urban, aquaculture, and environmental preservation sites. Polymer types were more diverse at the urban site compared to other sites, and expanded polystyrene was dominant in the aquaculture site. An increase in MP pollution and polymer types was observed from bottom to top of cores, and historical trends of MP pollution reflect local influences. Our results indicate that the characteristics of MPs are determined by human activities, and MP pollution should be addressed according to the characteristics of each site.

The effects of environmental Microplastic on wharf roach (Ligia exotica): A Multi-Omics approach.

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.

Particle-size distribution of polycyclic aromatic hydrocarbons in urban road dust of Masan, Korea.

Concentrations and compositions of polycyclic aromatic hydrocarbons (PAHs) in particle size fractions of road dust sampled from contrasting areas of an industrialised city in Korea are reported. The largest amounts of road dust were present in industrial areas, followed by areas subject to heavy traffic, and the lowest amounts were associated with a residential area. The highest concentrations of PAHs were recorded in road dust sampled from the areas with the heaviest traffic (0.45-4.1 µg/g), followed by industrial areas (0.1-3.56 µg/g), with the lowest concentrations associated with a residential area (0.32-1.95 µg/g). PAH concentrations in the fractionated dust from the industrialised areas exhibited an inverse correlation with particle size. Although a similar general pattern was observed in the areas of heavy traffic, some increased concentrations associated with larger particles possibly reflect petrogenic contributions. Particles in road dusts from the residential area were generally smaller than those from the other areas, with PAH composition dominated by pyrogenic sources. PAH compositional profiles, evaluated through diagnostic isomeric ratios, indicate that exhaust emissions, rather than crankcase oils or tire and asphalt abrasion, are the major polluting source.

Spatial distribution and temporal trends of classical and emerging persistent organic pollutants (POPs) in black-tailed gull (Larus crassirostris) eggs from Korea.

This study monitored the spatiotemporal trends of persistent organic pollutants (POPs) contamination along the Korean coasts using eggs of the black-tailed gull, a resident bird that occupies a high trophic position in the marine food web. Black-tailed gull eggs were collected from three breeding islands located in the western (Seoman-do), southern (Hong-do), and eastern (Dok-do) seas of Korea during 2015-2019, and egg contents were analyzed for classical and emerging POPs. Among the target analytes, levels of emerging POPs such as brominated flame retardants (BFRs) and perfluoroalkyl acids (PFAAs) were significantly higher in eggs from Seoman-do than other islands. Global positioning system tracking data show that seagulls from Seoman-do traveled frequently to two neighboring major cities (Incheon and Seoul), indicating that the accumulation of BFRs and PFAAs in bird eggs is directly affected by the pollution characteristics of urban areas. Overall, the ratios of PFAA and BFR to the total POPs in eggs from the islands increased over time, while the proportion of classical POPs decreased. A shift from classical POPs to BFRs and PFAAs in seagull eggs was identified. Interestingly, perfluorooctanoic acid (PFOA), which exhibits limited bioaccumulation, was detected at higher levels in eggs from Seoman-do, indicating widespread use of PFOA and maternal transfer to seabird eggs. Continuous monitoring of PFAAs in marine environments of Korea is needed. This study demonstrates that monitoring of seabird eggs is effective for detecting spatial and temporal trends of POPs in the marine environment, and provides insights into emerging POPs such as PFAAs.

Underwater hidden microplastic hotspots: Historical ocean dumping sites.

Three ocean dumping sites located in the Yellow Sea (YS) and East Sea (ES) of South Korea have accumulated terrestrial waste from 1988 to 2015. Most of this waste comprised industrial wastewater and sewage sludge, which are sources of microplastics. In this study, we investigated the spatiotemporal distribution and characteristics of microplastics in surface and core sediments of the YS, South Sea (SS) and ES, including at dumping sites (YDP and EDP). The mean abundance of microplastics in surface sediments was ranked in order of EDP (59,457 ± 49,130 particles/kg d.w.), ES (5,047 ± 9,404 particles/kg d.w.), YDP (3,965 ± 3,213 particles/kg d.w.), SS (314 ± 488 particles/kg d.w.) and YS (288 ± 400 particles/kg d.w.). EDP and YDP showed about 14- and 12-fold higher microplastic abundances, and more diverse polymer compositions, than the ES and YS, respectively. The historical trend of microplastic pollution in age-dated core sediments from EDP and YDP aligned well with the amount of historical ocean dumping. As the level of ocean dumping has gradually reduced since 2006, and was finally banned in 2015, the microplastic abundance decreased accordingly. Interestingly, spherical polystyrene (PS) primary microplastic was the dominant type in EDP sediments (78%) and other surface sediments in the ES (52%). More than 60 million tons of sewage and wastewater sludge were dumped at EDP, and extremely high abundances of up to 130,000 particles/kg d.w. were observed in EDP surface sediments. PS primary microplastics were continuously present in the EDP and ES sediment cores in the dumping period and are suspected to have originated from industrial wastewater sludge. The particle transportation model results showed that PS was dispersed throughout the ES during ocean dumping. In addition, deep circulation can contribute to the dispersion of particles after sinking. These results indicate that ocean dumping sites represent an underwater hotspot and source of microplastics in seafloor sediments.

Levels and profiles of perfluorinated alkyl acids in liver tissues of birds with different habitat types and trophic levels from an urbanized coastal region of South Korea.

Contamination status and characteristics of perfluorinated alkyl acids (PFAAs) including perfluorinated carboxylic acids (PFCAs) and perfluorinated sulfonic acids (PFSAs) was examined using liver tissue of birds - black-tailed gulls (Larus crassirostris), domestic pigeons (Columba livia var. domestica), pacific loons (Gavia pacifica), herons (Ardea cinerea), and egrets (Egretta garzetta and Ardea alba) - with different trophic levels, habitat types and migratory behaviors from an industrialized coastal region of South Korea. A wide range of PFAAs (1.09 ng/g to 1060 ng/g; median = 52.6 ng/g) were detected in bird livers from the Korean coasts with high detection frequency. Accumulation features of PFAAs in birds indicated that primarily trophic position and secondly habitat type influence the levels and composition of PFAAs, e.g., relatively high PFAA levels and high composition of odd-numbered long carbon chain PFCAs (perfluoroundecanoic acid (PFUnDA) and perfluorotridecanoic acid (PFTriDA)) and PFOS in higher trophic and marine birds. The prevalence of long carbon chain (≥14) PFCAs likely implies a wide use of fluorotelomer-based substances in Korea. Interspecies comparison in the accumulation profile of persistent organic pollutants (including polychlorinated biphenyls (PCBs), organochlorine pesticides, polybrominated diphenylethers (PBDEs), and PFAAs) reveals relatively high load of PFAAs in inland (pigeons) and estuarine (egrets/herons) species compared to marine bird species, indicating wide use of PFAAs in the terrestrial environment.

What type of plastic do sea turtles in Korean waters mainly ingest? Quantity, shape, color, size, polymer composition, and original usage.

Globally, sea turtles are at high risk of ingesting plastic. However, research on plastic ingestion by sea turtles in East Asia is scant, and no quantitative or qualitative investigation has been conducted in Korean waters. This study examined the plastic ingestion of sea turtles stranded, floating, or incidentally captured in Korean waters between 2012 and 2018. The quantity, shape, color, size, polymer type, and original usage of plastic debris (>1 mm) ingested by sea turtles were analyzed after being sorted from the gastrointestinal tracts of 34 turtles (21 loggerheads (Caretta caretta), 9 green turtles (Chelonia mydas), 2 leatherbacks (Dermochelys coriacea), and 2 olive ridleys (Lepidochelys olivacea)). The ingestion frequencies of greens, loggerheads, olive ridleys, and leatherbacks were 100%, 81%, 50%, and 50%, respectively. The mean amount of plastic ingested was 108 ± 253 mg/kg (38 ± 61 n/ind.). The ingested debris tended to be films and fibers (>80%), light in color (white and transparent; 65%), and light polymers (polyethylene, polypropylene, polypropylene [poly (ethylene:propylene)], expanded polystyrene; 93%). The original uses were identified for 187 pieces; single-use plastics (e.g., plastic bag and packaging) and fishing and aquaculture items (e.g., twine and net) were found to dominate. Green turtles (264 ± 433 mg/kg) ingested significantly higher amounts of plastic than loggerheads (72.8 ± 156 mg/kg). Green turtles ingested mostly fibers (51%), such as rope, twine, and net, while loggerheads ingested largely films (61%), such as plastic bags and packaging. Interspecies differences in quantities and shapes of ingested debris may be related to their distinct feeding habits and geographical range of movement. The present study demonstrates that sea turtles foraging in Korean waters are considerably affected by marine plastic debris, and indicates that proper waste management of single-use plastics and fishing gears is urgently needed to mitigate the damage that plastic debris causes to marine wildlife.

Identification of novel polar aryl hydrocarbon receptor agonists accumulated in liver of black-tailed gulls in Korea using advanced effect-directed analysis.

Although bioaccumulation of persistent organic pollutants in seabirds has been examined, few studies have been conducted to identify previously unidentified substances. Here, aryl hydrocarbon receptor (AhR) agonists were identified in livers of black-tailed gulls from South Korea using effect-directed analysis combined with full-scan screening analysis. Significant AhR-mediated potencies were observed in the polar fractions of liver extracts using H4IIE-luc bioassay. Eight known polar AhR agonists accounted for 11-20% of the total AhR-mediated potencies in the polar fractions; hydrocortisone and rutaecarpine were the major contributors. Twenty-two AhR agonist candidates in the polar fractions were identified using liquid chromatography-quadrupole time-of-flight mass spectrometry during a six-step selection process. Of these, [10]-gingerol, angelicin, corticosterone, eupatilin, etofenprox, oxadixyl, and tretinoin were identified as novel AhR agonists. The contribution to potencies increased with inclusion of novel AhR agonists (27-52%); corticosterone and [10]-gingerol contributed significantly. Quantitative structure-activity relationship suggested that the novel AhR agonists have other potential toxic effects, including carcinogenicity and mutagenicity. Polar AhR agonists have been used for pharmaceuticals and pesticides. Some novel AhR agonists have log KOW > 2 and log KOA ≥ 6, which indicates that these compounds can be biomagnified in air-breathing organisms, such as seabirds.