Environmental Degradation of Microplastics: How to Measure Fragmentation Rates to Secondary Micro- and Nanoplastic Fragments and Dissociation into Dissolved Organics.

Understanding the environmental fate of microplastics is essential for their risk assessment. It is essential to differentiate size classes and degradation states. Still, insights into fragmentation and degradation mechanisms of primary and secondary microplastics into micro- and nanoplastic fragments and other degradation products are limited. Here, we present an adapted NanoRelease protocol for a UV-dose-dependent assessment and size-selective quantification of the release of micro- and nanoplastic fragments down to 10 nm and demonstrate its applicability for polyamide and thermoplastic polyurethanes. The tested cryo-milled polymers do not originate from actual consumer products but are handled in industry and are therefore representative of polydisperse microplastics occurring in the environment. The protocol is suitable for various types of microplastic polymers, and the measured rates can serve to parameterize mechanistic fragmentation models. We also found that primary microplastics matched the same ranking of weathering stability as their corresponding macroplastics and that dissolved organics constitute a major rate of microplastic mass loss. The results imply that previously formed micro- and nanoplastic fragments can further degrade into water-soluble organics with measurable rates that enable modeling approaches for all environmental compartments accessible to UV light.

Hygroscopicity of Microplastic and Mixed Microplastic Aqueous Ammonium Sulfate Systems.

A growing body of research suggests the presence and long-range transport of microplastics in the atmosphere. However, the interactions between these microplastics and atmospheric aerosol are poorly understood. Environmental microplastics vary in color, morphology, and chemical composition and become oxidized over time by UV, mechanical, and biological action. Once introduced to the atmosphere, these microplastics will likely become mixed with atmospheric aerosol. Determining how microplastics interact with aerosol particles and how they may alter aerosol physical properties, including water uptake and loss, is necessary to understand the impact of these microplastics on our environment. Herein, we investigate the effect of microplastics on the water activity of bulk water and ammonium sulfate solutions. We compare a variety of plastic compositions and microplastic morphologies including plastics that have been aged by UV irradiation and mechanical forces in the lab. In addition, we investigate the water uptake and loss in microplastic samples through dynamic vapor sorption. We find an increase in total water sorption for UV-aged plastics compared to pristine plastics. Finally, we investigate the effect of fractional surface coverage on the equilibration time scale.

Evaluation of the Resistance of a Polypropylene Geotextile Against Ultraviolet Radiation.

The exposure to solar radiation (mainly due to the action of ultraviolet radiation) is one of the main causes for the premature failure of many polymeric materials, including the geotextiles. In this work, a nonwoven polypropylene geotextile (stabilized with a known amount of a hindered amine light stabilizer) was exposed to ultraviolet-aging tests, both in the laboratory (accelerated conditions) and outdoors (natural conditions). The damage occurred in the geotextile (caused by the ultraviolet-aging tests) was evaluated quantitatively (by monitoring changes in its mass per unit area, thickness, and tensile properties) and qualitatively (by scanning electron microscopy). The results, among other findings, showed that: (1) the ultraviolet-aging tests (both in the laboratory and outdoors) induced relevant damage in the polypropylene fibers of the geotextile (transverse cracks), leading to the deterioration of its tensile behavior, (2) the amount of degradation increased with the increase of the ultraviolet radiant energy, (3) the laboratory tests caused a faster deterioration of the polypropylene fibers than the outdoor tests, and (4) the degradation found by scanning electron microscopy in the polypropylene fibers correlated well with the deterioration occurred in the tensile behavior of the geotextile.

Effect of UV aging on translucency of currently used esthetic CAD-CAM materials.

OBJECTIVES: To evaluate the relative translucency parameter (RTP) values of computer-aided design (CAD)-computer-aided manufacturing (CAM) materials after UV aging. MATERIALS AND METHODS: 70 specimens (n = 10) of Bruxzir Anterior (BA); E.max Cad (EC); Lava Ultimate (LU); Cerasmart (CE); Vita Enamic (VE); Vita Suprinity (VS); Vita Mark II (VM) were prepared (1 mm ± 0.01 mm). Color measurements were performed using a spectrofotometer (VITA Easyshade). RTP values of the specimens before (RTP1 ) and after UV aging (RTP2 ) were evaluated. Statistical analyses were done with repeated measurements of two-way-ANOVA with Bonferroni test (P < 0.05). RESULTS: Evaluating RTP1 and RTP2 values; significant differences were found (P < 0.05). There were no significant difference between the RTP1 values of CE and VS (P = 0.779); EC and VM (P = 0.952); VM and LU (P = 0.995); EP and LU (P = 0.653). Evaluating RTP2 values; VE and BA were found significantly different from the others (P < 0.05). For all evaluated groups TP values decreased after UV aging (P < 0.05). The most RTP reduction was observed for LU; while VM and EC were less affected. CONCLUSION: Glass ceramic VE showed the highest RTP and zirconia-based BA was the most opaque restorative CAD-CAM material. UV aging caused the CAD-CAM materials get more opaque. CLINICAL SIGNIFICANCE: In cases where translucency is needed chosing VE would give better esthetic results; while zirconia-based BA should be used if more opaque restoration is needed. Clinicians should be aware of that restorations get more opaque after usage.

Impact of aging of primary and secondary polystyrene nanoplastics on the transmission of antibiotic resistance genes in anaerobic digestion.

Sewage sludge is a significant reservoir of nano/microplastics (NPs/MPs) and antibiotic resistance genes (ARGs). Research has revealed that NPs/MPs may exert an inhibitory effect on anaerobic digestion (AD) of sludge. Moreover, NPs/MPs can influence microbial community diversity and composition, potentially increasing ARGs dissemination. The morphological changes to NPs/MPs surface due to aging contribute to modifying hydrophobic properties. To date, there is limited comprehension regarding how various surface properties of NPs influence ARGs dissemination during AD. This study investigated the impact of primary aged/non-aged and secondary aged/non-aged polystyrene nanoplastics (PSNPs) on ARGs and mobile genetic elements (MGEs) propagation during AD. The findings indicated that the UV-aging process resulted in surface oxidation and distinct morphological characteristics in both primary and secondary PSNPs, while the surface oxidation effect was more pronounced in the secondary aged PSNPs. High concentrations (150 µg/L) of primary and secondary PSNPs inhibited methane production, with secondary PSNPs causing greater inhibition by 16 to 20 % compared to control. In contrast, low concentration (25 µg/L) had negligible or slightly positive effects on methane production. PSNPs at 150 µg/L reduced total VFA concentration, indicating an inhibitory effect on the fermentation step in the AD process. Primary and secondary PSNPs exhibited changes in EPS characteristics. ARGs abundance was enriched in reactors amended with PSNPs, with the highest abundance of 8.54 × 105 copies/g sludge observed in the secondary aged PSNPs (150 µg/L) reactor. Reactors exposed to aged PSNPs exhibited a relatively higher abundance of ARGs compared to reactors exposed to non-aged PSNPs. Exposure to PSNPs increased the microbial community diversity within the digesters and triggered the enrichment of Comamonadaceae and Syntrophaceae, belonging to Proteobacteria phylum. On the other hand, archaeal communities tended to shift towards hydrogenotrophic methanogens in PSNPs reactors. The correlation analysis showed that Comamonadaceae were positively correlated with the majority of ARGs and intl1. A positive correlation was observed between MGEs and most ARGs, suggesting that the increased proliferation of ARGs under PSNPs exposure may be linked to the abundance of MGEs, which in turn promotes the growth of hosts carrying ARGs. These findings suggest that aged and non-aged NPs could substantially impact the spread of ARGs and MGEs, which also led to notable alterations in the composition of the microbial community. Overall, this study provides valuable insights into the multifaceted impacts of PSNPs with various characteristics on AD processes, microbial communities, and ARGs proliferation, highlighting the urgent need for comprehensive assessments of NPs pollutants in the environment.

Role of UV radiation and oxidation on polyethylene micro- and nanoplastics: impacts on cadmium sorption, bioaccumulation, and toxicity in fish intestinal cells.

This study investigated the role of ultraviolet (UV) radiation and oxidation in high-density polyethylene microplastics (2-15 µm) and nanoplastics (0.2-9.9 µm) (NMPs) on particle chemistry, morphology, and reactivity with cadmium (Cd). Additionally, toxicity of NMPs alone and with Cd was evaluated using RTgutGC cells, a model of the rainbow trout (Oncorhynchus mykiss) intestine. The role on NMPs on Cd bioaccumulation in RTgutGC cells was also evaluated. Dynamic light scattering indicated that after UV radiation NPs agglomerated size increased from 0.8 to 28 µm, and to 8 µm when Cd was added. Oxidized MPs agglomerated size increased from 11 and 7 to 46 and 27 µm in non-UV- and UV-aged oxidized MPs when adding Cd, respectively. Cd-coated particles exhibited generally significantly higher zeta potential than non-Cd-coated particles, while attenuated total reflectance-Fourier transform infrared spectroscopy showed that the functional chemistry of the particles was oxidized and modified after being exposed to UV radiation. Presence of NMPs resulted in a significant decrease in Cd bioaccumulation in RTgutGC cells (100.5-87.9 ng Cd/mg protein) compared to Cd alone (138.1 ng Cd/mg protein), although this was not quite significant for co-exposures with UV-aged NPs (105.7 ng Cd/mg protein). No toxicity was observed in RTgutGC cells exposed to NMPs alone for 24 h. Moreover, co-exposures with Cd indicated that NMPs reduce the toxicity of Cd. Altogether these results show that UV aging enhances NMP surface reactivity, increasing Cd absorption in solution, which resulted in a reduction in Cd bioavailability and toxicity.

UV aging may enhance adsorption capacity of Poly (butylene adipate-co-terephthalate) (PBAT) to heavy metals and toxicity to zebrafish.

Compared with the fossil-based plastics, biodegradable plastics are more easily decomposed into small-sized particles (e.g., microplastics). However, the role of aged biodegradable plastics in being vector of co-existed pollutants and potential toxicological effects remain to be elucidated. The present study selected micro-sized biodegradable polymer Poly (butylene adipate-co-terephthalate) (PBAT) as the object, aiming to explore its aging process, environmental behavior with heavy metals (Cu and Pb), and the toxic effects on zebrafish. The results showed that distinct changes such as cracks and severe deformation can be observed on the surface of PBAT after 60 days of UV aging, and the functional groups changed consequently. The maximum adsorption capacity of aged PBAT for Cu and Pb reached 0.967 and 0.939 mg·g-1, which increased by 1.32 and 1.46 times, respectively. The results of 7-day acute toxicology experiments suggested that the adsorption behavior of aged PBAT may alleviate the toxic effects of heavy metals Cu and Pb on zebrafish in short-term exposure, however it could simultaneously cause a serious imbalance of intestinal microorganisms in zebrafish. As demonstrated, the coexistence of aged PBAT and heavy metals (Cu, Pb) can seriously reduce the intestinal microbial diversity and richness of zebrafish, which may induce more serious toxicity and disease in long-term exposure to pollutants. This study could provide fundamental data for better understanding on the adsorption behavior and ecological risk of aged biodegradable plastics with coexisted pollutants.

Nanoplastics inhibit carbon fixation in algae: The effect of aging.

Despite the considerable efforts devoted to the toxicological assessment of nanoplastics, the effect of UV-irradiation induced aging, a realistic environmental process, on the toxicity of nanoplastics toward microalgae and its underlying mechanisms remain largely unknown. Herein, this study comparatively investigated the toxicities of polystyrene nanoplastics (nano-PS) and the UV-aged nano-PS on the eukaryotic alga Chlorella vulgaris, focusing on evaluating their inhibitory effects on carbon fixation. Exposure to environmentally relevant concentrations (0.1-10 mg/L) of nano-PS caused severe damage to chloroplast, inhibited the photosynthetic efficiency and electron transport, and suppressed the activities of carbon fixation related enzymes. Multi-omics results revealed that nano-PS interfered with energy supply by disrupting light reactions and TCA cycle and hindered the Calvin cycle, thereby inhibiting the photosynthetic carbon fixation of algae. The above alterations partially recovered after a recovery period. The aged nano-PS were less toxic than the pristine ones as evidenced by the mitigated inhibitory effect on algal growth and carbon fixation. The aging process introduced oxygen-containing functional groups on the surface of nano-PS, increased the hydrophilicity of nano-PS, limited their attachment on algal cells, and thus reduced the toxicity. The findings of this work highlight the potential threat of nanoplastics to the global carbon cycle.

Impact of non-aged and UV-aged microplastics on the formation of halogenated disinfection byproducts during chlorination of drinking water and its mechanism.

Microplastics (MPs) are ubiquitously present in source water and undergo ultraviolet (UV) aging in aquatic environments before entering drinking water treatment plants. The presence of MPs in drinking water can impact the formation of halogenated disinfection byproducts (DBPs) during chlorine disinfection, yet the exact effect of MPs on DBP formation remain unclear. In this study, we conducted an investigation into the influence of non-aged and UV-aged MPs on halogenated DBP formation in drinking water and unveiled the underlying mechanisms. In comparison to source water samples devoid of MPs, the total organic halogen concentration was reduced by 19%-43% and 4%-13% in the drinking water samples containing non-aged and aged MPs, respectively. The differing effects on halogenated DBP formation can be attributed to the alternation in physical and chemical characteristics of MPs following UV aging. Aged MPs exhibited larger surface area with signs of wear and tear, heightened hydrophilicity, surface oxidation, increased oxygen-containing functional groups and dechlorination during the UV aging process. Both non-aged and aged MPs possess the capability to adsorb natural organic matter, leading to a reduction in the concentration of DBP precursors in the source water. However, the release of organic compounds from aged MPs outweighed the adsorption of organics. Furthermore, as a result of the surface activation of MPs through the UV aging process, the aged MPs themselves can also serve as DBP precursors. Consequently, the presence of halogenated DBP precursors in source water increased, contributing to a higher level of DBP formation compared to source water containing non-aged MPs. Overall, this study illuminates the intricate relationship among MPs, UV aging, and DBP formation in drinking water. It highlights the potential risks posed by aged MPs in influencing DBP formation and offers valuable insights for optimizing water treatment processes.

Effects of a Complex Environment on Fatigue and Self-Healing Characterization of Asphalt Composites Containing Rock Asphalt.

In recent years, asphalt pavement has been subjected to varied environmental conditions during its service life, conditions that predispose it to deformation and cracking. To enhance the performance of asphalt pavement, rock asphalt has been selected as a modifier due to its good compatibility with virgin asphalt binder and its ability to improve the fatigue cracking resistance of asphalt mixtures. Although scholars have conducted some studies on rock asphalt mixtures, research on the fatigue and self-healing performance of these mixtures under conditions such as ultraviolet (UV) aging and freeze-thaw remains limited. This paper presents findings from a study that employs a combined fatigue-healing test to assess the impact of such complex environmental factors on the fatigue and self-healing properties of fine aggregate matrix (FAM) mixtures containing three types of rock asphalts, i.e., Buton, Qingchuan (QC), and Uintaite Modifier (UM). The analysis of fatigue-healing test results, grounded in viscoelastic continuum damage (VECD) theory, indicates that rock asphalt can extend the fatigue life of FAM mixtures, albeit with a concomitant decrease in their self-healing capabilities. The study further reveals that UV aging, freeze-thaw, and UV aging-freeze-thaw conditions all led to a diminution in the fatigue and self-healing properties of FAM mixtures. However, FAM mixtures containing rock asphalt demonstrated greater resilience against these reductions. Atomic force microscope (AFM) results indicate that UV aging reduced the number of bee-structures and enlarged their area, whereas the incorporation of rock asphalt enhanced the uniformity of these structures' distribution, thereby improving the fatigue cracking resistance of FAM mixtures. Fourier transform infrared spectroscopy (FTIR) analysis reveals that while UV aging increased the carbonyl and sulfoxide indices within the asphalt binder, rock asphalt is effective in mitigating this effect to a certain degree, thereby enhancing the aging resistance of FAM mixtures.

POSS(epoxy)8 reinforced poly (butylene adipate-co-terephthalate)/lignin biodegradable films: Fabrication, enhanced mechanical properties and UV aging resistance.

To reduce the white pollution, the eco-friendly biodegradable poly (butylene adipate-co-terephthalate) (PBAT)-based films had attracted increasing interests worldwide. However, the high-cost of the PBAT had limited the large-scale development and application. In this work, 10 wt% low-cost lignin was introduced into the PBAT to prepare composite films by melt blending and blow molding, and the POSS(epoxy)8 was selected as the compatibilizer to improve the compatibility of PBAT and lignin. The maximum tensile strength and the nominal strain at break subsequently increased by 48.2 % and 21.4 % respectively, while the water vapor permeability enhanced by 9.9 %. Furthermore, the UV aging resistance of PBAT/lignin films were significantly improved, with only 1 wt% POSS(epoxy)8 content. This work provides an efficient strategy to foster the end-user confidence in the low-cost and eco-friendly biodegradable polymer materials with efficient performance.

A review on fate and ecotoxicity of biodegradable microplastics in aquatic system: Are biodegradable plastics truly safe for the environment?

Plastic products are extensively used worldwide, but inadequate management of plastic waste results in significant plastic pollution. Biodegradable plastic (BPs) offers an alternative to traditional plastics, however, not all BPs can fully degrade under natural conditions. Instead, they may deteriorate into biodegradable microplastic (BMPs) at a faster rate than conventional plastic, thereby posing an additional hazard to aquatic environments. This study provides a comprehensive overview of the fate of BPs in aquatic systems and their eco-toxicological effects on aquatic organisms such as algae, invertebrates, and fish. The findings highlight that BMPs have comparable or heightened effects compared to conventional microplastics (MPs) which physiochemical characteristic of the polymer itself or by the chemical leached from the polymeric matrix can affect aquatic organisms. While BPs is not a flawless solution to address plastic pollution, future research should prioritize investigating their production, environmental behavior, ecological impact, and whether BMPs inflict greater harm than conventional MPs.

Fracture Performance Study of Carbon-Fiber-Reinforced Resin Matrix Composite Winding Layers under UV Aging Effect.

There is limited research on the fracture toughness of carbon-fiber-reinforced polymer (CFRP) materials under accelerated UV aging conditions. In this study, the primary focus was on investigating the influence of varying durations of ultraviolet (UV) irradiation at different temperatures on the Mode I, Mode II, and mixed-mode fracture toughness of CFRP laminates. The results indicate that with increasing UV aging duration, the material's Mode I fracture toughness increases, while Mode II fracture toughness significantly decreases. The mixed-mode fracture toughness exhibits an initial increase followed by a subsequent decrease. Furthermore, as the aging temperature increases, the change in the fracture toughness of the material is more obvious and the rate of change is faster. In addition, the crack expansion of the composite layer of crack-containing Type IV hydrogen storage cylinders was analyzed based on the extended finite element method in conjunction with the performance data after UV aging. The results reveal that cracks in the aged composite material winding layers become more sensitive, with lower initiation loads and longer crack propagation lengths under the same load. UV aging diminishes the overall load-bearing capacity and crack resistance of the hydrogen storage cylinder, posing increased safety risks during its operational service.

Adsorption of Pb(II) by UV-aged microplastics and cotransport in homogeneous and heterogeneous porous media.

To investigate the adsorption effects of aged microplastics (MPs) on Pb(II) and their co-transport properties in homogeneous (quartz sand) and heterogeneous (quartz sand with apple branches biochar) porous media, we explored the co-transport of UV-irradiated aged MPs and coexisting Pb(II) along with their interaction mechanisms. The UV aging process increased the binding sites and electronegativity of the aged MPs' surface, enhancing its adsorption capacity for Pb(II). Aged MPs significantly improved Pb(II) transport through homogeneous media, while Pb(II) hindered the transport of aged MPs by reducing electrostatic repulsion between these particles and the quartz sand. When biochar, with its loose and porous structure, was used as a porous medium, it effectively inhibited the transport capacity of both contaminants. In addition, since the aged MPs cannot penetrate the column, a portion of Pb(II) adsorbed by the aged MPs will be co-deposited with the aged MPs, hindering Pb(II) transport to a greater extent. The transport experiments were simulated and interpreted using two-point kinetic modeling and the DLVO theory. The study results elucidate disparities in the capacity of MPs and aged MPs to transport Pb(II), underscoring the potential of biochar application as an effective strategy to impede the dispersion of composite environmental pollutants.

Microplastic aging alters the adsorption-desorption behaviors of sulfamethoxazole in marine animals: A study in simulated biological liquids.

Antibiotics and microplastics (MPs) coexisting as unique environmental contaminants may cause unintended environmental issues. In this study, the adsorption-desorption behaviors of sulfamethoxazole (SMX) on both original and UV-aged MPs were examined. Polyhydroxyalkanoates (PHA) and polyethylene (PE), which represent degradable and refractory MPs, respectively, were chosen as two distinct types of MPs. Furthermore, simulated fish intestinal fluids (SFIF) and simulated mammalian stomach fluids (SMGF) were employed to evaluate the desorption behaviors of SMX from aged MPs. Our findings demonstrate that UV-aging altered the polarity, hydrophilicity, and structure of the MPs. Aged MPs showed a higher adsorption capacity than the original MPs and they have a higher desorption capacity than original MPs in simulated body fluids. PE has a higher SMX desorption capacity in SFIF and the opposite happened in SMGF. Our results highlight the importance of considering the different adsorption-desorption behaviors of antibiotics on MPs when evaluating their environmental impact.

[Characteristics of Microplastic-derived Dissolved Organic Matter(MPDOM) and the Complexation Between MPDOM and Sulfadiazine/Cu2].

Microplastic-derived dissolved organic matter(MPDOM) during the aging process could be complexed with organic pollutants, heavy metals, and other contaminants and thus affect their migration and transformation. In this study, two types of microplastics, polyethylene terephthalate(PET) and polystyrene(PS), were selected to investigate the spectral properties of MPDOM and their effect on the complexation between MPDOM and sulfadiazine(SDZ)/copper ion(Cu2+) using the fluorescence quenching method, various spectroscopic analysis techniques, and the Ryan-Weber quenching model. The results of UV-vis absorption spectroscopy analysis showed that the molecular weight of the two MPDOMs decreased; the aromaticity and humification increased; and the carboxyl, carbonyl, hydroxyl, and ester substituents on aromatic rings increased after aging. The fluorescence quenching process between MPDOM and SDZ/Cu2+ was static quenching. After quenching, the aromaticity and humification of the two MPDOMs were similar, and the molecular weights were comparable. Combined with three-dimensional fluorescence spectra and parallel factor analysis, two humic-like components and one protein-like component were identified. In addition, the protein-like components of MPDOM reacted preferentially with SDZ and were more sensitive to Cu2+. The results of the Ryan-Weber quenching model revealed that the binding ability of humic-like components to PET-DOM was higher in both SDZ and Cu2+ quenching systems, but the binding ability of MPDOM in the SDZ quenching system was generally stronger than that in the Cu2+ system.

Reduced adsorption of norfloxacin on UV aging microplastics in anoxic environment.

Over recent years, much attention has been paid to aging problem of microplastics and adsorption behavior of antibiotic on microplastics. In this study, four microplastics, including polystyrene (PS), polypropylene (PP), polyamide (PA) and polyethylene (PE), were photoaged by UV light in anoxic environment. The surface characteristics of microplastics and adsorption behavior of norfloxacin (NOR) on microplastics were investigated. Results indicated that the specific surface area and crystallinity increased, and hydrophobicity weakened of microplastics after UV aging. The content of C element decreased and the content of O barely changed in the aged microplastics. In addition, the adsorption of NOR on microplastics yielded a better fitness for the pseudo-second-order kinetics, Langmuir and Freundlich models. The adsorption capacities of NOR on PS, PA, PP, and PE at 288 K were 16.01, 15.12, 14.03, and 13.26 mg·g-1, respectively, while the adsorption capacities of NOR on aged microplastics were reduced to 14.20, 14.19, 11.50, and 10.36 mg·g-1, respectively, due to decrease of hydrophobicity and increase of crystallinity of microplastics after UV aging. The adsorption of NOR on microplastics decreased with the increase of temperature, implying the adsorption process was exothermic. Adsorption mechanism analysis showed that Van der Waals force was the main influential mechanism of the adsorption of NOR on PP and PE, and hydrogen bond was the main factor affecting the adsorption of NOR on PA, while the π-π interaction was the main mechanism impacting the adsorption of NOR on PS. Aging time and salinity significantly affect the adsorption of NOR on microplastics. With the increase of humic acid concentration and pH, the adsorption of NOR on microplastics first reduced and then rose. This study provides a basis for further clarifying the mechanism of UV aging microplastics and a reference for the study of combined pollution behavior of microplastics and antibiotics.

Adsorption behavior of UV aged microplastics on the heavy metals Pb(II) and Cu(II) in aqueous solutions.

As the "vector" of heavy metals in the aquatic environment, microplastics (MPs) have a great influence on the migration and transformation of heavy metals. In this study, the adsorption of polypropylene (PP), polyethylene (PE) and polystyrene (PS) on two models of heavy metals after UV aging and environmental variables (ionic coexistence, pH, salinity, and fulvic acid) were comprehensively explored on adsorption. The results show that new oxidation functional groups are formed and their hydrophilicity is enhanced after MPs aging. As a result, the adsorption experiments showed that the adsorption of contaminants by UV aged MPs exceeds that of pristine MPs. The adsorption amounts of Pb(II) and Cu(II) by PP, PE and PS increased by 1.45, 1.46, 1.25 and 1.63, 1.39, 1.22 times, respectively. Adsorption kinetic data were more consistent with the pseudo-second-order kinetic model, proving chemisorption to be the mechanism governing the interaction between metal ions and MPs. The Freundlich model could accurately predict the heavy metal adsorption isotherms on MPs, showing that non-homogeneous multilayer adsorption dominates the process. In Pb(II)-Cu(II) binary composite system, metal ion adsorption capacity on MPs is less than that of the single system adsorption capacity, which proves that there is a specific inhibitory effect between coexisting ions. Additionally, external factors like pH, salinity, and fulvic acid content have a big impact on adsorption behavior. According to mechanism analysis, the adsorption process mainly relies on electrostatic interaction, surface complexation, and van der Waals force.

UV aging of microplastic polymers promotes their chemical transformation and byproduct formation upon chlorination.

The presence and accumulation of microplastics (MPs) in water and wastewater is a growing concern. When released to the water bodies, microplastics can be subject to surface weathering due to ultraviolet (UV) exposure. In this study, the effects of UV aging of six MP polymers from three groups (e.g., polyamide, polyester, and polyolefin) on their chlorine reactivity, chemical transformation, and formation of disinfection byproducts (DBPs) were studied. Polyamide (e.g., polyamide 6) in both virgin and UV-aged forms showed significantly higher chlorine demands than other MP polymers (915.5-947.9 versus 7.0-21.1 µmol/g MP in 24 h), and polyolefins were relatively inert to chlorine. UV aging enhanced the destructions of functional groups of polyamide and polyester upon chlorination, promoting the chlorine demands and leaching of organics by up to 1.7- and 2.4-fold, respectively. Polymer monomer and oligomers of polyamide 6 and toxic or endocrine disrupting additives (e.g., dimethyl phthalate and butyl octyl phthalate) were identified in leachates from chlorinated MP polymers by mass spectrometry. Meanwhile, up to >10-fold increases in the yields of trihalomethane, haloacetic acid, haloacetaldehyde, haloacetonitrile, and haloacetamide were observed from 30-day UV-aged MP polymers as compared to their virgin counterparts. Overall, this study reveals that UV aging can promote the reactivity and chemical transformation of MP polymers during chlorination, especially for polyamide and polyester, increase the release of polymer monomers, oligomers, and additives, and aggravate the role of MP polymers as DBP precursors.

UV-induced microplastics (MPs) aging leads to comprehensive toxicity.

Herein, the toxicity of 4 MPs and additives released from MPs during UV-aging was quantitatively evaluated by the transcriptional effect level index (TELI) based on E. coli whole-cell microarray assay, and MPs-antibiotics complex pollutants. Results showed that MPs and these additives had high toxicity potential, the maximum TELI was 5.68/6.85 for polystyrene (PS)/bis(2-ethylhexyl) phthalate (DEHP). There were many similar toxic pathways between MPs and additives, indicating that part of the toxicity risk of MPs was caused by the release of additives. MPs were compounded with antibiotics, the toxicity value changed significantly. The TELI values of amoxicillin (AMX) + polyvinyl chloride (PVC) and ciprofloxacin (CIP) + PVC were as high as 12.30 and 14.58 (P < 0.05). Three antibiotics all decreased the toxicity of PS and had little effect on polypropylene (PP) and polyethylene (PE). The combined toxicity mechanism of MPs and antibiotics was very complicated, and the results could be divided into four types: MPs (PVC/PE + CIP), antibiotics (PVC + TC, PS + AMX/ tetracycline (TC)/CIP, PE + TC), both (PP + AMX/TC/CIP), or brand-new mechanisms (PVC + AMX).