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.

Biodegradation Mechanism of Polystyrene by Mealworms (Tenebrio molitor) and Nutrients Influencing Their Growth.

A degradation mechanism of polystyrene (PS) in mealworms reared on expanded PS (EPS) was investigated by its decrease in molecular weight and change in chemical structure. A 33% decrease in molecular weight was observed for the digested PS in the frass after 1 week of feeding to mealworms. The FT-IR and py-GC/MS spectra of the digested PS showed radical oxidative reactions taking place in the mealworm body. The presence of hydroperoxide, alcohol and phenol groups was confirmed, and dimer fragments of styrene with quinone and phenol groups were obtained. The decrease in molecular weight and the alternation of benzene rings indicated that autoxidation and quinonization via phenolic intermediates occurred simultaneously in the mealworm body. The survival rate of mealworms reared on EPS was higher than that of starved worms, indicating that EPS was a nutrient source. However, no weight gain was observed in mealworms fed EPS alone. Comparison with the mixed diets with bran or urethane foams (PU) indicated that protein, phosphorus and magnesium components absent from EPS were required for mealworm growth.

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.

Degradation and fragmentation behavior of polypropylene and polystyrene in water.

The polystyrene (PS) retrieved from the beach exhibited no change in surface texture. In contrast to it, the retrieved polypropylene (PP) had a rumpled surface texture. Highly reactive sulfate radical generated by K2S2O8 was employed as degradation initiator of PP and PS, and their degradation behavior was studied in water. The PS carbonyl index value gradually went up down, and its molecular weight (MW) curve discontinuously shifted to a lower MW with the increase of the degradation time unlike the PP. It was found that the PP microplastic production rate was approximately three time higher than the PS from weight ratio dependence on degradation time. The higher microplastic production rate of PP arose from its crystallizability. The voids were produced by change in specific volume occurring by chemi-crystallization and then provoked the cracks leading to quick fragmentation. The SEM photographs suggested that the PP microplastic size facilely reached nm order by the cracking around lamella.

Synthesis and activity characteristics of visible light responsive polymer photocatalyst system with a styrene block copolymer containing TiO2 gel.

A polymer photocatalyst system was synthesized using a poly(styrene-block-acrylic acid) (PS-b-PAA) containing TiO2 gel without calcination, and its activity characteristics were assessed with methylene blue (MB) photodegradation test in water under visible light irradiation. The initial photodegradation activity was controllable by the polymer chain length and PAA/PS molar ratio. The longer polymer chain length provoked the activity decrease by macromolecular crowding effect. The lower molar ratio did an increase in the photocatalytic surface area by generation of a large number of anatase TiO2 crystal nuclei, leading to the activity increase. The copper phthalocyanine (CuPc) loading remarkably improved the activity. A higher active site was formed on the interface and showed good recycling performance.

Bioconversion of Birch Wood Hemicellulose Hydrolyzate to Xylitol.

A sugar solution containing 42.9 g l(-1) of xylose was prepared from the wood of Japanese white birch (Betula platyphylla var. japonica) by hydrolysis with 3 % sulfuric acid with a liquor-to-solid ratio of 4 (g g(-1)) at 120 °C for 1 h. During the acid hydrolysis, undesirable by-products were generated, such as acetic acid, furfural, and low-molecular-weight phenols, which inhibit bioconversion of xylose to xylitol. These inhibitors were successfully removed from the hydrolyzate by sorption onto a steam-activated charcoal followed by treatment with an anion exchange resin. Bioconversion of the detoxified hydrolyzate to xylitol by the yeast Candida magnoliae was investigated under the microaerobic conditions. The oxygen transfer rate (OTR) varied from 9.6 to 22.3 mmol O2 l(-1) h(-1). The best fermentative performance of C. magnoliae in the birch wood hydrolyzate (xylitol yield 0.74 g xylitol g xylose(-1); volumetric productivity 1.0 g l(-1) h(-1)) was obtained at the OTR of 12.6 mmol O2 l(-1) h(-1).

Degradation behavior of polymer blend of isotactic polypropylenes with and without unsaturated chain end group.

In this work, the relationship between the unsaturated chain end group content and the thermal oxidative degradation rate was systematically studied with binary polymer blends of isotactic polypropylene (iPP) with and without the unsaturated chain end group. The iPPs with and without the unsaturated chain end group were synthesized by a metallocene catalyst in the absence of hydrogen and by a Ziegler catalyst in the presence of one, respectively. The thermal oxidative degradation rate of the binary iPP blends was estimated from the molecular weight and the apparent activation energy (ΔE), which were obtained through size exclusion chromatography (SEC) and thermogravimetric analysis (TGA) measurements, respectively. These values exhibited a negative correlation against the mole content of the unsaturated chain end group. The thermal oxidative degradation rate apparently depends on the content of the unsaturated chain end group. This tendency suggests that the unsaturated chain end acts as a radical initiator of the iPP degradation reaction.