Preparation method of marine microplastic model in a short degradation time

Preparation method of marine microplastic model in a short degradation time | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Preparation method of marine microplastic model in a short degradation time Hisayuki Nakatani, Yuina Ohshima, Taishi Uchiyama, Motokucho Suguru, and 2 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-1976856/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract To establish a marine microplastic (MP) model, the sizes and O/C molar ratios of MP particles retrieved from the sea were measured using scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM/EDX) analysis. Most of the MP particles exhibit a diameter of <20 mm and O/C molar ratios of 0.1–0.2, indicating that they are mainly composed of polyethylene, polypropylene (PP), and polystyrene. An O/C ratio of 0.1 for PP was reached after being degraded for 75 days via an advanced oxidation process (AOP) in distilled water. The usage of SO 4 • − initiator overcame the inhibiting effect that seawater had on PP degradation and accelerated the process. The O/C molar ratio of a PP sample degraded via AOP for 15 days in seawater is the same as that of marine MP retrieved from the sea. The combination of seawater and SO 4 • − initiator thus led to excellent acceleration of the degradation process. Nanosized PP particles were obtained over 15 days of AOP degradation, showing that the size of the MP could be controlled according to the degradation time. Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Introduction Waste from the production of plastic presents a major issue when discarded in the marine environment 1 – 14 , as it spreads to the sea and leads to MP pollution. MP mainly comprises polypropylene (PP), polyethylene (PE), and polystyrene (PS) products and is generated by exposure to visible and/or UV light 12 – 14 . In our previous study, PP degradation tests were performed in distilled water via an advanced oxidation process (AOP) using SO 4 • −15 , where SO 4 • − functions as a highly-efficient initiator for the degradation of the plastic. However, many types of organic and inorganic constituents exist in the sea. In particular, Cl − reacts with OH• and inhibits photodegradation (autoxidation) initiation 16 , 17 . It is known that the generation of marine MP involves autoxidation in the presence of seawater. Therefore, to investigate the effects of marine MP on marine ecosystems, it is necessary to develop an accelerated degradation method that can be used to quickly establish a marine MP model. However, the effects of Cl − inhibiting the autoxidation process make it difficult to establish a model. A new initiator is thus needed to replace OH• to promote autoxidation in seawater. It is believed that SO 4 • − would also be an effective initiator in seawater, as it is converted to OH• by Cl − 18 , with some produced OH• simultaneously inhibited by it. There is a competition between the two species; however, the preponderance of the OH• formation promotes the autoxidation process. In addition, SO 4 • − is gradually converted to SO 4 2− , which affects the pH of alkaline seawater, with the equilibria of the reaction dependent on pH 19 . This change in pH accelerates the autoxidation process. It is considered that the utilization of SO 4 • − shortens the time required to prepare the marine MP model because of these effects. In this study, the size and O/C molar ratios of marine MP particles retrieved from the sea were determined by scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM/EDX) analysis to establish a new method for preparing a marine MP model. A PP model was prepared via AOP degradation using SO 4 • − as an autoxidation initiator in seawater. The degraded sample was studied in terms of its degradation behavior, shape, O/C molar ratio, and size to study the action of seawater on the plastic. The obtained results were then evaluated in terms of their equivalence with marine MP. Materials And Methods Materials. PP was supplied by Prime Polymer Co., Ltd. (product name: J-700GP). The MFR and density were 8 g/10min and 0.9 g/cm 3 . Potassium persulfate (K 2 S 2 O 8 ) was purchased from Wako Pure Chemical Industries. Sea water was retrieved from Nagasaki fishing port in Nagasaki city, Nagasaki, Japan (around S1 in Table 1). Scanning electron microscope (SEM) with energy dispersive x-ray spectroscopy analysis. The SEM / EDX analysis was carried out with a JSM-7500FAM (JEOL) with 5.0 kV. The working distance was about 3×4 mm. Samples placed in dried oven maintained at 27°C for 30 min and were sputter-coated with gold before SEM imaging. Particle size measurement. The fragment sample size was measured with an optical microscope (Nikon ECLIPSE 50/POL) or with a dynamic light scattering method (Otsuka Electronics Co., Ltd. ELSZ-2000ZS). MP retrieving from the sea. MP retrieving was carried out at 26th July 2021 using the training vessel T/V Kakuyo-maru (155 gross tonnage: Faculty of Fisheries, Nagasaki University) 20 , 21 . The sampling stations were summarized in Table 1. Each sampling of 1 L sea water was carried out in one day. The samples denoted as “D” were collected using a Conductivity Temperature Depth profiler (CTD) system at ca. 50 m below the sea level, and on the other hand the surface sampling (denoted as “S “ ) was carried out with a 3 L stainless bucket. Filtration for SEM/EDX observation of MP retrieved from the sea. Filtration was carried out with a polycarbonate membrane filter (Merck Isopore™ membrane) with 0.8 µm or 8 µm pore size without pretreatment. Degradation using advance oxidation process (AOP). The PP film was molded into thin films (30×30×0.060 mm) by compression molding at 180°C under 10 MPa for 11 min. The AOP degradation procedure was according to reports 18 , 22 . 1) Each five pieces of the film were put into a 100 ml glass vessel equipped with a 20 ml aqueous solution containing 0.54 g K 2 S 2 O 8 at ca. 65 °C for 12 h under stirring with a stirrer tip speed of ca. 100 rpm. 2) The equal amount of K 2 S 2 O 8 aqueous solution was added to compensate for the consumption of oxidant, and its degradation was carried out for 12 h under the same conditions. 3) And then only the five pieces of the film moved to a new 100 ml glass vessel equipped with the 20 ml aqueous solution containing 0.54 g K 2 S 2 O 8 , and their AOP degradations were restarted under the same conditions. The AOP degradation was carried out for a predetermined number of days using 1) to 3) as one set. The pH value of solution was changed from 8 to 3 during the one set. Results And Discussion Retrieved MP sizes and their O/C molar ratios. Figure 1 shows an SEM image and EDX analysis of a sample of tiny plastic particles retrieved from the sea (sampling station: S1-B) that have a particle size of around 450 nm and an O/C molar ratio of 0.15. This low ratio suggests that the particles are composed of artificial plastic material. The particles may be some phytoplankton; however, their body is composed of polysaccharides such as cellulose, the O/C ratio of which is much high, e.g., 0.83. The results reveal that marine MP can be distinguished from the phytoplankton according to the O/C molar ratio. Figure 2 (a) shows the relationship between the O/C molar ratio and the long diameter of MP samples retrieved from the sea. PE, PP, PS, polyvinylchloride (PVC), and polyethylene terephthalate (PET) are produced globally on a huge scale. The total amount of these commercially produced plastics constitutes around 80% of all thermoplastics 23 , 24 . For example, PP and PE represent 22% and 23% of the Japanese manufacturing of resins (in 2018), respectively. Consequently, most marine MP is composed of PE, PP, PS, PVC, and PET 25 . As shown in Fig. 2 (a), most of the MP samples show O/C molar ratios of < 0.4. The MP contained almost no PET with the 0.4 O/C molar ratio. Similarly, only a small proportion of the MP particles were identified as PVC with a high chlorine content. The O/C molar ratios indicate that the MP samples retrieved from the sea mainly composed of PE, PP and PS. Most of the MP particles exhibit diameters of < 20-µm long and O/C molar ratios of 0.1–0.2. These results thus provide an index of size and the degree of degradation (degree of oxidation) for modeling. Figure 2 (b) shows the relationship between the AOP degradation time and the O/C molar ratio of a PP sample in distilled water. The ratios gradually increased with up down. This behavior can be attributed to repeated oxidation and peeling off 15 , 26 . After 75 days, an O/C of 0.1 was achieved, indicating that it takes a long time using the AOP degradation method to achieve the same ratio for PP as that of marine MP. To investigate the effect that MPs have on marine organisms, it is thus necessary to develop a method to more quickly establish an MP model. Inhibiting and accelerating effects on autoxidation. Salinity lowers the degradation level of polyolefins such as PP and PE 17 , 27 , 28 . The refractive index of seawater increases due to salinity, and the utilization rate of UV light decreases in the degradation 27 , 28 . Wu et al. reported that aqueous Cl − acts as an inhibitor in the photooxidation of PP in seawater 17 . Figure 3 shows the transformation of radical species from SO 4 • − to OH• in seawater. In the case of PP photodegradation in seawater, Cl − reacts with OH• generated by solar irradiation and converts to ClOH• − , which is a less reactive molecule 17 . To avoid the inhibitory effect of Cl − , it is thus necessary to change the initiator of the oxidation degradation (autoxidation) reaction from OH• to another radical species. Considering the reactivity of radical species, SO 4 • − is suitable for autoxidation in seawater. As shown in Fig. 3 , the SO 4 • − initiator is transformed by Cl − 18 . A large amount of the SO 4 • − is converted into OH•, with some of the OH• converted into ClOH• − . However, since the production of ClOH• − requires re-reaction with Cl − , the residual amount of OH• increases. The initiation efficiency of autoxidation is greatly improved in seawater due to the reactivity of OH• being higher than that of SO 4 • − . Moreover, the reaction between Cl − and OH• also occurs and produces Cl•. As shown in Fig. 3 , two Cl• atoms couple to produce Cl 2 , which then reacts with H 2 O and forms ClOH, with the equilibria of the two reactions dependent on pH 19 . Since the pH of seawater is around 8, the equilibrium is biased toward the less reactive ClO − , which suppresses the autoxidation of PP in seawater. It is noted here that as the SO 4 • − gradually converts to SO 4 2− , the pH value of the K 2 S 2 O 8 in seawater solution decreases from ca. 8 to ca. 3 by the time of daily exchange (see Materials and methods section). This procedure ensures that there is a bias in the ClOH-rich equilibrium 19 for a period of time before the exchange of fresh K 2 S 2 O 8 seawater solution. The ClOH has a longer lifetime 18 and migrates deeply into the polymer matrix before dissociating into radicals and then initiates autoxidation 19 . The autoxidation proceeds from the PP interior as well as the surface, and the rate of MP formation is synergistically accelerated. The usage of SO 4 • − generates both OH• and ClOH, overcoming the inhibiting effect and accelerating the autoxidation process. Comparison of fragmentation behavior. Figure 4 shows SEM images of PP degraded via AOP for 15 days in seawater and pure water. Numerous micro pits can be observed on the surface of the seawater sample, which are traces of chemi-crystallization that is related to the autoxidation process 29 , 30 , showing that the PP degradation rapidly progresses. However, the surface of the pure water sample exhibits a lattice-like texture formed by cracks and is relatively smooth. The degree of degradation of the PP in pure water is thus considerably less than that of the seawater sample. Figure 5 shows SEM images and EDX analysis around the peeling-off location on the PP sample degraded via AOP for 15 days in seawater. Much microsized peeling-off marks can be observed, and the O/C molar ratios are around 0.17, 0.13, and 0.13 (see arrows in Fig. 5 ). These values are similar to those of the MP samples retrieved from the sea, indicating that a MP sample with the same degree of degradation can be prepared in a short degradation time of 15 days. Moreover, it was determined that the combination of seawater and K 2 S 2 O 8 initiator promotes excellent accelerated degradation of the plastic. In our previous study, PP film degradation tests were performed in water with a specific photocatalyst under visible light irradiation 26 or using the same AOP treatment 15 . The results revealed that MP particles are generated by planar exfoliation via autoxidation in the presence of water. Therefore, it is believed that the size of the MP is dependent on the degree of degradation, i.e., the degradation time. Figure 6 shows the long diameter distributions of PP degraded via AOP over 9, 12, and 15 days. After 9, 12 and 15 days of degradation, 79, 136 and 279 MP particles were recovered by filtration, respectively, indicating that the size is dependent on the AOP degradation time. The size distribution narrows with increasing AOP degradation time, with a bias toward smaller sizes. As shown in Fig. 7 , it is confirmed that nanosized PP particles are obtained over 15 days of AOP degradation. These results suggest that the size of the MP particles can be controlled according to the degradation time. Conclusion To establish a marine MP model, the MP samples retrieved from the sea were measured in terms of their sizes and O/C molar ratios, with most of them showing a size of < 20 µm in diameter and O/C molar ratios of 0.1–0.2, indicating that the marine MP mainly comprises PE, PP, and PS. After 75 days of the AOP degradation of PP in distilled water, an O/C of 0.1 was reached. It took a long time for the O/C ratio of the AOP degradation of PP in water using a SO 4 • − initiator in water to reach the same value as that of the marine MP. However, the SO 4 • − initiator was converted into OH• by aqueous Cl − in seawater, and the initiation efficiency was greatly improved in seawater. Moreover, the SO 4 • − gradually converted to SO 4 2− and led to a bias toward a ClOH-rich equilibrium. The ClOH dissociated into OH•. The use of SO 4 • − overcame the Cl − inhibiting effect on the autoxidation process and provided an accelerating effect in seawater. The O/C molar ratio of the PP sample degraded via AOP over 15 days in seawater was the same as that of the marine MP. The combination of seawater and K 2 S 2 O 8 initiator thus promoted excellent accelerated degradation. Much microsized peeling-off marks were observed for the PP sample degraded via AOP over 15 days in seawater, with O/C molar ratios of around 0.17, 0.13, and 0.13. These values are similar to those of MP samples recovered from the sea, indicating that an MP sample with the same degree of degradation of the sea-derived MP can be prepared in a short degradation time of 15 days. The combination of seawater and SO 4 • − initiator promoted excellent accelerated degradation of the plastic. Nanosized PP particles were obtained over 15 days of AOP degradation, showing that the size of MP could be controlled according to the degradation time. Declarations Data availability The data that support the findings of this study are available from the corresponding author, [HN], upon reasonable request. Acknowledgements This work was supported by the Environment Research and Technology Development Fund, No. 1MF-2204 from Ministry of the Environment, Government of Japan, by the Grant-in-Aid for Scientific Research, No. 20K05587 from Japan Society for the Promotion of Science, by Taihei Environmental Science Center Co., Ltd. and by financial supports of Nagasaki University organization for marine science and technology and for function enhancement program of research. Author contributions H.N. proposed the study and wrote the whole manuscript. M.Y. and Y.K. performed retrieving the MP samples from the sea. Y.O., and T.U. performed the experiment and analyzed the experimental data. All authors reviewed the manuscript. References Derraik, J. G. B. The pollution of the marine environment by plastic debris: a review. Mar. Poll. Bull. 44 (9), 842–852 (2002). Barnes, D. K. A., Galgani, F., Thompson, R. C., Barlaz, M. Accumulation and fragmentation of plastic debris in global environments. 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Polymer 38 (26), 6379–6387 (1997). Craig, I. H., White, J. R., Kin, P. C. Crystallization and chemi-crystallization of recycled photo-degraded polypropylene. Polymer 46 (2), 505–512 (2005). Table Table 1 Sampling station, coordinates, and depth. Additional Declarations No competing interests reported. Cite Share Download PDF Status: Posted Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-1976856","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":130342572,"identity":"fd2864dd-e098-472d-9e85-4220ef8cd286","order_by":0,"name":"Hisayuki Nakatani","email":"data:image/png;base64,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","orcid":"","institution":"Nagasaki University","correspondingAuthor":true,"submittingAuthor":false,"prefix":"","firstName":"Hisayuki","middleName":"","lastName":"Nakatani","suffix":""},{"id":130342573,"identity":"8ba3f844-4add-4da1-b383-fd6eae300096","order_by":1,"name":"Yuina Ohshima","email":"","orcid":"","institution":"Nagasaki University","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Yuina","middleName":"","lastName":"Ohshima","suffix":""},{"id":130342574,"identity":"1dafbca2-21ce-4779-a2aa-de17e4d330b0","order_by":2,"name":"Taishi Uchiyama","email":"","orcid":"","institution":"Nagasaki University","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Taishi","middleName":"","lastName":"Uchiyama","suffix":""},{"id":130342575,"identity":"ecf3fa19-bb98-43e2-a28b-907ef8ad49a3","order_by":3,"name":"Motokucho Suguru","email":"","orcid":"","institution":"Nagasaki University","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Motokucho","middleName":"","lastName":"Suguru","suffix":""},{"id":130342576,"identity":"4da761e0-e6ca-455e-98ad-a7ec1280277d","order_by":4,"name":"Mitsuharu Yagi","email":"","orcid":"","institution":"Nagasaki University","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Mitsuharu","middleName":"","lastName":"Yagi","suffix":""},{"id":130342577,"identity":"54a1f321-242b-4dab-a515-ffa5edc7c496","order_by":5,"name":"Yusaku Kyozuka","email":"","orcid":"","institution":"Nagasaki University","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Yusaku","middleName":"","lastName":"Kyozuka","suffix":""}],"badges":[],"createdAt":"2022-08-19 04:44:17","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-1976856/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-1976856/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":25564626,"identity":"b3970227-27c8-4f28-8278-1236940add52","added_by":"auto","created_at":"2022-08-23 17:41:52","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":4082229,"visible":true,"origin":"","legend":"\u003cp\u003eSEM photograph and EDX analysis of a plastic tiny particle sample retrieved by the sea.\u0026nbsp;\u003c/p\u003e\u003cp\u003e\u003cbr\u003e\u003c/p\u003e","description":"","filename":"Figure1.png","url":"https://assets-eu.researchsquare.com/files/rs-1976856/v1/5b4da75f4aa4e1fda0e73684.png"},{"id":25565202,"identity":"2c4a5445-2913-4409-9b8e-db923e74199e","added_by":"auto","created_at":"2022-08-23 17:46:52","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":149992,"visible":true,"origin":"","legend":"\u003cp\u003e(a) Relationship between O/C molar ratio and\u0026nbsp;long diameter (mm) of MP samples retrieved from the sea. (b)\u0026nbsp;Relationship between AOP degradation time and O/C molar ratio AOP using a PP sample in distilled water.\u003c/p\u003e\u003cp\u003e\u003cbr\u003e\u003c/p\u003e","description":"","filename":"Figure2.png","url":"https://assets-eu.researchsquare.com/files/rs-1976856/v1/ed2ea623dbe5698577b9953f.png"},{"id":25564628,"identity":"62cb7120-3810-45c0-bb61-5878cf57c6d5","added_by":"auto","created_at":"2022-08-23 17:41:52","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":246321,"visible":true,"origin":"","legend":"\u003cp\u003eA transformation of radical species from SO\u003csub\u003e4\u003c/sub\u003e•\u003csup\u003e−\u003c/sup\u003e to OH• in seawater, mechanisms for transfer reaction to Cl\u003csup\u003e−\u003c/sup\u003e and generation of chemical composition of Cl\u003csub\u003e2\u003c/sub\u003e solution in function of pH.\u003c/p\u003e\u003cp\u003e\u003cbr\u003e\u003c/p\u003e","description":"","filename":"Figure3.png","url":"https://assets-eu.researchsquare.com/files/rs-1976856/v1/670bc4f4ed0848ead0cecb11.png"},{"id":25564630,"identity":"bf0a4215-949d-40f0-9b6c-64319b9cc163","added_by":"auto","created_at":"2022-08-23 17:41:52","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":7742082,"visible":true,"origin":"","legend":"\u003cp\u003eSEM photographs of 15 days-AOP degradation PP in seawater and pure water.\u003c/p\u003e","description":"","filename":"Figure4.png","url":"https://assets-eu.researchsquare.com/files/rs-1976856/v1/dfef07425bc448a24477ccf8.png"},{"id":25565203,"identity":"886e8903-9a10-45cd-813b-346331d8afc9","added_by":"auto","created_at":"2022-08-23 17:46:52","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":1595126,"visible":true,"origin":"","legend":"\u003cp\u003eSEM photograph and EDX analysis around peeling-off on 15 days-AOP degraded PP sample in the seawater.\u0026nbsp;\u003c/p\u003e\u003cp\u003e\u003cbr\u003e\u003c/p\u003e","description":"","filename":"Figure5.png","url":"https://assets-eu.researchsquare.com/files/rs-1976856/v1/0caa6e3e0d55b049ecbccd45.png"},{"id":25564625,"identity":"98acff48-8671-4249-8c39-c676d7d1fdd8","added_by":"auto","created_at":"2022-08-23 17:41:52","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":197153,"visible":true,"origin":"","legend":"\u003cp\u003eLong diameter distributions of 9-, 12- and 15 days-AOP degraded PP samples in the seawater.\u0026nbsp;\u003c/p\u003e\u003cp\u003e\u003cbr\u003e\u003c/p\u003e","description":"","filename":"Figure6.png","url":"https://assets-eu.researchsquare.com/files/rs-1976856/v1/59606f1c054556b7d2929fe3.png"},{"id":25565204,"identity":"41a1950b-c538-4e58-804c-8dbcec8b3262","added_by":"auto","created_at":"2022-08-23 17:46:52","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":120255,"visible":true,"origin":"","legend":"\u003cp\u003eNanosized particle diameter distribution of 15 days-AOP degraded PP sample in the seawater.\u0026nbsp;\u003c/p\u003e\u003cp\u003e\u003cbr\u003e\u003c/p\u003e","description":"","filename":"Figure7.png","url":"https://assets-eu.researchsquare.com/files/rs-1976856/v1/a2dfc7b5ebd620935e2d293d.png"},{"id":28310315,"identity":"363946dc-0909-41be-97e4-140034511e17","added_by":"auto","created_at":"2022-10-27 06:59:33","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1820870,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-1976856/v1/e9b2d910-a3d5-4564-a87c-41ae341315fa.pdf"}],"financialInterests":"No competing interests reported.","formattedTitle":"Preparation method of marine microplastic model in a short degradation time","fulltext":[{"header":"Introduction","content":"\u003cp\u003eWaste from the production of plastic presents a major issue when discarded in the marine environment\u003csup\u003e\u003cspan additionalcitationids=\"CR2 CR3 CR4 CR5 CR6 CR7 CR8 CR9 CR10 CR11 CR12 CR13\" citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e\u003c/sup\u003e, as it spreads to the sea and leads to MP pollution. MP mainly comprises polypropylene (PP), polyethylene (PE), and polystyrene (PS) products and is generated by exposure to visible and/or UV light\u003csup\u003e\u003cspan additionalcitationids=\"CR13\" citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e\u003c/sup\u003e. In our previous study, PP degradation tests were performed in distilled water via an advanced oxidation process (AOP) using SO\u003csub\u003e4\u003c/sub\u003e\u0026bull;\u003csup\u003e\u0026minus;15\u003c/sup\u003e, where SO\u003csub\u003e4\u003c/sub\u003e\u0026bull;\u003csup\u003e\u0026minus;\u003c/sup\u003e functions as a highly-efficient initiator for the degradation of the plastic. However, many types of organic and inorganic constituents exist in the sea. In particular, Cl\u003csup\u003e\u0026minus;\u003c/sup\u003e reacts with OH\u0026bull; and inhibits photodegradation (autoxidation) initiation\u003csup\u003e\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e,\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e\u003c/sup\u003e. It is known that the generation of marine MP involves autoxidation in the presence of seawater. Therefore, to investigate the effects of marine MP on marine ecosystems, it is necessary to develop an accelerated degradation method that can be used to quickly establish a marine MP model. However, the effects of Cl\u003csup\u003e\u0026minus;\u003c/sup\u003e inhibiting the autoxidation process make it difficult to establish a model. A new initiator is thus needed to replace OH\u0026bull; to promote autoxidation in seawater. It is believed that SO\u003csub\u003e4\u003c/sub\u003e\u0026bull;\u003csup\u003e\u0026minus;\u003c/sup\u003e would also be an effective initiator in seawater, as it is converted to OH\u0026bull; by Cl\u003csup\u003e\u0026minus;\u0026thinsp;18\u003c/sup\u003e, with some produced OH\u0026bull; simultaneously inhibited by it. There is a competition between the two species; however, the preponderance of the OH\u0026bull; formation promotes the autoxidation process. In addition, SO\u003csub\u003e4\u003c/sub\u003e\u0026bull;\u003csup\u003e\u0026minus;\u003c/sup\u003e is gradually converted to SO\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e2\u0026minus;\u003c/sup\u003e, which affects the pH of alkaline seawater, with the equilibria of the reaction dependent on pH\u003csup\u003e\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e\u003c/sup\u003e. This change in pH accelerates the autoxidation process. It is considered that the utilization of SO\u003csub\u003e4\u003c/sub\u003e\u0026bull;\u003csup\u003e\u0026minus;\u003c/sup\u003e shortens the time required to prepare the marine MP model because of these effects.\u003c/p\u003e \u003cp\u003eIn this study, the size and O/C molar ratios of marine MP particles retrieved from the sea were determined by scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM/EDX) analysis to establish a new method for preparing a marine MP model. A PP model was prepared via AOP degradation using SO\u003csub\u003e4\u003c/sub\u003e\u0026bull;\u003csup\u003e\u0026minus;\u003c/sup\u003e as an autoxidation initiator in seawater. The degraded sample was studied in terms of its degradation behavior, shape, O/C molar ratio, and size to study the action of seawater on the plastic. The obtained results were then evaluated in terms of their equivalence with marine MP.\u003c/p\u003e"},{"header":"Materials And Methods","content":"\u003cp\u003e \u003cb\u003eMaterials.\u003c/b\u003e PP was supplied by Prime Polymer Co., Ltd. (product name: J-700GP). The MFR and density were 8 g/10min and 0.9 g/cm\u003csup\u003e3\u003c/sup\u003e. Potassium persulfate (K\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e8\u003c/sub\u003e) was purchased from Wako Pure Chemical Industries. Sea water was retrieved from Nagasaki fishing port in Nagasaki city, Nagasaki, Japan (around S1 in Table\u0026nbsp;1).\u003c/p\u003e \u003cp\u003e \u003cb\u003eScanning electron microscope (SEM) with energy dispersive x-ray spectroscopy analysis.\u003c/b\u003e The SEM / EDX analysis was carried out with a JSM-7500FAM (JEOL) with 5.0 kV. The working distance was about 3\u0026times;4 mm. Samples placed in dried oven maintained at 27\u0026deg;C for 30 min and were sputter-coated with gold before SEM imaging.\u003c/p\u003e \u003cp\u003e \u003cb\u003eParticle size measurement.\u003c/b\u003e The fragment sample size was measured with an optical microscope (Nikon ECLIPSE 50/POL) or with a dynamic light scattering method (Otsuka Electronics Co., Ltd. ELSZ-2000ZS).\u003c/p\u003e \u003cp\u003e \u003cb\u003eMP retrieving from the sea.\u003c/b\u003e MP retrieving was carried out at 26th July 2021 using the training vessel T/V Kakuyo-maru (155 gross tonnage: Faculty of Fisheries, Nagasaki University)\u003csup\u003e\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e, \u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e\u003c/sup\u003e. The sampling stations were summarized in Table\u0026nbsp;1. Each sampling of 1 L sea water was carried out in one day. The samples denoted as \u0026ldquo;D\u0026rdquo; were collected using a Conductivity Temperature Depth profiler (CTD) system at ca. 50 m below the sea level, and on the other hand the surface sampling (denoted as \u0026ldquo;S \u0026ldquo; ) was carried out with a 3 L stainless bucket.\u003c/p\u003e \u003cp\u003e \u003cb\u003eFiltration for SEM/EDX observation of MP retrieved from the sea.\u003c/b\u003e Filtration was carried out with a polycarbonate membrane filter (Merck Isopore\u0026trade; membrane) with 0.8 \u0026micro;m or 8 \u0026micro;m pore size without pretreatment.\u003c/p\u003e \u003cp\u003e \u003cb\u003eDegradation using advance oxidation process (AOP).\u003c/b\u003e The PP film was molded into thin films (30\u0026times;30\u0026times;0.060 mm) by compression molding at 180\u0026deg;C under 10 MPa for 11 min. The AOP degradation procedure was according to reports \u003csup\u003e\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e, \u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e\u003c/sup\u003e. 1) Each five pieces of the film were put into a 100 ml glass vessel equipped with a 20 ml aqueous solution containing 0.54 g K\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e8\u003c/sub\u003e at ca. 65 \u0026deg;C for 12 h under stirring with a stirrer tip speed of ca. 100 rpm. 2) The equal amount of K\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e8\u003c/sub\u003e aqueous solution was added to compensate for the consumption of oxidant, and its degradation was carried out for 12 h under the same conditions. 3) And then only the five pieces of the film moved to a new 100 ml glass vessel equipped with the 20 ml aqueous solution containing 0.54 g K\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e8\u003c/sub\u003e, and their AOP degradations were restarted under the same conditions. The AOP degradation was carried out for a predetermined number of days using 1) to 3) as one set. The pH value of solution was changed from 8 to 3 during the one set.\u003c/p\u003e"},{"header":"Results And Discussion","content":"\u003cp\u003e \u003cb\u003eRetrieved MP sizes and their O/C molar ratios.\u003c/b\u003e Figure\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e shows an SEM image and EDX analysis of a sample of tiny plastic particles retrieved from the sea (sampling station: S1-B) that have a particle size of around 450 nm and an O/C molar ratio of 0.15. This low ratio suggests that the particles are composed of artificial plastic material. The particles may be some phytoplankton; however, their body is composed of polysaccharides such as cellulose, the O/C ratio of which is much high, e.g., 0.83. The results reveal that marine MP can be distinguished from the phytoplankton according to the O/C molar ratio. Figure\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e(a) shows the relationship between the O/C molar ratio and the long diameter of MP samples retrieved from the sea. PE, PP, PS, polyvinylchloride (PVC), and polyethylene terephthalate (PET) are produced globally on a huge scale. The total amount of these commercially produced plastics constitutes around 80% of all thermoplastics\u003csup\u003e\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e, \u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e\u003c/sup\u003e. For example, PP and PE represent 22% and 23% of the Japanese manufacturing of resins (in 2018), respectively. Consequently, most marine MP is composed of PE, PP, PS, PVC, and PET\u003csup\u003e\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e\u003c/sup\u003e. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e(a), most of the MP samples show O/C molar ratios of \u0026lt;\u0026thinsp;0.4. The MP contained almost no PET with the 0.4 O/C molar ratio. Similarly, only a small proportion of the MP particles were identified as PVC with a high chlorine content. The O/C molar ratios indicate that the MP samples retrieved from the sea mainly composed of PE, PP and PS. Most of the MP particles exhibit diameters of \u0026lt;\u0026thinsp;20-\u0026micro;m long and O/C molar ratios of 0.1\u0026ndash;0.2. These results thus provide an index of size and the degree of degradation (degree of oxidation) for modeling. Figure\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e(b) shows the relationship between the AOP degradation time and the O/C molar ratio of a PP sample in distilled water. The ratios gradually increased with up down. This behavior can be attributed to repeated oxidation and peeling off\u003csup\u003e\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e, \u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e\u003c/sup\u003e. After 75 days, an O/C of 0.1 was achieved, indicating that it takes a long time using the AOP degradation method to achieve the same ratio for PP as that of marine MP. To investigate the effect that MPs have on marine organisms, it is thus necessary to develop a method to more quickly establish an MP model.\u003c/p\u003e \u003cp\u003e \u003cb\u003eInhibiting and accelerating effects on autoxidation.\u003c/b\u003e Salinity lowers the degradation level of polyolefins such as PP and PE\u003csup\u003e\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e, \u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e, \u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e\u003c/sup\u003e. The refractive index of seawater increases due to salinity, and the utilization rate of UV light decreases in the degradation\u003csup\u003e\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e, \u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e\u003c/sup\u003e. Wu et al. reported that aqueous Cl\u003csup\u003e\u0026minus;\u003c/sup\u003e acts as an inhibitor in the photooxidation of PP in seawater\u003csup\u003e\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e\u003c/sup\u003e. Figure\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e shows the transformation of radical species from SO\u003csub\u003e4\u003c/sub\u003e\u0026bull;\u003csup\u003e\u0026minus;\u003c/sup\u003e to OH\u0026bull; in seawater. In the case of PP photodegradation in seawater, Cl\u003csup\u003e\u0026minus;\u003c/sup\u003e reacts with OH\u0026bull; generated by solar irradiation and converts to ClOH\u0026bull;\u003csup\u003e\u0026minus;\u003c/sup\u003e, which is a less reactive molecule\u003csup\u003e\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e\u003c/sup\u003e. To avoid the inhibitory effect of Cl\u003csup\u003e\u0026minus;\u003c/sup\u003e, it is thus necessary to change the initiator of the oxidation degradation (autoxidation) reaction from OH\u0026bull; to another radical species. Considering the reactivity of radical species, SO\u003csub\u003e4\u003c/sub\u003e\u0026bull;\u003csup\u003e\u0026minus;\u003c/sup\u003e is suitable for autoxidation in seawater. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e, the SO\u003csub\u003e4\u003c/sub\u003e\u0026bull;\u003csup\u003e\u0026minus;\u003c/sup\u003e initiator is transformed by Cl\u003csup\u003e\u0026minus;\u0026thinsp;18\u003c/sup\u003e. A large amount of the SO\u003csub\u003e4\u003c/sub\u003e\u0026bull;\u003csup\u003e\u0026minus;\u003c/sup\u003e is converted into OH\u0026bull;, with some of the OH\u0026bull; converted into ClOH\u0026bull;\u003csup\u003e\u0026minus;\u003c/sup\u003e. However, since the production of ClOH\u0026bull;\u003csup\u003e\u0026minus;\u003c/sup\u003e requires re-reaction with Cl\u003csup\u003e\u0026minus;\u003c/sup\u003e, the residual amount of OH\u0026bull; increases. The initiation efficiency of autoxidation is greatly improved in seawater due to the reactivity of OH\u0026bull; being higher than that of SO\u003csub\u003e4\u003c/sub\u003e\u0026bull;\u003csup\u003e\u0026minus;\u003c/sup\u003e. Moreover, the reaction between Cl\u003csup\u003e\u0026minus;\u003c/sup\u003e and OH\u0026bull; also occurs and produces Cl\u0026bull;. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e, two Cl\u0026bull; atoms couple to produce Cl\u003csub\u003e2\u003c/sub\u003e, which then reacts with H\u003csub\u003e2\u003c/sub\u003eO and forms ClOH, with the equilibria of the two reactions dependent on pH\u003csup\u003e\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e\u003c/sup\u003e. Since the pH of seawater is around 8, the equilibrium is biased toward the less reactive ClO\u003csup\u003e\u0026minus;\u003c/sup\u003e, which suppresses the autoxidation of PP in seawater. It is noted here that as the SO\u003csub\u003e4\u003c/sub\u003e\u0026bull;\u003csup\u003e\u0026minus;\u003c/sup\u003e gradually converts to SO\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e2\u0026minus;\u003c/sup\u003e, the pH value of the K\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e8\u003c/sub\u003e in seawater solution decreases from ca. 8 to ca. 3 by the time of daily exchange (see \u003cspan refid=\"Sec2\" class=\"InternalRef\"\u003eMaterials and methods\u003c/span\u003e section). This procedure ensures that there is a bias in the ClOH-rich equilibrium\u003csup\u003e\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e\u003c/sup\u003e for a period of time before the exchange of fresh K\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e8\u003c/sub\u003e seawater solution. The ClOH has a longer lifetime\u003csup\u003e\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e\u003c/sup\u003e and migrates deeply into the polymer matrix before dissociating into radicals and then initiates autoxidation\u003csup\u003e\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e\u003c/sup\u003e. The autoxidation proceeds from the PP interior as well as the surface, and the rate of MP formation is synergistically accelerated. The usage of SO\u003csub\u003e4\u003c/sub\u003e\u0026bull;\u003csup\u003e\u0026minus;\u003c/sup\u003e generates both OH\u0026bull; and ClOH, overcoming the inhibiting effect and accelerating the autoxidation process.\u003c/p\u003e \u003cp\u003e \u003cb\u003eComparison of fragmentation behavior.\u003c/b\u003e Figure\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e shows SEM images of PP degraded via AOP for 15 days in seawater and pure water. Numerous micro pits can be observed on the surface of the seawater sample, which are traces of chemi-crystallization that is related to the autoxidation process\u003csup\u003e\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e, \u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e\u003c/sup\u003e, showing that the PP degradation rapidly progresses. However, the surface of the pure water sample exhibits a lattice-like texture formed by cracks and is relatively smooth. The degree of degradation of the PP in pure water is thus considerably less than that of the seawater sample. Figure\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e shows SEM images and EDX analysis around the peeling-off location on the PP sample degraded via AOP for 15 days in seawater. Much microsized peeling-off marks can be observed, and the O/C molar ratios are around 0.17, 0.13, and 0.13 (see arrows in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e). These values are similar to those of the MP samples retrieved from the sea, indicating that a MP sample with the same degree of degradation can be prepared in a short degradation time of 15 days. Moreover, it was determined that the combination of seawater and K\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e8\u003c/sub\u003e initiator promotes excellent accelerated degradation of the plastic.\u003c/p\u003e \u003cp\u003eIn our previous study, PP film degradation tests were performed in water with a specific photocatalyst under visible light irradiation\u003csup\u003e\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e\u003c/sup\u003e or using the same AOP treatment\u003csup\u003e\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u003c/sup\u003e. The results revealed that MP particles are generated by planar exfoliation via autoxidation in the presence of water. Therefore, it is believed that the size of the MP is dependent on the degree of degradation, i.e., the degradation time. Figure\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e shows the long diameter distributions of PP degraded via AOP over 9, 12, and 15 days. After 9, 12 and 15 days of degradation, 79, 136 and 279 MP particles were recovered by filtration, respectively, indicating that the size is dependent on the AOP degradation time. The size distribution narrows with increasing AOP degradation time, with a bias toward smaller sizes. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e, it is confirmed that nanosized PP particles are obtained over 15 days of AOP degradation. These results suggest that the size of the MP particles can be controlled according to the degradation time.\u003c/p\u003e"},{"header":"Conclusion","content":"\u003cp\u003eTo establish a marine MP model, the MP samples retrieved from the sea were measured in terms of their sizes and O/C molar ratios, with most of them showing a size of \u0026lt;\u0026thinsp;20 \u0026micro;m in diameter and O/C molar ratios of 0.1\u0026ndash;0.2, indicating that the marine MP mainly comprises PE, PP, and PS. After 75 days of the AOP degradation of PP in distilled water, an O/C of 0.1 was reached. It took a long time for the O/C ratio of the AOP degradation of PP in water using a SO\u003csub\u003e4\u003c/sub\u003e\u0026bull;\u003csup\u003e\u0026minus;\u003c/sup\u003e initiator in water to reach the same value as that of the marine MP. However, the SO\u003csub\u003e4\u003c/sub\u003e\u0026bull;\u003csup\u003e\u0026minus;\u003c/sup\u003e initiator was converted into OH\u0026bull; by aqueous Cl\u003csup\u003e\u0026minus;\u003c/sup\u003e in seawater, and the initiation efficiency was greatly improved in seawater. Moreover, the SO\u003csub\u003e4\u003c/sub\u003e\u0026bull;\u003csup\u003e\u0026minus;\u003c/sup\u003e gradually converted to SO\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e2\u0026minus;\u003c/sup\u003e and led to a bias toward a ClOH-rich equilibrium. The ClOH dissociated into OH\u0026bull;. The use of SO\u003csub\u003e4\u003c/sub\u003e\u0026bull;\u003csup\u003e\u0026minus;\u003c/sup\u003e overcame the Cl\u003csup\u003e\u0026minus;\u003c/sup\u003e inhibiting effect on the autoxidation process and provided an accelerating effect in seawater. The O/C molar ratio of the PP sample degraded via AOP over 15 days in seawater was the same as that of the marine MP. The combination of seawater and K\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e8\u003c/sub\u003e initiator thus promoted excellent accelerated degradation.\u003c/p\u003e \u003cp\u003eMuch microsized peeling-off marks were observed for the PP sample degraded via AOP over 15 days in seawater, with O/C molar ratios of around 0.17, 0.13, and 0.13. These values are similar to those of MP samples recovered from the sea, indicating that an MP sample with the same degree of degradation of the sea-derived MP can be prepared in a short degradation time of 15 days. The combination of seawater and SO\u003csub\u003e4\u003c/sub\u003e\u0026bull;\u003csup\u003e\u0026minus;\u003c/sup\u003e initiator promoted excellent accelerated degradation of the plastic. Nanosized PP particles were obtained over 15 days of AOP degradation, showing that the size of MP could be controlled according to the degradation time.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eData availability\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe data that support the findings of this study are available from the corresponding author, [HN], upon reasonable request.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAcknowledgements\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThis work was supported\u0026nbsp;by the Environment Research and Technology Development Fund, No. 1MF-2204 from Ministry of the Environment, Government of Japan, by the Grant-in-Aid for Scientific Research, No. 20K05587 from Japan Society for the Promotion of Science, by Taihei Environmental Science Center Co., Ltd. and by financial supports of Nagasaki University organization for marine science and technology and for function enhancement program of research.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthor contributions\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eH.N. proposed the study and wrote the whole manuscript. M.Y. and Y.K. performed retrieving the MP samples from the sea. Y.O., and T.U. performed the experiment and analyzed the experimental data. All authors reviewed the manuscript.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n \u003cli\u003e\u003cspan\u003eDerraik, J. G. B. The pollution of the marine environment by plastic debris: a review. Mar. Poll. Bull. \u003cstrong\u003e44\u003c/strong\u003e(9), 842\u0026ndash;852 (2002).\u003c/span\u003e\u003c/li\u003e\n \u003cli\u003e\u003cspan\u003eBarnes, D. K. A., Galgani, F., Thompson, R. C., Barlaz, M. Accumulation and fragmentation of plastic debris in global environments. Phil. Trans. R. Soc. B \u003cstrong\u003e364\u003c/strong\u003e(1526), 1985\u0026ndash;1998 (2009).\u003c/span\u003e\u003c/li\u003e\n \u003cli\u003e\u003cspan\u003eThompson, R. C., Swan, S. H., Moore, C. J., vom Saal, F. S. Our plastic age. P \u003cem\u003ePhil. Trans. R. Soc. 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Chemi-crystallization. Polymer \u003cstrong\u003e38\u003c/strong\u003e(26), 6379\u0026ndash;6387 (1997).\u003c/span\u003e\u003c/li\u003e\n \u003cli\u003e\u003cspan\u003eCraig, I. H., White, J. R., Kin, P. C. Crystallization and chemi-crystallization of recycled photo-degraded polypropylene. Polymer \u003cstrong\u003e46\u003c/strong\u003e(2), 505\u0026ndash;512 (2005).\u003c/span\u003e\u003c/li\u003e\n\u003c/ol\u003e"},{"header":"Table","content":"\u003cp\u003eTable 1 Sampling station, coordinates, and depth.\u003c/p\u003e\n\u003cp\u003e\u003cimg 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QEQk+fi+H282m9j3/cJ8m80mFpHYcZzGdYZhmFlv/mOaZhe7AjyJUioOwzCO43/HeToGNptNbNt28t1xnMI8tm1nvqfXWUfHilKqdLrv+5Uxo6e12Y5t24Uyx3Ecm6aZ2TfTNAvb0nGv97uOUqryPBGGYWZb+BjS5/b8sdgmdnTM5WNws9lktpGev20domMkf9w1xXwcl8dCfh35fUhvx/f9Qmzl4zwdw0qp2vioi3fqVLwG3/cLx3S+TkE7B5N45E+UVY0T/XvbxEMra6joE/SB5Xd4w/IVuWmameO8LBHPNxLyFb/v+6XLla2nrEGi11EWj5rjOK1O8L7vx6ZpNjb44vhfIqQbffq7ThqatqcrnbJyk3h8XFWN4raxkz8ubNtOYmqz2RTqnTYNbd2YL2vQN8W8Lmc6+Ukr2y/btjNxXJaE5es9x3GSfcknW2XbbHuhAXgJZbFbloyg2UF0tdK3sr99+5b8tlgsxLbtwryLxULiON7LdgeDgfi+LyLSuosI0KV+v5/5vt1uZTqdJt9Ho1FhGcMw5OTkJLOO9PE8m83kv//+q92u67oyn88L2xd57IJhWZY4jlO6fRGR+/t7+fr1a+02dFkWi0Xh94eHh6Ts6f1QSsmvX79EROTv379i27b0+32JoihzvqiyWCxEKSWWZXHL/cC1iZ3tdpv5LiJydnYm6/VaRB7rjMvLy2Ra2256k8lEbm5uSqc1xbw2GAxKly/br5OTk0yXp/w2Hh4exHGczG/39/cym80kiiIxTbNye3XKungBL6EsdkVEwjDk3L+jg0g8tPxJq01DBvioDMOobKykrddr+fLlS/J9sVjIcrlM+lwvl8vShEILgkDu7+8rk4rv37+LiMjx8XFlP+6Tk5PGhspwOGzcn7KG3P39vYg8Npb0OaHf79fuU9p2uxUREaVUq/lxOPKxIyJye3tbOq9uvIRhmMTBeDyW6+vr2m24rivj8bjV8VoW81EUyXw+b1w27fb2Vsbjcem01Wold3d3lcnN379/K5etE0URDTzgAziIxGMwGIhpmrJerzMD/gaDQWVjaF8syxKR8qtGwGvQA0nDMBSlVO1V1dVqJY7jFBo119fXEj921WxMCObzeeldCO3m5kaUUnJ3dydxHEsYhhKGYWbgdlkjJl/OusaXjr90gyeKIgnDMLmKNRqNkn2pK2+ZzWYjIlI62ByHqSx2Li4uZL1eZ+4Y3t3dici/uwb9fj+JLZ3UVomiqDap1+pivt/v71Q/6cZ/2TK9Xk8syxLP8wqxoGNql3pXKZUkYST2wMdwEImHyGNDSd/6tSxrpyfk7CL/BA7btvfWdQvYh+l0KnEcJ90A664+LpfLxkZ/nclk0qoRf3FxkczX7/fFcRxZr9etrnBGUSR3d3eNjRmd0OQbMp8+fWqxJ/UGg0FSZrqDQKQ8dqbTqdi2ndRBvV5PPM8T0zSftI228bVLzLfZZtVdGJ0wKaUKCdZThGGYrDMMw2etC3gOwzCSu+Panz9/RCnV+u44Hh1M4iHy7+Srx3ZYliWu6+51G/okqT+e53WW5ADPMRqNCv2w0wzDaOzm0cTzvMxVS8/zksZ/XUwcHx+33sbV1VUSZ+mEwrKsQj/0dGzatv3kvuZldKPS8zy5urrayzrxPtXFjh5HmG5Mz2aznbcRBEFyF19/wjBMYqEsaW+K+SaTyaRVWZvu1DzFLt0fgX0bj8eFboq3t7dyfn7+SiV6vw4i8QiCINPI0Sd+pVRmIF+T/HPK6557rum7HbrLFfCWHB8flz4Xv814iTbyibht26KUkjiOkzsU5+fn8uPHj8Kyba8k6QsK+cac7/uVDSDXdcXzvJ27VDXRg813Oa/gY9kldpRSYtv2k5LfwWBQiC+9vjiOK2OnKuabuK4rZ2dnrcuqlJKjo6Odt1NHxytdGvHSdH2lL1brxH/fdcghOIjEQ+TxtnfergPqRqNR4UTfBn1T8VZZllW4gjkcDmU2m2UaLq7rdvYivG/fvkkYhpm7j5Zl7RyfbRmGIZeXlxKGYSdXULu42ov3oW3s6ItYtm2/eMOlLOab6NhMd2cMgqCyx4DrumIYxt7uJqYZhvGsrmLAU223W7m8vJReryenp6d0o3+qjh7T+6boZ4rnn4de9xIj2cN7POI4Tt4pwDP98drS75WRivfL6Jfi5T/7emlX/vn/Wv5FnG3eC1JFr6vsPR77iEUd6/pTdp7Iv0wOH0M+PtL/921iR9cH0tE7KvJ1WpuYb5J+t1XVutL7tWvdmVe1refsA4C3oxfHHz9lC4JAHh4e5OjoSE5PT5Pfy642ua6b6SahlKq9ghlFUeMdDcdxnjVAFwAAAHjvDiLxAAAAAPC6DmaMBwAAAIDXQ+IBAAAAoHMkHgAAAAA6R+IBAAAAoHMkHgAAAAA6R+IBAAAAoHMkHgAAAAA6R+IBAAAAoHMkHgAAAAA6R+IBAAAAoHMkHgAAAAA6R+IBAAAAoHMkHgAAAAA6R+IBAAAAoHMkHgAAAAA6R+IBAAAAoHMkHgAAAAA6R+IBAAAAoHMkHgAAAAA6R+IBAAAAoHMkHgAAAAA6R+IBAAAAoHMkHgAAAAA6R+IBAAAAoHMkHgAAAAA6R+IBAAAAoHMkHgAAAAA6R+IBAAAAoHMkHgAAAAA6R+IBAAAAoHMkHgAAAAA6R+IBAAAAoHMkHgAAAAA6R+IBAAAA5BiGIb1eL/kEQZCZ7rpuMs113Vcq5ftC4gEcmPSJdDKZFKavVqvMiXa1WhXmGQ6HlSfiOqvVSgzDaFW+9HxRFFWWpWodTeUeDoel04fDoQRBULpvuhxN66irqPC+TSYT6fV6EkVRYVqb2NHHVtXxkT7GmmKlrGxlMd0U87rxVCV/3Lc5b+T/PukYnkwmlfuWXkfZZ9e/CfBUq9VKzs/PJY7j5DMYDJLpruvKjx8/kmk/fvwg+WgjPiAiknx83483m03s+35hvs1mE4tI7DhO4zrDMMyst+xTtg3gNSil4jAM4zj+d5ynj8/NZhPbtp18dxynMI9t25nv6XXW0bGilCqd7vt+LCKxaZqV09psx7bt0rgzTTOzb6ZpFral417vdx2lVOV5IgzDzLbwMaTP6/ljsU3s6JjLx+Bms8lsIz1/WTyU0TGSP+6aYj6Oy2Mhv478PqS34/t+IbbycZ6OYaVUbXzUxXvbvwfwXE11Wz529XGLegfzF8qfKKsaJ/r3tomHVtVQ0Y2TqsYW8JLyJ1HTNDPHeVmSnG8k5Ct+3/dbJddKqdIGiV5HXZLuOE6rhrzv+7Fpmo0Nvjj+lwjpikN/10lD0/Z0IlNWbhKPj6uqUdw2dvLHhW3bSUxtNptCvdOmoa0b82UN+qaY1+VMN6DSyvbLtu1MHJclYfn60HGcZF/yDbaybba90AB0QR+DZcl8enpe07GNOD6Irlb6Vva3b9+S3xaLhdi2XZh3sVhIHMd72/Z2uxXHcSQMw9Lb08BL6vf7me/b7Vam02nyfTQaFZYxDENOTk4y60h3IZnNZvLff//Vbtd1XZnP54Xtizx2wbAsSxzHKd2+iMj9/b18/fq1dhu6LIvFovD7w8NDUvb0fiil5NevXyIi8vfvX7FtW/r9vkRRlDlfVFksFqKUEsuySrve4HC0iZ3tdpv5LiJydnYm6/VaREQGg4FcXl4m09p205tMJnJzc1M6rSnmtXQXkrSy/To5Ocl0ecpv4+HhQRzHyfx2f38vs9lMoigS0zQrt1eHOhQv5ejoSOI4ljAMxfO8QvfBP3/+iFKqdFldp6DcQSQeWv6k1aYhsw/T6VSUUuJ5Ho0TvBmGYVQ2VtLW67V8+fIl+b5YLGS5XCZ9rpfLZWlCoQVBIPf395VJxffv30VE5Pj4uLIf98nJSWNDZTgcNu5PWUPu/v5eRB4bS/qc0O/3a/cpbbvdiohUVkI4XPnYERG5vb0tnVfXDWEYJnEwHo/l+vq6dhuu68p4PG51vJbFfBRFMp/PG5dNu729lfF4XDpttVrJ3d1dZXLz9+/fymXrRFFE/YkXo+ubfr8vcRyLbdtyfn7+yqX6GA4i8RgMBmKapqzX68yAv8FgUNkY2reLiwsREfn9+/eLbA+oogeShmEoSqnaq6qr1Uocxyk0aq6vr0sH25WZz+eldyG0m5sbUUrJ3d1dcoUpDMPMwO2yRky+nHWNLx3n6QZPFEUShmFyBXo0GiX7UlfeMpvNRkSkdLA5DlNZ7FxcXMh6vc7cMby7uxORf3cNdEMnjuMkqa0SRVFtUq/VxXy/39+pHtSN/7Jler2eWJYlnucVYkHH1C71rlIqScJI7PGaFouFhGFI8rsHB5F4iDw2lPStX8uydnpCDvCRTKdTieNYfN8XEam9+rhcLhsb/XUmk0mrRvzFxUUyX7/fF8dxZL1etzrJR1Ekd3d3jY0ZndDkGzKfPn1qsSf1BoNBUma6g0CkPHam06nYtp3UQb1eTzzPE9M0n7SNtvG1S8y32WbVXRidMCmlCgnWU4RhmKwzDMNnrQt4rnTye3x8XDgmdX21jzrlIzuYxEPk38lXj+2wLItHn+FgjUajQj/sNMMwGrt5NPE8L3PV0vO8pPFf1yg5Pj5uvY2rq6ukD246obAsq9APPU49FtG27Sf3NS+jG5We58nV1dVe1on3qS529DjCdGN6NpvtvI0gCJK7+PpT1R9da4r5JpPJpFVZm+7UPMUu3R+BruhjUF/oSt891D1a9lWnfFQHkXgEQZBp5OgTv1IqM5CvSf455XXPPc/78eOHiEjjIFzgJR0fH5c+F7/NeIk20g193dhXSkkcx8mJ+/z8PImPNKVUq4aGvqCQb8z5vl/ZAHJdVzzP27lLVRM92HyX8wo+ll1iRykltm0/qaEyGAwK8aXXF8dxZexUxXwT13Xl7OysdVmVUnJ0dLTzduroeKVLI16aYRiyXC4zvzmOk7l7OJvNkruKqHYQiYeIFA4YEdl5QN1oNCqc6NtwXVfCMEyemAO8FZZlFa5gDodDmc1mmWPVdd3OXoT37ds3CcMwc/fRsqyd47MtwzDk8vJSwjDsJB67uNqL96Ft7OiLWLZt7z35bVIW8010bKa7MwZBUNljwHVdMQyjkyu/hmE8q6sY0Eb+jeU3NzeF43k6ncr5+Xkyz3w+f7Fxw+9al8/qfSv0M8Xzz0Ove4mR7Pk9Hrz0CK9Nx0H6k6eP1/xnX8dv/vn/Wv5FnM956aZeV9l7PKTimey70LGuP2XnifzL5PAx5OMj/X/fJnb0O2ako3dU5Ou0NjHfJP1uq6p1pfdr17ozr2pbz9kHAG9HL473+NKKNyoIAnl4eJCjoyM5PT1Nfi+72uS6bqabhFKq9gpmFEWNT9vo6soqAAAA8F4cROIBAAAA4HUdzBgPAAAAAK+HxAMAAABA50g8AAAAAHSOxAMAAABA50g8AAAAAHSOxAMAAABA50g8AAAAAHSOxAMAAABA50g8AAAAAHSOxAMAAABA50g8AAAAAHSOxAMAAABA50g8AAAAAHSOxAMAAABA50g8AAAAAHSOxAMAAABA50g8AAAAAHSOxAMAAABA50g8AAAAAHSOxAMAAABA50g8AAAAAHSOxAMAAABA50g8AAAAAHSOxAMAAABA50g8AAAAAHSOxAMAAABA50g8AAAAAHSOxAMAAABA50g8AAAAAHSOxAMAAABA50g8AAAAAHSOxAMAAABA50g8AAAAAHSOxAMAAABoYBiG9Ho96fV6EkXRaxfnXSLxAA5M+sQ5mUwK01erVTK91+vJarUqzDMcDpPpQRC03vZqtRLDMFqVLz1fFEWVZalaR1O5h8Nh6fThcChBEJTumy5H0zrS8+zy98HbN5lMKhsdbWJHH1tVx0f6GGuKlXR52jaGyrbpuq70er3Gbelju2q9ZR9dnnQMTyaTyn2rWs8ufxOgC4ZhyMXFhcRxLJvNRpRSJB9PcFCJR75CCIKgtGLIn8hd161cZ74hkv+UNUyA12IYhtzc3CQnTs/zMjEQBIHc3d1JHMcSx7YkPMQAACAASURBVLE4jiOWZWXmmUwmMh6Pk3nG43Grk28URWJZVuV03WgzDEPiOJbtdptM+/37t4iI/Pfff43bmUwmEoZh4ffhcCj9fj8pt/4tbb1ey+fPn+XXr18iIjIYDDLT08srpWS9XhfOD9fX1xKGodi2LXEcF9aB96vX64nneaXT2sROEARyenoqYRgmMXh6eppJBJRSyTqWy2VtHeK6rpydnSXzm6ZZ2xiqWtft7a2Yplm5HV3PrdfrynLofdKfzWYjpmlKv98XkWwM39zcyPn5eem64jgW3/dFRArrjOOYxAOvQsfxdDoVkce6wTRN+f79+2sW6106mMSj1+slDYE4juXu7k5OT08L80VRlDTM9EcfaGV0Q8RxHBGRwol3vV63upIEvISbm5ukIaBPnH/+/EmmPzw8yGKxSL5Pp1NRSsnd3V3yWxRFMhqNku/z+TxpVNQ5Pz+vbNysViuxLEt835fr6+vC9D9//oht20nZq6xWq9JGVxAEsl6v5du3b8lvi8VC1ut10ujTy3358kXu7+/Ftu3abRmGIbZty+XlZes7MXjf0o3ivDaxM5/PM8fxYDAQ27ZlPp+LyONxqusSPb3O8fFxJhb19svise4C2na7ldlsVjk9X8/lffr0qRCbP3/+lPF4nHz/8+dPkoiEYShfv36t3F6dsvMD0LXlcllIlsfjsdzc3LxSid6vg0g8dMMi3+goa1h8//49qQSeazAYJJUUDRO8BfnGwXa7zSTW6UaMZhiGnJycZNaRPp5ns1njnQjXdWU+n5cmDvpOiOM4pdsXEbm/v2/VUJnNZpnGn/bw8JCUPb0fSqnk7sbfv3+TRmEURZnzRZXFYiFKKbEsi1vuB65N7Gy328x3EZGzs7PkTsJgMJDLy8tkWlM3vfw29fF9dHSU+T2KIrm9va1NLp5zZ65s2Zubm8x54f7+XmazmURRJKZpPml7ZV1DgZdQFrsij3flOPfv5iASDy1/0so3ZKIoEs/zxLIsbufiw9Pdrpqs12v58uVL8n2xWMhyuUy6Ey6Xy9o7EUEQyP39fWVSoW9VHx8fV/bjPjk5aWyoDIfDxv0pa8jd39+LyGNyos8J/X6/8e6KpruEKaVazY/DkY8dkcduTWV04yUMwyQOxuPxTlf4gyAQpVQhVs7PzyvXE0XR3i62pcthGEYhhgaDgfz9+zdzJ6StKIpo4AEfwEEkHrpLie72pK/WDgaDTGPo79+/mf7fuwxmraL7tFc1uoCXpgeShmEoSqnaq6qr1Uocxyk0IK6vr5NYaUoI5vN56V0I7ebmJumSEsexhGEoYRhm+qPXdXfU5RyPx5XJgo6/dIMniiIJwzC5ijUajZJ9qStvmc1mIyLVfehxeMpi5+LiQtbrdaZe0V2x9HzpcUTpcU5t/Pz5U5bLZeY313ULv6X1+/2910/5blYi/2IqX+/WUUolSRiJPfAxHETiIfLYUNL9Uy3LKk0q0g2o7XYrvu/v3IUiP7hcjysB3orpdJrpq1539XG5XDY2+utMJpNWjfiLi4tkvn6/L47jyHq9bj1o/e7urrExoxOafEPm06dPLfak3mAwSMpMdxCIlMfOdDoV27aTOkgPVq8b2N1WEASFO4P6osJLP+DA87y9JDPpweVlD4wAXophGMndce3Pnz+ilGp9dxyPDibxEPnX4NJjOyzLqh1wNxqNxDTNVgNntfwTODzP28udE2DfRqNR5WBRkccT7XMHcnqel7lq6Xle0vivi4nj4+PW27i6ukriLJ1Q5LtMpq8k6/PAU/ual9GNSs/z5Orqai/rxPtUFzuLxaLQmK4be9GG7i6VT3R+/vwpl5eXSWzoB6qcnp52dncuCIK9JFJ5u3R/BPatbCD57e1t5dPZUO0gEo/8Y3P1iV8plRnIVyZ9oss/o73N06r03Y66x4gCr+X4+Lh0PFOb8RJt5BNx27aTx4XqK6Ln5+fy48ePwrJtryTpCwr5xpzv+5VdVVzXFc/zdu5S1UQPNm86r+Dj2iV2lFJi2/azk9+qMRzpJEc/aVHksWtgV0+HKutmtS86XunSiJem6yt9sVo/KXHfdcghOIjEQ0RK+7i2GVAXRVHyZI7RaFRoSLVB31S8VZZlFa62DodDmc1mmUa/67qdvQjv27dvEoZh5u6jZVl7H/CqGYYhl5eXEoZhJ1dQd+2Xj4+jbezoi1i2bT+74dLr9QrH3Gs2zPfVzaqKYRidJTZAne12m9xBPD09pRv9Ex1M4rFerwsn49lsVvus/slkIp8/f35W42Q4HCYvEwNeU/6Nyb1erzA43DAMWa/Xcnp6mpnv9va2s37i+rn+6S4hvu/vtfGS3vfz83OJ4/jJca0H5+uHVZR119RXlvGxGIaR3L1WSmX+79vEjn7zt2VZEobhs5IO/VI/keLYws+fPz9jL8v1er3kTl5VV8nVavXsuk7/fUSyg8v1JwxDHtaCV7PrhWcU9eID+OsFQSAPDw9ydHSUeWlg/mrTZDLJvJW2TeMniqLGOxqO4zxrgC4AAADw3h1E4gEAAADgdR1MVysAAAAAr4fEAwAAAEDnSDwAAAAAdI7EAwAAAEDnSDwAAAAAdI7EAwAAAEDnSDwAAAAAdI7EAwAAAEDnSDwAAAAAdI7EAwAAAEDnSDwAAAAAdI7EAwAAAEDnSDwAAAAAdI7EAwAAAEDnSDwAAAAAdI7EAwAAAEDnSDwAAAAAdI7EAwAAAEDnSDwAAAAAdI7EAwAAAEDnSDwAAAAAdI7EAwAAAEDnSDwAAAAAdI7EAwAAAEDnSDwAAAAAdI7EAwAAAEDnSDwAAAAAdI7EAwAAAEDnSDwAAAAAdI7EAwAAAEDnSDwAAAAAdI7EAwAAAEDnSDwAAAAAdI7EAwAAAMgxDEN6vV7yCYIgM9113WSa67qvVMr3hcQDODDpE+lkMilMX61WmRPtarUqzDMcDitPxHVWq5UYhtGqfOn5oiiqLEvVOprKPRwOS6cPh0MJgqB033Q5mtZRV1HhfZtMJtLr9SSKosK0NrGjj62q4yN9jDXFSro8+lNWrrS6xlMTfWxXrbfso8uTjuHJZFK5b1Xr2eVvAuzDarWS8/NzieM4+QwGg2S667ry48ePZNqPHz9IPtqID4iIJB/f9+PNZhP7vl+Yz7btzLyO41SuMwzDzLxln7JtAK9BKRWHYRjHcRxvNpvC8bnZbGLbtpPvjuMU5rFtO/M9vc46OlaUUqXTfd+PRSQ2TbNyWpvt6PjNx51pmpl9M02zsC0d73q/6yilKs8PYRhmtoWPIX1ezx+LbWJHx1w+BjebTWYb6fnL4iG9jfT6TdOsjRM9Pb09/XvddvL1XFk5yv4e6XWmY1gpVRsfdfFeV05gn5rqtnws6eMW9Q7mLyQimRNdVeNEnxR3VdVQ0Y2Tp6wT2Lf8SdQ0zUzDuSxJzjcS8hW/7/utkmulVGyaZmks6BN21Xocx2nVkPd9P2lc1TX44vhfY0pXHPq7ThqatqcTmarzCInHx1TVKG4bO/njwrbtJKY2m00hka1raJcdd1Vx5DhOZeKhlCr8VqaqnitbNn+BQm8/josNtrxdLjQAXdDHYL7tmJ+e13RsI44PoquVvq387du35LfFYiG2bRfm/f79u8zn871te7vdiuM4EoZhabcW4CX1+/3M9+12K9PpNPk+Go0KyxiGIScnJ5l1pLuQzGYz+e+//2q367quzOfzwvZFHrtgWJYljuOUbl9E5P7+Xr5+/Vq7DV2WxWJR+P3h4SEpe3o/lFLy69cvERH5+/ev2LYt/X5foijKnC+qLBYLUUqJZVmNXVzwsbWJne12m/kuInJ2dibr9VpERAaDgVxeXibTmrrp5bepj++jo6PM71EUye3trcxms8p1pbuQ7Kps2Zubm8x54f7+XmazmURRJKZpPml71KF4KUdHRxLHsYRhKJ7nFbox/vnzR5RSpcvqOgXlDiLx0PInrXxDJooi8TxPLMvaaz/S6XQqSinxPI/GCd4MwzDk5uamcb71ei1fvnxJvi8WC1kul0mf6+VyWZpQaEEQyP39fWVS8f37dxEROT4+ruzHfXJy0thQGQ6HjftT1pC7v78XkcfkRJ8T+v1+7T6lbbdbEZHKSgiHKx87IiK3t7el8+q6IQzDJA7G47FcX1+33l4QBKKUKsTK+fl55XqiKNrrxTZdDsMwCjE0GAzk79+/Mh6Pd15nFEXUn3gxOob6/b7EcSy2bcv5+fkrl+pjOIjEYzAYiGmasl6vMwP+BoNBpjH09+/fZJCQiOw0mLXJxcWFiIj8/v17L+sDnkoPJA3DUJRStVdVV6uVOI5TaEBcX1+XDrYrM5/PS+9CaDc3N6KUkru7u+QKUxiGmYHb6bsyVeUcj8eVyYKO83SDJ4oiCcMwuQI9Go2Sfakrb5nNZiMiUjrYHIepLHYuLi5kvV5n6pW7uzsR+Xe3Qjd04jhOktq2fv78KcvlMvOb67qF39L6/X7lRYGn+vnzZyG50DGVr3frKKWSJIzEHq9psVhIGIYkv3twEImHyGNDyXEcERGxLKs0qUg3oLbbrfi+TxcKfDjT6VTiOBbf90VEaq8+LpfLxkZ/nclk0qoRf3FxkczX7/fFcRxZr9etYi+KIrm7u2tszOiEJt+Q+fTpU4s9qTcYDJIy0x0EIuWxM51OxbbtpA7q9XrieZ6Ypvns7QVBULgzqC8qPKcb1VN4nreXZCYMwyQJC8NwDyUDni6d/B4fHxeOSV1f7aNO+cgOJvEQ+dfg0mM7LMuqffTZaDQS0zS5S4EPaTQaJcl4GcMwdurmUcbzvMxVS8/zksZ/3d3E4+Pj1tu4urpK+uCmE4p8l8n0lWR9HnhqX/MyulHpeZ5cXV3tZZ14n+piZ7FYFBrTdWMv2tDdpfKJzs+fP+Xy8jKJjdPTUxEROT097ezuXBAEe0mk8nbp/gh0RR+DOrFO9xjQbcWXTvTfm4NIPIIgyDRy9IlfKZUZyFcmfaLLP6O9zXPPtR8/foiINA7CBV7S8fFx6XimNuMl2kg39HVjXyklcRwnJ+7z8/MkPtKUUq0aGvqCQr4x5/t+ZVcV13XF87ydu1Q10YPNm84r+Lh2iR2llNi2/eyGStUYjnSSE8dx0iVws9k8+6JClbJuVvui45UujXhphmEUuiw6jpM51mezWdKTANUOIvEQkdI+rm0G1EVRlCQLo9Go0JBqw3VdCcMweWIO8FZYllW42jocDmU2m2WOVdd1O3sR3rdv3yQMw8zdR8uy9j7gVTMMQy4vLyUMw07icdd++fg42saOvohl2/azk99er1c45l6zYb6vblZVDMPoLLEBtPwby29ubgoXCKbTqZyfnyfzzOfzTo/9D6Pr5/W+BfoZ/vnnoTe9xMi27dqXB6Y1vceDlx7htek4SH/y9PGa/+zr+LVtu/Q9HvkXlD3npZtl7zJI7/tz36+hY11/ys4R+ZfJ4WPIx0f6/75N7Oj3aMge3lFR9/Laqnqr7IWFbeW3URajvu8/+7iv2qe68xaA96MXxy0v279jQRDIw8ODHB0dJX1cRaRwtWkymYjnecl33/cbs9coihqfttHVlVUAAADgvTiIxAMAAADA6zqYMR4AAAAAXg+JBwAAAIDOkXgAAAAA6ByJBwAAAIDOkXgAAAAA6ByJBwAAAIDOkXgAAAAA6ByJBwAAAIDOkXgAAAAA6ByJBwAAAIDOkXgAAAAA6ByJBwAAAIDOkXgAAAAA6ByJBwAAAIDOkXgAAAAA6ByJBwAAAIDOkXgAAAAA6ByJBwAAAIDOkXgAAAAA6ByJBwAAAIDOkXgAAAAA6ByJBwAAAIDOkXgAAAAA6ByJBwAAAIDOkXgAAAAA6ByJBwAAAIDOkXgAAAAA6ByJBwAAAIDOkXgAAAAA6ByJBwAAAIDOkXgAAAAA6ByJBwAAAIDOkXgAAAAADQzDkF6vJ71eT6Ioeu3ivEskHsCBSZ84J5NJYfpqtUqm93o9Wa1WhXmGw2EyPQiC1tterVZiGEar8qXni6KosixV62gq93A4LJ0+HA4lCILSfdPlaFpHep5d/j54+yaTSWWjo03s6GOr6vhIH2NNsZJfp+u6pdObYt51Xen1erXbSO9b2TrSZS+bno7hyWRSuW/pv03Zp+3fBNg3wzDk4uJC4jiWzWYjSimSjyc4qMQjXyEEQZCpGPKNivSnSt0yVQ0T4LUYhiE3NzfJidPzvEwMBEEgd3d3EsexxHEsjuOIZVmZeSaTiYzH42Se8Xjc6uQbRZFYllU5XTdsDMOQOI5lu90m037//i0iIv/991/jdiaTiYRhWPh9OBxKv99Pyq1/S1uv1/L582f59euXiIgMBoPM9PTySilZr9eFxt719bWEYSi2bUscx4V14P3q9XrieV7ptDaxEwSBnJ6eShiGSQyenp5mkg+lVLKO5XLZWIdMJhM5PT2tnN4U8yIit7e3Yppm5TpWq5VYlpWUK4qiQnLhuq4opSrXkY7hm5sbOT8/L50vjmPxfV9EJPk7pT8kHngNOmam06mIPNYNpmnK9+/fX7NY71N8IEQktm07+W7bdiwise/7md/yfN8v/T3PcZw4/+fcbDaxiBR+B15LGIaZ76Zpxo7jJN/T8aAppTIxYJpmZrrv+6XLla3HNM1YKVWY5vt+IR7THMdpFYe+78emaRbWpWMxvf9hGMYiEm82m8z3MAxj27Ybt2eaZul5RK+rTXnx/uhjNR9LbWMnf1zYtp3E1GazycSjXqYNESksG8fNMa/LqeOgjFKqMZ7S85Yd+47jJPuSjrsyVX9j4LWUxa7v+6X1GeodxB0PfTXp27dvyW+LxUJs287M9/Xr18Kyy+Wy9Pc2BoNBcuWmbRcRoEv9fj/zfbvdJldwRERGo1FhGcMw5OTkJLOO9PE8m80a70S4rivz+bywfZF/d0IcxyndvojI/f19qziczWayWCwKvz88PCRlT++HUiq5u/H371+xbVv6/b5EUZQ5X1RZLBailBLLsrjlfuDaxM52u818FxE5OzuT9XotIo91xuXlZTJtH930mmJeq7ozFwSBhGGYifHBYCBKqeQuRhv39/cym80kiiIxTfNJdwKrungBXSuLXZHHu3Kc+3dzEImHlj9p5RsyZSfC9XpNVwl8SLoLRpP1ei1fvnxJvi8WC1kul0l3wuVyWZpQaEEQyP39fWVSoW9VHx8fV/bjPjk5aYzD4XDYuD9lDbn7+3sReUxO9Dmh3+/X7lOa7hJW180EhykfOyKP3ZrK6MZLGIZJHIzHY7m+vt5becpiPooimc/nlcuUJe3a3d3dTtsfDAby9+9fGY/HOy0n8lhOGnjA+3cQiYfui7derzMD/gaDQWVjSOTxLkX+rsiudJ/2uu0AL0kPJA3DUJRStVdVV6uVOI5TaHRcX18nfa6bEoL5fF56F0K7ubkRpVTSPz4MQwnDMNO3vewKbb6c4/G4MlnQ8Zdu8ERRJGEYJlexRqNRsi915S2z2WxEpDhmBIerLHYuLi5kvV5n7hjqxrueLz2OKD3O6TnqYr7f779I/aRjqqneTVNKJUkYiT3wMRxE4iHy2FByHEdEHpOBNk/IeUo3q/zgcj3AFHgrptNpZgBn3dXH5XLZ2OivM5lMWjXiLy4ukvn6/b44jiPr9br1oPW7u7vGxoxOaPINmU+fPrXYk3qDwSApM91BIFIeO9PpVGzbTuogPVi9bmD3PuwS829JenB52QMjgJdiGEZyd1z78+ePKKVa3x3Ho4NJPET+nXz1XQzLsiofPxhFkWy32527WcW5J3B4nrfTY0CBlzIajZJkvIxhGM/u5uF5Xuaqped5SeO/LiaOj49bb+Pq6iqJs3RCYVlWpstW+kqyPg88ta95Gd2o9DxPrq6u9rJOvE91sbNYLAqN6dls9iLlaor5MkdHRyIihYsAYRjK2dnZ3srWZJfuj8C+jcfjQjfF29vbyqezodpBJB75x+bqE79SKjOQL+3379+FAyr/jPam556LSHK3o+4xosBrOT4+Ln08ZZvxEm3kE3HbtpPHheo7FOfn5/Ljx4/Csm2vJOkLCvnGnO/7lV1VXNcVz/N27lLVRA82rzqv4OPbJXaUUmLb9ouOI6yK+SplA8l1V602j7feJx2vdGnES9P1lb5YHQSBrNfrvdchh+AgEg+Rx9veeXUD6sq6WY1Go0JDqg36puKtsiyrcLV1OBzKbDbLNPpd1+3sRXjfvn2TMAwzdx8ty6qNz+cwDEMuLy8lDMNOrqDuq18+3p+2saMvYtm2/eINl7KYbzKfzzMXz+bzeenYr5dgGMa76SqGj2W73crl5aX0ej05PT2lG/1Tdfy43jdBP3M8/zz0queNh2G487OZy97jEcdx8k4BnumP15Z+r4xUvF9GKVWYpyx2nsq27dLY0u/Q0J827wWpotdV9t6BfcSijnX9KXt3wmazIeY/oHx8pP/v28SOrg9kj++oyB+P6fhqE/NP2U7ZMa/fvfHcbZX9Dfe1DwBeXy+OP37KFgSBPDw8yNHRUeYNr1VXm/SV1zaDaqMoaryj4TjOswboAgAAAO/dQSQeAAAAAF7XwYzxAAAAAPB6SDwAAAAAdI7EAwAAAEDnSDwAAAAAdI7EAwAAAEDnSDwAAAAAdI7EAwAAAEDnSDwAAAAAdI7EAwAAAEDnSDwAAAAAdI7EAwAAAEDnSDwAAAAAdI7EAwAAAEDnSDwAAAAAdI7EAwAAAEDnSDwAAAAAdI7EAwAAAEDnSDwAAAAAdI7EAwAAAEDnSDwAAAAAdI7EAwAAAEDnSDwAAAAAdI7EAwAAAEDnSDwAAAAAdI7EAwAAAEDnSDwAAAAAdI7EAwAAAEDnSDwAAAAAdI7EAwAAAEDnSDwAAAAAdI7EAwAAAEDnSDwAAAAAdI7EAwAAAEDnSDwAAACAHMMwpNfrJZ8gCDLTXddNprmu+0qlfF9IPIADkz6RTiaTwvTVapU50a5Wq8I8w+Gw8kRcZ7VaiWEYrcqXni+KosqyVK2jqdzD4bB0+nA4lCAISvdNl6NpHXUVFd63yWQivV5PoigqTGsTO/rYqjo+0sdYU6zk11nV8GmKed14qpPet7J1pMteNj0dw5PJpHLf0n+bsk/bvwnwXKvVSs7PzyWO4+QzGAyS6a7ryo8fP5JpP378IPloIz4gIpJ8fN+PN5tN7Pt+Mj0Mw8w86U+VumXS2wLeAqVUHIZhHMdxvNlsCsfnZrOJbdtOvjuOU5jHtu3M9/Q66+hYUUqVTvd9PxaR2DTNymlttmPbdmncmaaZ2TfTNAvbEpHYcZxkv+sopZL588IwzGwLH0P6vJ4/FtvEjo65fAxuNpvMNtLzl8VDmj7eq47FppiP4/JYSNPxl54/f3zr/RWR0mM/HcNKqdr4qIv3pr8HsC9NdVs+dvNxgnIH8xfKnwzLGidVJ8s2DYiqhopunFQ1toCXlD+JmqaZaayUJcn5RkK+4vd9v1VyrZSKTdMsjQV9wq5aj+M4reLQ9/3YNM3GBl8c/0uEdMWhv+ukoWl7uvFVVm4Sj4+rqlHcNnbyx4Vt20lMbTabQvLQtqFdlwTn15efTymVaUCV7UdTPKXnLTv2HcdJ9iXfYMvb5UID0AV9DDYl0nlNxzbi+CC6Wulb2d++fUt+WywWYtt2Zr6vX78Wll0ul6W/t7XdbsVxHAnDsPL2NPBS+v1+5vt2u5XpdJp8H41GhWUMw5CTk5PMOtJdSGazmfz333+123VdV+bzeWH7Io9dMCzLEsdxSrcvInJ/f98qDmezmSwWi8LvDw8PSdnT+6GUkl+/fomIyN+/f8W2ben3+xJFUeZ8UWWxWIhSSizLKu16g8PRJna2223mu4jI2dmZrNdrEREZDAZyeXmZTNtHN72mmNfSXUjSgiCQMAwzMT4YDEQpJb9//25djvv7e5nNZhJFkZimWbm9OtSheClHR0cSx7GEYSie5xW6V/7580eUUqXL6joF5Q4i8dDyJ618Q6bsRLher590gkybTqeilBLP82ic4M0wDENubm4a51uv1/Lly5fk+2KxkOVymfS5Xi6XpQmFFgSB3N/fVyYV379/FxGR4+Pjyn7cJycnjXE4HA4b96esIXd/fy8ij8mJPif0+/3afUrbbrciIpWVEA5XPnZERG5vb0vn1XVDGIZJHIzHY7m+vt5becpiPooimc/nlcuUJe3a3d3dTtsfDAby9+9fGY/HOy0n8lhO6k+8FF3f9Pt9ieNYbNuW8/PzVy7Vx3AQicdgMBDTNGW9XmcG/A0Gg8rGkMjjwKL8XZGnuri4EBHZ6QoR0AU9kDQMQ1FK1V5VXa1W4jhOodFxfX1dOtiuzHw+L70Lod3c3IhSSu7u7pIrTGEYZgZul12hzZdzPB5XJgs6ztMNniiKJAzD5Ar0aDRK9qWuvGU2m42ISOlgcxymsti5uLiQ9XqduWOoG+96Pt3QieM4SWqfqy7m+/1+bT24LzqmmurdNKVUkoSR2OM1LRYLCcOQ5HcPDiLxEHlsKDmOIyIilmW1ekLOc7tZAW/RdDqVOI7F930Rkdqrj8vlsrHRX2cymbRqxF9cXCTz9ft9cRxH1ut1q5N8FEVyd3fX2JjRCU2+IfPp06cWe1JvMBgkZaY7CETKY2c6nYpt20kd1Ov1xPM8MU2z07LsEvNvSRiGSRIWhuFrFwcHLp38Hh8fF45JXV/to075yA4m8RD5d/LVdzEsy6p89FkURbLdbp/dzQp4q0ajUZKMlzEM49ndPDzPy1y19DwvafzXJf7Hx8ett3F1dZX0wU0nFJZlZbpspa8k6/PAU/ual9GNSs/z5Orqai/rxPtUFzuLxaLQmJ7NZi9SrqaYL3N0dCQiUrgIEIahnJ2d7a1sTXbp/gh0RR+D+kJX+u6h7tFCu7HeQSQeQRBkGjn6xK+UygzkS/v9+3ehP1/+Ge1Nzz1P+/Hjh4hI4yBc4CUdHx+XPhe/zXiJNtIN+4XD4QAAEx9JREFUfd3YV0pJHMfJifv8/DyJjzSlVKuGhr6gkG/M+b5f2VXFdV3xPG/nLlVN9GDzqvMKPr5dYkcpJbZtv2hDpSrmq5QNJNeNrZeuz3S80qURL80wDFkul5nfHMfJ3D2czWbJXUVUO4jEQ0QKB4yI1A6oK+tmNRqNCg2pNlzXlTAMkyfmAG+FZVmFq63D4VBms1nmWHVdt7MX4X379k3CMMzcfbQsqzY+n8MwDLm8vJQwDDuJx331y8f70zZ29EUs27b3nvw2KYv5JvP5XCzLynwvG/v1EgzDeDddxfB+5d9YfnNzU7hAMJ1O5fz8PJlnPp+/yHipd+8lntn72vQzx/PPQ6963rh+wdEumt7jwUuP8Np0HKQ/efp4zX/2dfzatl0aW/kXcT7npZt6XWXvHZCKZ7LvIv2iNKl4d0L+ZXL4GPLxkf6/bxM7+h0zssd3VOSPx3R8tYn5p2yn7JhPv/fgOdsq+xvuax8AvL5eHLe8bP+OBUEgDw8PcnR0JKenp8nvVVeb9JXXNoNqoyhqfNpGV1dWAQAAgPfiIBIPAAAAAK/rYMZ4AAAAAHg9JB4AAAAAOkfiAQAAAKBzJB4AAAAAOkfiAQAAAKBzJB4AAAAAOkfiAQAAAKBzJB4AAAAAOkfiAQAAAKBzJB4AAAAAOkfiAQAAAKBzJB4AAAAAOkfiAQAAAKBzJB4AAAAAOkfiAQAAAKBzJB4AAAAAOkfiAQAAAKBzJB4AAAAAOkfiAQAAAKBzJB4AAAAAOkfiAQAAAKBzJB4AAAAAOkfiAQAAAKBzJB4AAAAAOkfiAQAAAKBzJB4AAAAAOkfiAQAAAKBzJB4AAAAAOkfiAQAAAKBzJB4AAAAAOkfiAQAAAKBzJB4AAAAAOkfiAQAAAKBzJB4AAABAA8MwpNfrSa/XkyiKXrs47xKJB3Bg0ifOyWRSmL5arZLpvV5PVqtVYZ7hcJhMD4Kg9bZXq5UYhtGqfOn5oiiqLEvVOprKPRwOS6cPh0MJgqB033Q5mtaRnmeXvw/evslkUtnoaBM7+tiqOj7Sx1hTrIiIuK6bWV9e29jR62k6XtP7mF5nU+zoedJlLfvQmMNbZRiGXFxcSBzHstlsRCnF8foU8QERkeTj+3682Wxi3/cz82w2m8x8m82mdp1hGGbmz39M0+xyl4CdKKXiMAzjOP53rKdjYLPZxLZtJ98dxynMY9t25nt6nXV0rCilSqf7vl8ZM3pam+3Ytl0ocxzHsWmamX0zTbOwLRGJHcdJ9ruOUiqZPy8Mw8y28DGkz+35Y7FN7OiYy8dgup5JH3ebzaa2DtHHqqaUKszfJnb0sdxU5+n5yuZpGzv6PJCPT70/TXUu8Bp83y/UXfk6Be0cTOIhIpkDpKxx0qZSqFJ2sk0nMcBbkG98mKaZabiUNQaUUoUGe5rv+6XLla3HNM3SxEM3jqrW4zhOqxO87/uxaZqNsR3H/xpAOr71d500NG1PVzpl5Sbx+LiqGvJtYyd/XNi2ncTUZrMpJLJ1iUdZGfLx1TZ2muo7pVTlRYNdYqcu8QDeqrLYLYs3NDuIrlb6lu+3b9+S3xaLhdi2nZlvPp+LbdvS7/dFRGQwGIht2zKfz5+03cFgIL7vi4i07iICdEkf29p2u5XpdJp8H41GhWUMw5CTk5PMOtLH82w2k//++692u67rynw+L2xf5LEriGVZ4jhO6fZFRO7v7+Xr16+129BlWSwWhd8fHh6Ssqf3Qyklv379EhGRv3//JvEfRVHmfFFlsViIUkosy+KW+4FrEzvb7TbzXUTk7OxM1uu1iDzWGZeXl8m0pm5P+Xj68+dPob5qGzt1JpOJhGEo2+22dPpTYqdsG8BbVRa7IiJhGHLu39FBJB5a/sSWPxk3VQrAR2IYhtzc3DTOt16v5cuXL8n3xWIhy+Uy6ZO9XC5LEwotCAK5v7+vTCq+f/8uIiLHx8eVfdtPTk5kMBjUlnM4HDbuT1lD7v7+XkQekxN9Tuj3+7X7lKYbY0qpVvPjcORjR0Tk9va2dF7deAnDMImD8Xgs19fXrbbluq6IFBOgNrFTJ4oi8TxPHMfJjA9LX3x4auyktTkXAfgAXvuWy0vR3S+k5hbvU/vHxnF5V6s4julqhTdHH6vSok+37/ulYxh2kY4p27YLt6Z1Fw59G1t3xdhlfFS6u1dVVw7JjS/R8z11/9Ll091U9G90tfq42tYJZbFTNWbqOXVEfpzhU4+7qq5Wen/TY7l0mZ8yHqNuXCTwVimlCvG8y9hD/HMwdzyur6/FcRwREbEsq/QpHxcXF7JerzO/393diUjxlnaV/BM6bNuWOI73tBfA802nU4njOOkGOB6PK+ddLpeZrli7mkwmpV2f8i4uLpL5+v2+OI4j6/W61S3sKIrk7u6u8o6KFoZh5mqyvkPx6dOnFntSbzAYJGWmywhEymNnOp2KbdtJHdTr9cTzPDFN88nb6ff7Ej+O1xQREc/zOnmS2na7TepBHas/f/588vp830/KHccxdwzxphmGkdwd1/78+SNKqSfd4TtkB5N4iPxrcOmxHZZlJben9fTnVgrpE2kcx+J53k6PAQVeymg0SpLxMoZhtO7mUcXzPFFKZeJJN/7rYuL4+Lj1Nq6urpI4SycUlmVlumylG2j6PGCa5rO6oaTp84fneXJ1dbWXdeJ9qoudxWKRHINhGIrI49ikfdDrewn7ThTOz8/3uj5gn8bjcaE74O3tLcftExxE4hH8/+3dvU7jTBfA8RPpvQqEolUm17DFCiiTXMAWeCsqJKdGoUlJY2vrWKKiWlNwAYRiCxJtsdcQR2iFntvwW6zGa4/HifMxBJL/T0qR2PgD+XjmeD48nRYqOfrGr5QqDOTLL7MVCuYc7bY50036KZTneds6HWBrms2m9V0BdcZL1GEm4r7vi1JK0jTNWig6nY7c3t6W/rbukyT9QMGM2ziOKwfDhmEoURTVao1ZhR5sbt5XcDhWiR2llPi+v7XkV8fL0dHRVrYnItnEEbYHBWdnZ1vbj45F27txgF3T5ZV+WD2dTmU8Hm+9DDkE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Most of the MP particles exhibit a diameter of \u0026lt;20 mm and O/C molar ratios of 0.1–0.2, indicating that they are mainly composed of polyethylene, polypropylene (PP), and polystyrene. An O/C ratio of 0.1 for PP was reached after being degraded for 75 days via an advanced oxidation process (AOP) in distilled water. The usage of SO\u003csub\u003e4\u003c/sub\u003e•\u003csup\u003e−\u003c/sup\u003e initiator overcame the inhibiting effect that seawater had on PP degradation and accelerated the process. The O/C molar ratio of a PP sample degraded via AOP for 15 days in seawater is the same as that of marine MP retrieved from the sea. The combination of seawater and SO\u003csub\u003e4\u003c/sub\u003e•\u003csup\u003e−\u003c/sup\u003e initiator thus led to excellent acceleration of the degradation process. Nanosized PP particles were obtained over 15 days of AOP degradation, showing that the size of the MP could be controlled according to the degradation time.\u003c/p\u003e","manuscriptTitle":"Preparation method of marine microplastic model in a short degradation time","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2022-08-23 17:41:50","doi":"10.21203/rs.3.rs-1976856/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"bfe98ead-c4af-4248-8a20-b857f397e9d4","owner":[],"postedDate":"August 23rd, 2022","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2022-10-27T06:59:21+00:00","versionOfRecord":[],"versionCreatedAt":"2022-08-23 17:41:50","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-1976856","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-1976856","identity":"rs-1976856","version":["v1"]},"buildId":"7rjqhiLT3MXkJMwkYKINL","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}