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.

Photosynthesis enhancement in four marine microalgal species exposed to expanded polystyrene leachate.

Due to its widespread use, large amounts of expanded polystyrene (EPS) have been released into the marine environment, where it is broken down into small pieces with large surface areas. As such, chemical additives may be released into the environment, which can affect marine organisms; however, studies of the effects of such additives are lacking. We assessed the effects of leachate from EPS on the photosynthetic activities of four microalgal species (Dunaliella salina, Scenedesmus rubescens, Chlorella saccharophila, and Stichococcus bacillaris). They were exposed to EPS leachate for seven days and their photosynthetic activities were analyzed based on seven parameters. Overall, leachate exposure increased photosynthetic activity in all four species, albeit to different degrees and showing slightly different trends among the seven parameters. Based on chemical analysis, hexabromocyclododecane concentrations were higher in small-fragment leachate, whereas UV326 concentrations were higher in low-concentration-large-sphere leachate; bisphenol-A and total organic carbon showed no major differences among leachates. Thus, we speculate that exposure to trace chemicals influenced microalgal photosynthesis and overall growth. These results support further investigation of the impacts of plastic debris and chemical additives on marine ecosystems and organisms.

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.

Imposex in Reishia clavigera as an Indicator to Assess Recovery of TBT Pollution After a Total Ban in South Korea.

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

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.

Occurrence and characteristics of microplastics in greywater from a research vessel.

The discharge of greywater from ships, an uncounted sea-based source of microplastics (MPs), is a growing concern. Yet, empirical data on MPs from this source are currently limited. Here, the abundances and characteristics of MPs in greywater from a research vessel were investigated according to water usage type (e.g., galley, cabin, and laundry). The mean abundance of MPs was highest in greywater from the laundry (177,667 n/m3), followed by the cabins (133,833 n/m3) and galley (75,000 n/m3). However, no significant differences were found in the MP abundances among greywater types due to high variability of triplicate samples collected every five days. Fiber-type MPs accounted for 66% of the total MP abundance and fragment-type MPs for 34%. Microplastics in the size range of 100-200 µm exhibited the highest levels among size classes. The dominant polymer identified in all greywater samples was polyester (53%), followed by polypropylene (23%). Marine coating origin MPs (6%) were also observed in all types of greywater. The greywater generation rate during the cruise was 0.15 m3/person∙day. Annual MP emissions per person by the greywater discharge of the research vessel was estimated to be 4.1 × 106 n/person∙year (equivalent to 3.0 g/person∙year).

Differential impact of planktonic and periphytic diatoms on aggregation and sinking of microplastics in a simulated marine environment.

Aggregation between microalgae and microplastics (MPs) significantly influences the MPs distribution in marine environment. We investigated the effects of two diatoms, the planktonic Pseudo-nitzschia pungens and the periphytic Navicula sp., on the formation and sinking of aggregates when they were cultured with four different types of MPs: small and large polyethylene terephthalate (PET) fibers, and low-density and high-density polyethylene (PE) spheres. Navicula sp. formed aggregates with all MPs within one week, but P. pungens only formed aggregates with PE spheres after 9 weeks. The PE-Navicula sp. aggregates settled about 100 times faster than the PE-P. pungens aggregates (12.2 vs. 0.1 mm s-1), and this difference was most likely due to aggregate shape rather than size. Our findings indicate that the periphytic Navicula sp. had a greater effect on the settling of MPs than the planktonic P. pungens. These findings have implications for understanding the behavior of MPs in marine environments.

Experimental study on color and texture as cues for plastic debris ingestion by captive sea turtles.

Sea turtles face considerable risks from ingesting marine debris. They are primarily visual feeders, so color may be important for identifying food suitability or enhancing prey detection. Here, we investigated the impacts of color and texture on foraging behavior in relation to plastic consumption. We experimentally assessed the influences of color and texture as attractors for sea turtles using edible jellyfish. The findings showed that the colors of objects significantly affected selective preferences, as evidenced by different behaviors by sea turtles in response to different colors. They exhibited diet-related selectivity toward colors similar to common aquarium food, and texture had a significant impact on complete ingestion. The results suggest that plastic resembling natural prey is more likely ingested. Also, sea turtles were attracted by the color yellow, suggesting that visually distinctive items can attract them. Our results provide fundamental knowledge, helping mitigate the effects of plastic pollution on wildlife.

Identifying the source rookery of green turtles (Chelonia mydas) found in feeding grounds around the Korean Peninsula.

Determining the genetic diversity and source rookeries of sea turtles collected from feeding grounds can facilitate effective conservation initiatives. To ascertain the genetic composition and source rookery, we examined a partial sequence of the mitochondrial control region (CR, 796 bp) of 40 green turtles (Chelonia mydas) collected from feeding grounds around the Korean Peninsula between 2014 and 2022. We conducted genetic and mixed-stock analyses (MSA) and identified 10 CR haplotypes previously reported in Japanese populations. In the haplotype network, six, three, and one haplotype(s) grouped with the Japan, Indo-Pacific, and Central South Pacific clades, respectively. The primary rookeries of the green turtles were two distantly remote sites, Ogasawara (OGA) and Central Ryukyu Island (CRI), approximately 1,300 km apart from each other. Comparing three parameters (season, maturity, and specific feeding ground), we noted that OGA was mainly associated with summer and the Jeju Sea, whereas CRI was with fall and the East (Japan) Sea ground. The maturity did not show a distinct pattern. Our results indicate that green turtles in the feeding grounds around the Korean Peninsula originate mainly from the Japan MU and have genetic origins in the Japan, Indo-Pacific, and Central South Pacific clades. Our results provide crucial insights into rookeries and MUs, which are the focus of conservation efforts of the Republic of Korea and potential parties to collaborate for green turtle conservation.

Habitat use of loggerhead (Caretta caretta) and green (Chelonia mydas) turtles at the northern limit of their distribution range of the Northwest Pacific Ocean.

Verifying habitats, including the foraging and nesting areas for sea turtles, enables an understanding of their spatial ecology and successful planning of their conservation and management strategies. Recently, the observation frequency and bycatch of loggerhead (Caretta caretta) and green (Chelonia mydas) turtles have increased in the northern limit of their distribution range, in the northern part of the East China Sea and East (Japan) Sea. We conducted satellite tracking to investigate the habitat use of seven loggerhead and eight green turtles from June 2016 to August 2022 in this area, where little is known about their spatial ecology. We applied a 50 percent volume contour method to determine their main foraging areas and analyzed 6 environmental variables to characterize their habitats. Loggerhead turtles mainly stayed in and used the East China Sea as a foraging area during the tracking period, while two individuals among them also used the East Sea as a seasonal foraging area. Most green turtles also used the East China Sea as a foraging area, near South Korea and Japan, with one individual among them using the lower area of the East Sea as a seasonal foraging area. Notably, one green turtle traveled to Hainan Island in the South China Sea, a historical nesting area. Our results showed that the two sea turtle species included the East Sea as a seasonal foraging area, possibly owing to the abundance of food sources available, despite its relatively lower sea temperature. Considering that loggerhead and green sea turtles were observed using the northern part of the East China Sea and East Sea more frequently than previously known and that the sea temperature gradually increases due to climate change, conservation and management activities are required for sea turtles in these areas.

Fragmentation of nano- and microplastics from virgin- and additive-containing polypropylene by accelerated photooxidation.

Plastic is ubiquitous in the environment, where it gradually weathers and fragments into nanoplastics (NPs) and microplastics (MPs); however, the weathering process and fragmentation rate are poorly understood. In this study, we quantitatively determined the abundances and size distributions of NPs and MPs produced from virgin polypropylene (PP) and additive-containing PP (PPa) sheets via photooxidation with water in a simulated sunlight chamber followed by vortexing. The fragmentation rate of PP and PPa were approximately 1.1 × 108 particles/cm2 and 1.0 × 108 particles/cm2, respectively, during 176 days of exposure in the chamber (corresponding to 2.7 years of exposure in an outdoor environment in the Republic of Korea). However, quadratic regression analysis of the relationship between total particles produced and exposure duration revealed that the PP fragmentation rate was faster than the PPa fragmentation rate after a sunlight exposure duration equivalent to 2.7 years. Furthermore, the mechanical stress of vortexing after photooxidation played an important role in the production of MPs; it had a smaller role in the production of NPs. The sizes of fragmented particles produced by photooxidation and mechanical stress followed a power law distribution, with a scaling exponent of α = 2.87 ± 0.15, which was similar to a three-dimensional fragmentation pattern. This study provides valuable insights into the weathering and fragmentation processes of plastics. Further studies on the environmental fate and impact of NP and MP production from plastic weathering and fragmentation, as well as the potential influence of plastic additives on these processes.

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.

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.

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.