Effects of microplastics on reproductive characteristics and mechanisms of the marine rotifer Brachionus plicatilis.

Microplastic pollution, especially secondary microplastics (MPs), poses a significant threat to marine ecosystems. Despite its prevalence, the impact of natural-aged MPs on marine organisms, hindered by collection challenges, remains poorly understood. This study focused on 1-3 µm natural-aged MPs collected from Japan's coastal sea, investigating their effects on the rotifer Brachionus plicatilis sensu stricto and its reproductive mechanisms. Rotifers exposed to varying MP concentrations (0, 20, and 200 particles/mL) over 14-day batch cultures exhibited reduced population growth and fertilization rates. Down-regulation of reproductive genes and up-regulation of oxidative stress-related genes were observed, indicating MP-induced disruptions. Enhanced activities of superoxide dismutase and acetylcholinesterase and elevated malondialdehyde levels further emphasized oxidative stress. These findings underscore the detrimental impact of MPs on rotifer reproductivity, shedding light on the underlying mechanisms.

Effect of Copper Antifouling Paint on Marine Degradation of Polypropylene: Uneven Distribution of Microdebris between Nagasaki Port and Goto Island, Japan.

Microplastics (MP) encompass not only plastic products but also paint particles. Marine microdebris, including MP, was retrieved from five sampling stations spanning Nagasaki-Goto island and was classified into six types, primarily consisting of MP (A), Si-based (B), and Cu-based (C) paint particles. Type-A particles, i.e., MP, were exceedingly small, with 74% of them having a long diameter of 25 µm or less. The vertical distribution of type C, containing cuprous oxide, exhibited no depth dependence, with its dominant size being less than 7 µm. It was considered that the presence of type C was associated with a natural phenomenon of MP loss. To clarify this, polypropylene (PP) samples containing cuprous oxide were prepared, and their accelerated degradation behavior was studied using a novel enhanced degradation method employing a sulfate ion radical as an initiator. Infrared spectroscopy revealed the formation of a copper soap compound in seawater. Scanning electron microscopy/energy-dispersive X-ray spectroscopy analysis indicated that the chemical reactions between Cl- and cuprous oxide produced Cu+ ions. The acceleration of degradation induced by the copper soap formed was studied through the changes in the number of PP chain scissions, revealing that the presence of type-C accelerated MP degradation.

Study on the onset mechanism of bio-blister degradation of polyolefin by diatom attachment in seawater.

It is essential to develop a mechanism for lowering the molecular weight of polyolefins to achieve biodegradation in seawater. In this study, a polypropylene/polylactic acid blend sample was first subjected to photodegradation pretreatment, and it was confirmed that in pure water, the acid generated promotes the polypropylene degradation (autoxidation), while in alkaline seawater, the promotion was inhibited by a neutralization reaction. In the autoxidation of polyolefins in alkaline seawater, aqueous Cl- was also the inhibitor. However, we found that autoxidation could be initiated even in seawater by lowering the pH and using dissociation of ClOH (called blister degradation). The blister degradation mechanism enabled autoxidation, even in seawater, by taking advantage of the ability of diatoms to secrete transparent exopolymer particles (TEP) to prevent direct contact between the surface layer of polyolefins and alkaline seawater. We named blister degradation in seawater with diatoms as bio-blister degradation and confirmed its manifestation using linear low-density polyethylene (LLDPE)/starch samples by SEM, IR, DSC and GPC analysis.

Differences in the Residual Behavior of a Bumetrizole-Type Ultraviolet Light Absorber during the Degradation of Various Polymers.

The alteration of an ultraviolet light absorber (UVA: UV-326) in polymers (PP, HDPE, LDPE, PLA, and PS) over time during degradation was studied using an enhanced degradation method (EDM) involving sulfate ion radicals in seawater. The EDM was employed to homogeneously degrade the entire polymer samples containing the UVA. The PP and PS samples containing 5-phr (phr: per hundred resin) UVA films underwent rapid whitening, characterized by the formation of numerous grooves or crushed particles. Notably, the UVA loss rate in PS, with the higher glass transition temperature (Tg), was considerably slower. The behavior of crystalline polymers, with the exception of PS, was analogous in terms of the change in UVA loss rate over the course of degradation. The significant increase in the initial loss rate observed during EDM degradation was due to microplasticization. A similar increase in microplasticization rate occurred with PS; however, the intermolecular interaction between UVA and PS did not result in as pronounced an increase in loss rate as observed in other polymers. Importantly, the chemical structure of UVA remained unaltered during EDM degradation. These findings revealed that the primary cause of UVA loss was leaching from the polymer matrix.

Rapid oxidative fragmentation of polypropylene with pH control in seawater for preparation of realistic reference microplastics.

Various tiny plastic particles were retrieved from the sea and studied using scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM/EDX) analysis to prepare realistic reference microplastics (MP). Most of the MP exhibited a diameter of < 20 × 10-6 m and 0.1-0.2 molar ratios of oxygen to carbon atoms (O/C), indicating that they primarily comprised polyethylene (PE), polypropylene (PP), and polystyrene (PS). It took a long time to reproduce such O/C ratios in standard laboratory weathering methods. For example, degrading of 30 × 30 × 0.060 mm PP film required 75 days for the 0.1 ratio, even with an advanced oxidation process (AOP) using a sulfate radical anion (SO4·-) initiator in distilled water at 65 °C. However, seawater drastically improved the PP degradation performance of AOP under a weak acid condition to achieve the 0.1 ratio of PP film in only 15 days. The combination of seawater and the SO4·- initiator accelerated the degradation process and showed that the MP's size could be controlled according to the degradation time.