Aging Processes of Polyethylene Mulch Films and Preparation of Microplastics with Environmental Characteristics.

In this study, we explored the aging processes of a commercial polyethylene (PE) mulch film under UV irradiation and compared the laboratory aged films with films aged in nature. Overall, the aged films obtained from laboratory conditions were similar with that from natural conditions. Among the investigated factors, UV irradiation was crucial in the aging of the films, producing cracks and oxygen-containing functional groups on the films surface, constantly with natural aging. The formation of cracks induced a decrease of mechanical strength as well as the formation of MPs on the surface. The chemical oxidations detected by Fourier-transform infrared spectroscopy (FTIR) usually happened after the observed physical changes during aging. Moreover, a protocol was developed for laboratory preparation of MPs with characteristics similar with that from environmental aging and PE MPs with sizes of 2-400 µm could be produced in large amounts at relatively short period of time.

Aging Significantly Affects Mobility and Contaminant-Mobilizing Ability of Nanoplastics in Saturated Loamy Sand.

Plastic debris, in particular, microplastics and nanoplastics, is becoming an emerging class of pollutants of global concern. Aging can significantly affect the physicochemical properties of plastics, and therefore, may influence the fate, transport, and effects of these materials. Here, we show that aging by UV or O3 exposure drastically enhanced the mobility and contaminant-mobilizing ability of spherical polystyrene nanoplastics (PSNPs, 487.3 ± 18.3 nm in diameter) in saturated loamy sand. Extended Derjaguin-Landau-Verwey-Overbeek calculations and pH-dependent transport experiments demonstrated that the greater mobility of the aged PSNPs was mainly the result of surface oxidation of the nanoplastics, which increased not only the surface charge negativity, but more importantly, hydrophilicity of the materials. The increased mobility of the aged PSNPs significantly contributed to their elevated contaminant-mobilizing abilities. Moreover, aging of PSNPs enhanced the binding of both nonpolar and polar contaminants, further increasing the contaminant-mobilizing ability of PSNPs. Interestingly, aging enhanced binding of nonpolar versus polar compounds via distinctly different mechanisms: increased binding of nonpolar contaminants (tested using pyrene) was mainly the result of the modification of the polymeric structure of PSNPs that exacerbated slow desorption kinetics; for polar compounds (4-nonylphenol), aging induced changes in surface properties also resulted in irreversible adsorption of contaminants through polar interactions, such as hydrogen bonding. The findings further underline the significant effects of aging on environmental fate and implications of nanoplastics.

Polystyrene Nanoplastics-Enhanced Contaminant Transport: Role of Irreversible Adsorption in Glassy Polymeric Domain.

Nanoplastics (NPs) are becoming an emerging pollutant of global concern. A potential risk is that NPs may serve as carriers to increase the spreading of coexisting contaminants. In this study, we examined the effects of polystyrene nanoplastics (PSNPs, 100 nm), used as a model NP, on the transport of five organic contaminants of different polarity in saturated soil. The presence of low concentrations of PSNPs significantly enhanced the transport of nonpolar (pyrene) and weakly polar (2,2',4,4'-tetrabromodiphenyl ether) compounds, but had essentially no effects on the transport of three polar compounds (bisphenol A, bisphenol F, and 4-nonylphenol). The strikingly different effects of NPs on the transport of nonpolar/weakly polar versus polar contaminants could not be explained with different adsorption affinities, but was consistent with the polarity-dependent extents of desorption hysteresis. Notably, desorption hysteresis was only observed for nonpolar/weakly polar contaminants, likely because nonpolar compounds tended to adsorb in the inner matrices of glassy polymeric structure of polystyrene (resulting in physical entrapment of adsorbates), whereas polar compounds favored surface adsorption. This hypothesis was verified with supplemental adsorption and desorption experiments of pyrene and 4-nonylphenol using a dense, glassy polystyrene polymer and a flexible, rubbery polyethylene polymer. Overall, the findings of this study underscore the potentially significant environmental implication of NPs as contaminant carriers.

Effects of food quantity on the ingestion and egestion of MPs with different colors by Daphnia magna.

Aquatic organism uptake and accumulate microplastics (MPs) through various pathways, with ingestion alongside food being one of the primary routes. However, the impact of food concentration on the accumulation of different types of MPs, particularly across various colors, remains largely unexplored. To address this gap, we selected Daphnia magna as a model organism to study the ingestion/egestion kinetics and the preference for different MP colors under varying concentrations of Chlorella vulgaris. Our findings revealed that as the concentration of Chlorella increased, the ingestion of MPs by D. magna initially increased and then showed a decline. During the egestion phase within clean medium without further food supply, an increase in food concentration during the ingestion phase led to a slower rate of MP discharge; while when food was present during the egestion phase, the discharge rate accelerated for all treatments, indicating the importance of food ingestion/digestion process on the MPs bioaccumulation. Furthermore, in the presence of phytoplankton, D. magna demonstrated a preference for ingesting green-colored MPs, especially at low and medium level Chlorella supply, possibly due to the enhanced food searching activities. Beyond gut passage, we also examined the attachment of MPs to the organism's body surface, finding that the number of adhered MPs increased with increasing food concentration, likely due to the intensified filtering current during food ingestion. In summary, this study demonstrated that under aquatic environment with increasing phytoplankton concentrations, the ingestion and egestion rates, color preferences, as well as surface adherence of MPs to filter feeding zooplanktons will be significantly influenced, which may further pose ecological risks. Our results offer novel insights into the unintentional accumulation of MPs by zooplankton, highlighting the complex interactions between food availability and MPs accumulation dynamics.

Insights into the accumulation, distribution and toxicity of pyrene associated with microplastics in rice (Oryza sativa L.) seedlings.

Microplastic and polycyclic aromatic hydrocarbons (PAHs) can be introduced into agroecosystems through various agricultural activities and may threaten food safety and human health. However, little research has focused on the behavior of microplastics-associated PAHs and their toxicity effects in agroecosystems, especially in crops. In the present study, we investigated the accumulation, distribution and toxicity of pyrene associated with polyethylene (PE) microplastics in rice (Oryza sativa L.). With quantitative analysis using 14C isotope labelling, the total accumulation efficiency of 14C-pyrene in rice seedlings was 22.4 ± 1.2% and 14.5 ± 0.3% when exposed to freely dissolved pyrene and PE-associated pyrene, respectively. The translocation of 14C-pyrene was significantly decreased by microplastics adsorption even when the amount of pyrene in the rice roots had no significant difference. Subcellular distribution of 14C-pyrene in rice suggested that PE microplastics-associated pyrene located more on cell walls than free dissolved pyrene. Furthermore, results showed free pyrene, but not PE-associated pyrene, significantly decreased the length and biomass of rice roots as well as increased the activities of antioxidant enzymes (superoxide dismutase and catalase). It indicated that the association with microplastics alleviated the phytotoxicity of pyrene in rice seedlings. These findings shed new light on the environmental behavior and effects of PAHs associated with microplastics in crops and will be helpful to its comprehensive risks assessment.

Photodissolution of submillimeter-sized microplastics and its dependences on temperature and light composition.

Photodissolution has the potential to efficiently remove microplastics from the surface ocean. Here, we examined the effects of temperature and incident sunlight composition on the photodissolution of submillimeter-sized microplastics of polypropylene (PP), polystyrene (PS), and thermoplastic polyurethane (TPU) in seawater. The photoproduction of dissolved organic carbon (DOC), chromophoric dissolved organic matter, and dissolved nitrogen (TPU only) was observed to increase exponentially within 7 days of full-spectrum irradiation. The temperature dependence of photodissolution increased with irradiation time for PP and PS but remained relatively constant for TPU. A 20 °C increase in temperature enhanced DOC photoproduction by 10 times for PP, three times for PS, and four times for TPU at 7-d irradiation, giving activation energies of 59.4-84.8 kJ mol-1. Photodissolution of all three polymers was exclusively driven by ultraviolet-B (UVB) radiation. PS-derived DOC was photomineralizable, while PP- and TPU-derived DOC appeared photo-resistant. Extrapolating the lab-based DOC photoproduction rates to warm surface oceans yields lifetimes of 6.5 years for PP, 3.6 years for PS, and 3.7 years for TPU. This study demonstrates that photodissolution of the tested microplastics is restricted to the thin UVB-penetrable surface ocean and that water temperature plays a critical role in controlling the photodissolution of these microplastics.

Effects of nano- and microplastics on the bioaccumulation and distribution of phenanthrene in the soil feeding earthworm Metaphire guillelmi.

Microplastics (MPs) and nanoplastics (NPs), are collectively referred to as fine plastic particles (FPs), have been reported for both the "vector" effect and "dilution" effect which alters the bioaccumulation of organic contaminants. However, which effect plays a dominant role, especially in terrestrial ecosystems, remains unknown. In the present study, we used 14C-radioactive labeling tracing technique to assess the sorption of a typical polycyclic aromatic hydrocarbon, phenanthrene on soil particles and FPs, as well as the contribution of vector effects of FPs on the bioaccumulation and distribution of phenanthrene by the geophagous earthworm Metaphire guillelmi. The results showed that the presence of FPs in soil decreased the bioaccumulation of 14C-Phenanthrene in M. guillelmi by decreasing the bioavailable fraction of phenanthrene in soil, and the decreasing effect was more dramatic for NPs treatments. In all cases, bioaccumulation of 14C-Phenanthrene in M. guillelmi was still determined by the free concentration of 14C-Phenanthrene in soil and limited vector effects was observed. Moreover, the different correlation coefficients between the free concentration of 14C-Phe in two soils and bioaccumulated 14C-Phenanthrene in earthworms indicated that soil properties remained a dominant factor that determines the bioaccumulation efficiency of 14C-Phenanthrene in the FPs-soil system. Although the total 14C-Phenanthrene bioaccumulation in earthworms did not increase, vector effects may be responsible for the increased relative distribution of 14C-phenanthrene in the organ region, compared with skin and gut regions, leading to unknown risks to organs that are sensitive to these contaminants.

Quantification of polystyrene plastics degradation using 14C isotope tracer technique.

14C-isotope tracer technique is an effective tool for quantitative analysis of compounds. Based on its unique 14C signal, 14C-isotope tracer has been widely used in degradation of pollutants, especially in a complex environmental matrix. In this chapter, we introduce methods and examples for studying the degradation of polystyrene (PS) plastics using the 14C-isotope tracer technique. 14C-based gel permeation chromatography (GPC), high performance liquid chromatography (HPLC) as well as liquid scintillation counter (LSC) are introduced for analyzing changes in the molecular weight of plastic polymers, generation of hydrophilic products, and complete mineralization of plastics during microbial and UV-induced degradation. With the 14C-isotope tracer technique, further studies on mechanisms for degradation of plastics/microplastics under complex natural environment conditions could be facilitated.

Quantifying the bioaccumulation of nanoplastics and PAHs in the clamworm Perinereis aibuhitensis.

The impact of nanometer-scale plastics (<1000 nm nanoplastics, NPs) on the bioaccumulation of hydrophobic organic pollutants, and especially polycyclic aromatic hydrocarbons (PAHs), in marine organisms has become of urgent concern. However, simultaneous determinations of the bioaccumulation of NPs and PAHs have been hindered by the lack of an efficient digestion method that removes background interference from the tissue without altering the surface properties of the plastic and destroying the PAHs. To solve this problem, an enzymatic digestion-based protocol using proteinase K and subsequent quantification methods were developed on a typical marine benthic invertebrate - the clamworm Perinereis aibuhitensis. Enzymatic digestion removed 91% of the biological tissues, comparable to the amount removed using 65% HNO3 (93% removed) and better than that removed using 30% H2O2 or 10% KOH digestion (76% and 66%, respectively). After enzymatic digestion, roughly 92% of the NPs and 88% of the amount of pyrene were recovered, without significant modification of the NPs or pyrene degradation. By contrast, the NP and pyrene recovery achieved with HNO3 digestion was only 1.4% and 0.1%, respectively. The newly developed protocol was successfully applied to a 96-h bioaccumulation study. The use of radioactively labeled 14C-pyrene and fluorescently labeled NPs allowed the simultaneous quantification of NPs and PAHs in the clamworm and revealed a bioconcentration factor (BCF) of 1.96 ±â€¯0.93 and 402.7 ±â€¯47.0, respectively. The quantification of NPs and pyrene indicated that NP-adsorbed pyrene accounted for <1% of the total pyrene accumulation in the clamworm body when the concentration of NPs in seawater was as low as 0.4 mg/L. Our enzymatic digestion and dual-labeling technique thus provides the first reported BCF value of NPs in a marine benthic organism and new insights into the vector effects of these particles on the bioaccumulation of organic contaminants in a marine ecosystem.

Mineralisation of 14C-labelled polystyrene plastics by Penicillium variabile after ozonation pre-treatment.

Large amounts of polystyrene (PS), one of the most widely used plastics in the world, end up in the environment through industrial discharge and littering, becoming one of the major components of plastic debris. Such plastics, especially the small-sized microplastics and nanoplastics, have received increasing concerns in terms of their potential environmental risks. Feasible approaches for the degradation of PS in waste materials and in the environment are highly desirable. Physicochemical pretreatments of PS may be applied to enhance biological degradation. In the present study, we synthesized 14C-labelled PS polymers, either uniformly labelled on the ring ([U-ring-14C]-PS) or labelled at the ß-carbon position of the alkyl chain ([ß-14C]-PS), and investigated the mineralisation of the 14C-PS polymers by the fungus Penicillium variabile CCF3219 as well as the effect of ozonation as a physico-chemical pre-treatment on the mineralisation by the fungi. Biodegradation of the 14C-PS polymers was studied in liquid medium (pH 7.5, without additional carbon substrate) with P. variabile for 16 weeks. During the incubation time, 14CO2 was captured to calculate the mineralisation of 14C-PS and the remaining polymers were analysed by means of scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) spectrometry and gel-permeation chromatography (GPC). The results showed that the fungi mineralised both labelled polymers, and that the [U-ring-14C]-PS with a lower molecular weight led to a higher mineralisation rate. Ozonation pre-treatment strongly enhanced mineralisation of [ß-14C]-PS. SEM analysis showed that the surface of the ozonated [ß-14C]-PS became uneven and rough after the incubation, indicating an attack on the polymer by P. variabile. FT-IR analysis showed that ozonation generated carbonyl groups on the [ß-14C]-PS and the amount of the carbonyl groups decreased after incubation of the [ß-14C]-PS with P. variabile. GPC analysis showed that the molecular weights of the ozonated [ß-14C]-PS decreased after incubation. The present data suggest that ozonation pretreatment could be a potential approach for degradation of PS waste and remediation of PS-contaminated sites.

Effects of nanoplastics and microplastics on toxicity, bioaccumulation, and environmental fate of phenanthrene in fresh water.

Contamination of fine plastic particles (FPs), including micrometer to millimeter plastics (MPs) and nanometer plastics (NPs), in the environment has caught great concerns. FPs are strong adsorbents for hydrophobic toxic pollutants and may affect their fate and toxicity in the environment; however, such information is still rare. We studied joint toxicity of FPs with phenanthrene to Daphnia magna and effects of FPs on the environmental fate and bioaccumulation of 14C-phenanthrene in fresh water. Within the five sizes particles we tested (from 50 nm to 10 µm), 50-nm NPs showed significant toxicity and physical damage to D. magna. The joint toxicity of 50-nm NPs and phenanthrene to D. magna showed an additive effect. During a 14-days incubation, the presence of NPs significantly enhanced bioaccumulation of phenanthrene-derived residues in daphnid body and inhibited the dissipation and transformation of phenanthrene in the medium, while 10-µm MPs did not show significant effects on the bioaccumulation, dissipation, and transformation of phenanthrene. The differences may be attributed to higher adsorption of phenanthrene on 50-nm NPs than 10-µm MPs. Our findings underlined the high potential ecological risks of FPs, and suggested that NPs should be given more concerns, in terms of their interaction with hydrophobic pollutants in the environment.

Highly active carbonaceous nanofibers: a versatile scaffold for constructing multifunctional free-standing membranes.

Translating the unique characteristics of individual nanoscale components into macroscopic materials such as membranes or sheets still remains a challenge, as the engineering of these structures often compromises their intrinsic properties. Here, we demonstrate that the highly active carbonaceous nanofibers (CNFs), which are prepared through a template-directed hydrothermal carbonization process, can be used as a versatile nanoscale scaffold for constructing macroscopic multifunctional membranes. In order to demonstrate the broad applicability of the CNF scaffold, we fabricate a variety of CNF-based composite nanofibers, including CNFs-Fe(3)O(4), CNFs-TiO(2), CNFs-Ag, and CNFs-Au through various chemical routes. Importantly, all of them inherit unique dimensionality (high aspect ratio) and mechanical properties (flexibility) of the original CNF scaffolds and thus can be assembled into macroscopic free-standing membranes through a simple casting process. We also demonstrate the wide application potentials of these multifunctional composite membranes in magnetic actuation, antibiofouling filtration, and continuous-flow catalysis.