Novel Chemical Routes for Carbon Dioxide and Methane Production from Lignin Photodegradation: The Role of Environmental Free Radicals.

Sunlight irradiation significantly mediates plant litter's carbon dynamics and volatile carbon release in semi-arid and arid ecosystems. In this process, carbon loss is controlled by lignin, but the mechanisms of production of CO2 and CH4 during lignin photolysis are ambiguous. In this study, the photomineralization of plant litter and the lignocellulosic component collectively indicate that lignin is a major source of CO2 and CH4 emissions. Characterization and free radical analysis reveal that the production of CO2 is due to the oxidation and ring-opening reaction of the coniferyl alcohol unit, with the subsequent decarboxylation of carboxylic acid as an oxidation product. This reaction involves o-quinone formation by the reactions between O2, superoxide radical (O2·-), and persistent free radicals (PFRs)-bearing lignin. Of this, O2·- contributes to 43.2% of the photogenerated CO2, as a new pathway, derived from the electron transfer from PFRs to O2. Interestingly, photoinduced demethylation of the dimethoxybenzene-type compounds as the photolysis products of lignin results in a never-before-reported CH4 formation chemical route independent of that of O2. This mechanistic insight into the role of lignin in volatile carbon production from the irradiative plant litter will contribute to a deeper understanding of carbon balance in water-limited ecosystems.

Sulfur-Containing Persistent Free Radicals and Reactive Species on Photoaged Microplastics: Identification and the Formation Mechanism.

The elemental composition may affect the persistent free radical (PFR) and reactive species (RS) formation associated with photoaging microplastics; however, a relevant study is still lacking. This study systematically investigated the formation, evolution, and types of PFRs and RS on sulfur-containing microplastics (S-MPs) under simulated sunlight. Electron paramagnetic resonance detection and power saturation curve analysis isolated three different PFRs on each photoaging poly(phenylene sulfide) (PPS) and polysulfone (PSF). Combining the results of characterization and density functional theory calculation, these observed PFRs on the irradiated S-MPs were classified as oxygen-centered radicals with an adjacent S atom (namely, thio-oxygen radicals), oxygen-centered and sulfur-centered radicals, where the thio-oxygen radicals on PPS were benzenethiol-like radicals, and oxygen-centered radicals and sulfur-centered radicals on PSF that were identified as benzenesulfonic-like radicals and phenyl sulfonyl-like radicals, respectively. Moreover, potential precursor molecule fragments of PFRs on the photoaging S-MPs, including p-toluenesulfinic acid and benzenesulfonic acid, were detected by pyrolysis-gas chromatography/mass spectrometry and liquid chromatography-mass spectrometry. Interestingly, reactive sulfur species (SO3•-) was also observed on irradiated S-MPs in addition to reactive oxygen species, which was mainly derived from the reaction of •OH and sulfonyl radicals. These results have implications for assessing the potential risks of atmospheric S-MPs.

In Vitro Assessment Reveals the Effects of Environmentally Persistent Free Radicals on the Toxicity of Photoaged Tire Wear Particles.

Tire wear particles (TWP) have been identified as one of the major sources of microplastics (MPs), and few studies have focused on their environmental behaviors and impacts. However, a thorough characteristic and toxicity assessment associated with environmentally persistent free radicals (EPFRs) on the photoaged TWP is missing. In this study, we investigated EPFRs in the process of TWP photoaging and evaluated their toxicity using in vitro bioassays. Our results showed that a total of around 1.0 × 1017 spins/g EPFRs (g-factors ranging 2.00308-2.00318) was formed on TWP with 60 days of light irradiation, which contained more than 29% of reactive EPFRs (r-EPFRs). Using macrophages as model cells for bioassays, TWP-associated EPFRs trigged endpoints, including the decrease of cell viability (27 to 45%) and the increase of oxidative stress response (46-93%) and inflammatory factor secretion. The enhancement of TWP toxicity with photoaging was confirmed to be attributed to the generated EPFRs combined with other TWP's chemical compositions (e.g., various metals and organics). Most importantly, the toxicity of photoaged TWP was closely correlated with the generated r-EPFRs, which induced reactive oxidant species (ROS) generation. This study provides direct evidence of toxicity on the photoaged TWP particles, revealing the potential contributions of EPFRs to the adverse effect on human health and highlighting the need for an improved understanding of the impacts of EPFRs on the risk assessment of TWP released into the environment.

Insight into the Photodegradation of Microplastics Boosted by Iron (Hydr)oxides.

Iron (hydr)oxides as a kind of natural mineral actively participate in the transformation of organic pollutants, but there is a large knowledge gap in their impacts on photochemical processes of microplastics (MPs). This study is the first to examine the degradation of two ordinary plastic materials, polyethylene (PE) and polypropylene (PP), mediated by iron (hydr)oxides (goethite and hematite) under simulated solar light irradiation. Both iron (hydr)oxides significantly promoted the degradation of MPs (particularly PP) with a greater effect by goethite than hematite, related to hydroxyl radical (•OH) produced by iron (hydr)oxides. Under light irradiation, the surface Fe(II) phase catalyzed the production of H2O2 and promoted the release of Fe2+, leading to the subsequent light-driven Fenton reaction which produced a large amount of •OH. As the iron (hydr)oxides were modified with NaF at various concentrations, the activity of the surface Fe(II) as well as the release of Fe2+ were greatly reduced, and thus the •OH formation and MP degradation were depressed remarkably. It is worth noting that the surface hydroxyl groups (especially ≡FeOH) affected the reaction kinetics of •OH by regulating the activity of Fe species. These findings unveil the distinct impacts and intrinsic mechanisms of iron (hydr)oxides in influencing the photodegradation of MPs.

The First Observation of the Formation of Persistent Aminoxyl Radicals and Reactive Nitrogen Species on Photoirradiated Nitrogen-Containing Microplastics.

Nitrogen-containing microplastics (N-MPs) are widely present in the atmosphere, but their potential health risks have been overlooked. In this study, the formation of persistent aminoxyl radicals (PAORs) and reactive nitrogen species (RNSs) on the N-MPs under light irradiation was investigated. After photoaging, an anisotropic triplet with the g-factor of ∼2.0044, corresponding to PAORs, was detected on the nonaromatic polyamide (PA) rather than amino resin (AmR) by electron paramagnetic resonance and confirmed by density functional theory calculations. The generated amine oxide portions on the photoaged PA were identified using X-ray photoelectron spectroscopy and Raman spectroscopy, which were considered to be the main structural basis/precursors of a PAOR. Surprisingly, RNSs were also observed on the irradiated PA. The generated ·NO due to the aphotolysis of nitrone groups simultaneously reacted with peroxide radicals and O2·- to yield ·NO2 and peroxynitrite, respectively, which were responsible for peroxyacyl nitrates (PAN) and CO3·- formation. Besides, a significantly higher oxidative potential and reductive potential were observed for the aged PA than AmR, which is assigned to the abundant RNSs, organic hydroperoxides and PANs, and a strong ability to transfer electrons from PAOR, respectively. This work provides important information for the potential risks of airborne N-MPs and may serve as a guide for future toxicological assessments.

Sorption properties of cadmium on microplastics: The common practice experiment and A two-dimensional correlation spectroscopic study.

Microplastics (MPs) that have accumulated in the environment are emerging as contaminating pollutants due to their interactions with metal ions. MPs change the migration and transformation of metal ions in the environment and afterward impact their environmental presence. Therefore, it is necessary to evaluate the interaction characteristics and mechanisms between Cd2+and MPs for assessing the ecological impacts of MPs. The traditional sequencing batch equilibrium test demonstrated that the sorption of Cd2+ onto MPs was related to the type of MPs present, the pH value of the solution, the ionic strength of the participants and the presence of humic acid. The sorption dynamics and isotherm experiment illustrated that the interactions were controlled by surface sorption and distribution effects. The specific surface area and surface charge were the main factors in managing the sorption process. FTIR spectra and a 2D-COS analysis showed that different functional groups played an important role in the sorption of Cd2+onto MPs. The results from this work afford new insights on how MPs may play an important role in the fate and transport of heavy metals and present a new analysis method for evaluating the environmental behavior of MPs and their role in transporting other contaminants.

Formation of Environmentally Persistent Free Radicals on Microplastics under Light Irradiation.

Microplastics (MPs) are presumed to be inert during aging under ambient conditions. In this study, four types of virgin MPs, including polystyrene (PS), phenol-formaldehyde resin (PF), polyethylene (PE), and polyvinyl chloride (PVC), were aged under simulated solar light irradiation. Surprisingly, several environmentally persistent free radicals (EPFRs), which are considered to be a type of emerging contaminant, were detected on the irradiated PS and PF, rather than PE and PVC, by electron paramagnetic resonance (EPR) spectroscopy. Depending on the photoaging duration time, the characteristic g-factors of the EPFRs produced on PS and PF were 2.0044-2.0049 and 2.0043-2.0044, respectively. The generated EPFRs on PS and PF decayed rapidly at the initial stage and then slowly disappeared with the elapsed aging time. Analyses by attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), nuclear magnetic resonance (NMR), and gel permeation chromatography (GPC) suggested that MPs might experience chemical chain scission, O2/H2O addition, and EPFR formation under the light irradiation. Accompanying with the formation of EPFRs, reactive oxygen species, such as O2•- and •OH, were also observed. The findings provide a novel insight to evaluate the potential hazards of MPs to organisms and ecosystems.

Biodegradable plastics fragments induce positive effects on the decomposition of soil organic matter.

The escalating accumulation of plastic waste in ecosystems poses a significant health concern to soil environment, yet the environmental effects of plastics remains largely unexplored. Biodegradable plastics could offer a viable alternative to conventional persistent plastics, but our understanding of their potential benefits or detrimental effects on the decomposition of plant debris by soil biomass is limited. In this study, we conducted a year-long field experiment to examine the environmental response and impact on plant debris decomposition in the presence of varying quantities of persistent versus biodegradable plastics. Our findings indicate that the decomposition rate decreased by 2.8-4.9% for persistent plastics, while it increased by 1.3-4.2% for biodegradable plastics. Persistent plastics primarily induced adverse effects, including a reduction in soil nutrients, microbial diversity, bioturbation, enzyme activity, easily decomposable carbon, and microbial biomass carbon in plant debris. In contrast, biodegradable plastics resulted in beneficial effects such as an increase in enzyme activity, microbial biomass carbon, and easily decomposable carbon. We also observed that the decomposition rate of plant residues and nutrient release are closely associated with changes in the organic carbon chemical structure induced by different plastic film fragments. A significant shift in alkoxy carbon content facilitated the release of nutrients and soluble carbon, while modifications in carboxyl and aromatic carbon content hindered their release. Overall, our study reveals over one year that biodegradable plastics primarily induce positive effects on the decomposition of soil organic matter.

Molecular insights into microbial transformation of bioaerosol-derived dissolved organic matter discharged from wastewater treatment plant.

Wastewater treatment plants (WWTP) are important sources of aerosol-derived dissolved organic matter (ADOM) which may threaten human health via the respiratory system. In this study, aerosols were sampled from a typical WWTP to explore the chemical molecular diversity, molecular ecological network, and potential toxicities of the ADOM in the aerosols. The high fluorescence index (>1.9) and biological index (0.66-1.17) indicated the strong autogenous microbial source characteristics of the ADOM in the WWTP. DOM and microbes in the wastewater were aerosolized due to strong agitation and bubbling in the treatment processes, and contributed to 74 % and 75 %, respectively, of the ADOM and microbes in the aerosols. The ADOM was mainly composed of CHO and CHOS accounting for 35 % and 29 % of the total number of molecules, respectively, with lignin-like (69 %) as the major constituent. 49 % of the ADOM transformations were thermodynamically limited, and intragroup transformations were easier than intergroup transformations. Bacteria in the aerosols involved in ADOM transformations exhibited both cooperative and divergent behaviors and tended to transform carbohydrate-like and amino sugar/protein-like into recalcitrant lignin-like. The microbial compositions were affected by atmosphere temperature and humidity indirectly by modulating the properties of ADOM. Tannin-like, lignin-like, and unsaturated hydrocarbon-like molecules in the ADOM were primary toxicity contributors, facilitating the expression of inflammatory factors IL-ß (2.2-5.4 folds), TNF-α (3.5-7.0 folds), and IL-6 (3.5-11.2 folds), respectively.

Earthworm activity effectively mitigated the negative impact of microplastics on maize growth.

Microplastic pollution can have detrimental effects on soil environments and inhibit crop growth. Earthworms, known as soil engineers, promote crop growth, but their role and impact on the amelioration of microplastic-polluted soil is not yet clear. In this study, we investigated the impact and pathways of earthworm activity on microplastic-contaminated soil by introducing varying densities (without earthworm:0, low-density: 1, medium-density: 2, high-density: 5 ind column-1) of earthworms (epi-endogeic) into soil contaminated with two types of microplastics: polyethylene and polyvinyl chloride. Our results showed that earthworms all survived in soil polluted with two types of microplastics. Meanwhile, earthworm activity increased nutrient content and enzyme activity by 0.2-36.1% and 2.9-34.3%, respectively, and significantly increased soil microbial biomass and community diversity index. Earthworm activity also decreased antioxidant enzyme activity and promoted maize plant growth, including agronomic traits such as plant height, biomass, root length, and root surface area. Furthermore, the nutrient content of maize organs increased by 1.1-29.7%. Partial least squares models confirmed that earthworm activity alleviated the stress effect of microplastic pollution on plant growth by improving soil structure, fertility, and microbial abundance and diversity. The greatest effect on maize growth was observed with the improvement of soil physical-chemical properties. Our results suggest that medium densities of earthworms have the greatest soil improvement effect and provide an important basis for bioremediation of farmland contaminated by microplastics and promoting green and efficient development in agriculture.

Formation of halogenated macromolecular organics induced by Br- and I- during plasma oxidation/chlorination of DOM: Highlighting competitive mechanisms.

Understanding the effects of halogens on the production of macromolecular disinfection byproducts (DBPs) is critical for drinking water safety. The effects of Br- and I- on the chemical diversity of dissolved organic matter (DOM) during plasma preoxidation and the subsequent formation of macromolecular halogenated DBPs after chlorination were deciphered. Plasma preoxidation changed DOM diversity from aromatic component-oriented to lignin and tannin component-oriented, resulting in 62.0% and 21.2% decreases in N-DBPs (CkHnOmNzClx formulas) and C-DBPs (CkHnOmClx formulas) after chlorination, respectively. Br- could induce the formation of organobromine compounds (OBrCs) during plasma oxidation; however, the intensities of OBrCs decreased by 56.3% (CHO formulas) and 75.2% (CHON formulas) after further chlorination. OBrCs still accounted for 79.8% of the total organohalogen compounds (OXCs, X=Cl or Br) due to the higher substitutability of bromine. I-promoted OIC production in the DOM preoxidation process, and OICs acted as intermediates to form OClCs during chlorination. When Br-and I-coexisted, Br- promoted OIC production in the DOM preoxidation process; therefore, more OBrCs and OClCs were generated due to intermediates of OICs in subsequent chlorination. Connections between OXCs and their precursors were established using network computation. The precursors of OClCs were located in the aromatic structure region (0.2 < H/C ≤ 0.7; O/C ≤ 0.67); those of OBrCs and OICs were located in the lignin (0.7 < H/C ≤ 1.5; 0.1 < O/C < 0.67) and tannin (0.6 ≤ H/C ≤ 1.5, 0.67 < O/C < 1.0) regions with relatively greater H/C and O/C ratios, respectively.

Is the impact of atmospheric microplastics on human health underestimated? Uncertainty in risk assessment: A case study of urban atmosphere in Xi'an, Northwest China.

Microplastic (MP) exposure in the environment has been commonly demonstrated to have adverse effects on human health. The majority of studies on MP were related to the aquatic and terrestrial systems, its potential risk for ecosystem and human health when exposed to the atmosphere is not well-understood. The presented study, taking Xi'an, a megacity in Northwest China, as an example, first estimated the possibility of local residents bearing MPs pollution. The results figured out an average abundance of MPs in TSP, PM10, and PM2.5 was 12.5, 3.5 and 0.8 particles/L, respectively. A total of 15 polymer types of MPs were identified in the atmosphere. Although a species sensitivity distribution (SSD) approach is acknowledged to be useful to estimate the potential risk of pollutants, the result of SSD when used to evaluate the risk of MPs is debatable. In this study, SSD-based risk assessment showed that the atmospheric MP pollution in Xi'an had not yet reached the level of threatening human. However, unlike chemicals, it is unreliable to assess risk using the relationship of dose-response for MPs because toxic effects of MPs can be influenced by not only the abundance but also the characteristics, e.g., morphological size, shape and oxidative potential. Since insufficient mechanistic understanding regarding the relative relationship between MP characteristics and their toxic effects and limitation of the quality and relevance of toxicity data, the uncertainty of risk assessment of the atmospheric MPs is inevitable and the risk of the atmospheric MPs was tended to be underestimated. This poses a challenge to manufacturers and public health authorities, as well as researchers alike, however, we are already being exposed to the atmospheric MPs.

Photodegradation of microplastics mediated by different types of soil: The effect of soil components.

Microplastics (MPs) have attracted considerable attention due to its worldwide distribution, environmental persistence, and ecological risks. In this work, the photodegradation of MPs mediated by five different types of soils were investigated. The results showed: after 20 d of xenon lamp irradiation, significant degradation of MP was observed on Harbin (S1), Huainan (S2), Jiangxi (S3), Shaanxi (S4) and Hainan (S5). The order of photodegradation rate of MP was S2 > S5 > S4 > S1 > S3. The components of the soil have some correlations with MPs photodegradation. The photodegradation of MP mediated by soil components (specifically, the clay, the iron oxides and MnO2) displayed positive effect, while the photodegradation of MPs mediated by organic carbon showed inhibition trend. It is worth noting that electrostatic interaction may be the dominant factor affecting the interaction between MPs photodegradation rate and different soils surfaces. This study is helpful to deepen the understanding of the photochemical behavior of MP in soil, and is of great significance to evaluate the environmental fate and mechanism mediated by MP in soil.

Exposed facets mediated interaction of polystyrene nanoplastics (PSNPs) with iron oxides nanocrystal.

Nanoplastics (NPs), which are often detected in the natural environment, are regarded as a group of emerging pollutants. Hematite is a substance that exists widely in the surface environment and has an important impact on the environmental behavior of pollutants. Clarifying the migration of NPs requires an in-depth understanding of intrinsic interaction mechanisms of NPs with iron-containing minerals. The interaction process of polystyrene nanoplastics (PSNPs) on the hematite exposed facets was systematically studied by experiments under different conditions, adsorption isotherm curves, Fourier Transform infrared (FTIR) spectroscopy and two-dimensional correlation spectroscopy (2D-COS) analyses. We found that PSNPs were adsorbed on the three exposed faces of hematite ({001}, {012}, and {100}) by electrostatic interaction, respectively, but the capacities for PSNPs were different. Adsorption models were established to explore the preferred interaction surface dependent on the exposed facets, and it was found that {012} surfaces were more favorable for PSNPs adsorption, while {001} surface has better adsorption capacity for PSNPs than {100} surface, which is due to the different density and proportion of hydroxyl groups on the exposed facets of hematite. These findings elucidated the dependence of PSNPs adsorption on the hematite facets, and illustrated t the effect of hematite on the migration of PSNPs in the environment.

The protective layer formed by soil particles on plastics decreases the toxicity of polystyrene microplastics to earthworms (Eisenia fetida).

The recent discovery of microplastics contaminants in most ecosystems has raised major health issues, yet knowledge on their impact on soil organisms is limited, especially their toxicity evolution with aging. Herein, the toxicity of polystyrene microplastic (PS-MP) to earthworm (Eisenia fetida) along with aging was investigated. Results showed that the 28 d-LC50 (50% lethal concentration) of PS-MP was 25.67 g kg-1, whereas that increased to 96.47 g kg-1 after PS-MP initially aged in soil for 28 days, indicating the toxicity of PS-MP decreased with aging. Laser scanning confocal microscope and scanning electron microscope (SEM) found that the toxicity of PS-MP to earthworm may be due to the ingestion of PS-MP by earthworms and the physical damage (e.g., epidermis abrasion and setae loss) of PS-MP to earthworms. Similarly, the levels of reactive oxygen species, antioxidant enzyme activities and malondialdehyde content increased with PS-MP concentrations from 0.1 to 1.5 g kg-1, but decreased with aging from 7 to 28 days. The integrated biomarker response index also confirmed that the toxicity of PS-MP decreased with aging. SEM found that PS-MP were progressively covered by soil particles during soil aging, inducing the formation of protective layer and increasing the particle size of PS-MP, which prevented direct contact with earthworms and decreased the ingestion of PS-MP, in turn decreased PS-MP toxicity. Overall, our study provides valuable insights for elucidating the effect of aging on the toxicity of microplastics.

The characteristics of dissolved organic matter release from UV-aged microplastics and its cytotoxicity on human colonic adenocarcinoma cells.

There are a large number of microplastic (MPs) in the sea or on land, most of which undergo physical, chemical or biological processes leading to the release of dissolved organic matter (DOM). In this study, we analyzed the change of Polyurethane microplastic (PU-MPs) valence bond under different aging conditions thanks to Fourier transform infrared spectroscopy (FTIR) and its surface characteristics using scanning electron microscopy (SEM) and also described the characteristics of DOM dissolved from PU (PU-DOM) under UV aging process in two different medium (water and air), based on Dissolved organic carbon (DOC) measurements, UV-visible spectrometer and Three-dimensional excitation emission matrices (3D-EEMs). The DOC data both showed that Under UV aging of different systems, PU-DOM concentration increases with the extension of aging time, and correspondingly, its toxicity to human colon adenocarcinoma cells also increases, but the release amount of PU-DOM under air aging is higher than that of PU-DOM in water. We speculate that it may be the refraction and scattering of water, which leads to the reduction of the intensity of UV radiation. 3D-EEMs identified tryptophan-like fluorescent component and tyrosine-like component, meanwhile, the liquid chromatography-mass spectrometer (LC-MS) data further confirmed the formation of acid substances. The results further confirmed that the composition of PU-DOM in different systems is the same, but the release amount is different. The contents of the produced conjugated carbonyls and Reactive oxygen species (ROS) because of light irradiation increased likewise. The cytotoxicity of PU-DOM was consistent with the changing trend of ROS level in PU-MPs, suggesting that the produced ROS induced the in vitro toxicities. The results not only highlight the adverse health effects of photoaged PU-MPs, but also provide new perspectives for the environmental risks of MPs.

Generation of environmental persistent free radicals (EPFRs) enhances ecotoxicological effects of the disposable face mask waste with the COVID-19 pandemic.

A large amount of disposable plastic face masks (DPFs) is produced and used during the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) pandemic, which results in an inevitable consequence of the dramatic increase of DPFs waste. However, the impact of DPFs exposure to the environment on their toxicity is rarely considered. In this study, a range of 76-276 items/L microplastics (MPs) was detected in the DPFs leachates, and fibrous (> 80.3%) and polypropylene (PP, > 89.2%) MPs were dominant. Co, Cu, Ni, Sr, Ti and Zn, were commonly detected in all leachates of the tested DPFs. Organics, such as acetophenone, 2,4-Di-tert-butylphenol, benzothiazole, bisphenol-A and phthalide, were found in the DPFs leachate, which were including organic solvents and plasticizer. Besides, we first found an emerging environmental risk substance, namely environmentally persistent free radicals (EPFRs), was generated in the DPFs leachates. The characteristic g-factors of the EPFRs was in a range of 2.003-2.004, identified as mixture of carbon- and oxygen-centered radicals. By means of in vitro toxicity assay, the DPFs leachate were confirmed to cause cytotoxicity and oxidative stress. Significantly, it is found that the formed EPFRs could contribute more toxic effects. Furthermore, when compared to N95 respirators, the tested surgical masks tend to release more MPs, leach more metals and organics, and generate more EPFRs. Surgical masks were thus showed higher risk than N95 respirators after exposure to water. This work highlights the importance of understanding the chemical complexity and possible toxicity of DPFs for their risk assessment.

Inorganic anions influenced the photoaging kinetics and mechanism of polystyrene microplastic under the simulated sunlight: Role of reactive radical species.

The photo-transformation of microplastic (MP) in natural water may involve interactions with various ingredients, but the photoaging kinetics and underlying mechanism are not well understood. This work systematically explored the photoaging process of polystyrene microplastic (PS-MP) in the presence of commonly-found inorganic anions, including NO3-, HCO3-, Br- and Cl-. The addition of these ions led to more obvious changes in the morphology, functional groups and molecular weight of photoaging PS-MP. The evolution of carbonyl index value for the photoaged samples conformed to pseudo-first-order kinetic model, and the photoaging rate constant (k) in the presence of inorganic anions at their environmentally relevant concentrations of 0.6 mM, 1.2 mM, 0.1 M and 0.1 mM was calculated to be kHCO3- = 0.0074 d-1, kNO3- = 0.01001 d-1, kCl- = 0.00783 d-1, and kBr- = 0.00888 d-1, which was higher than that in ultrapure water (k=0.00705 d-1). Electron paramagnetic resonance technique and quenching experiments demonstrated that photo-transformation of PS-MP was mainly mediated by indirect photolysis, i.e., the formation of reactive radical species. The photosensitivity of NO3- promoted more •OH production, thereby accelerated the indirect photoaging of PS-MP. Meanwhile, the presence of halide ions promoted the generation of reactive halogen species, which were also involved in the indirect photoaging of PS-MP. Interestingly, as •OH scavenger, HCO3- had no inhibitory effect on PS-MP photoaging, attributing to the oxidation of CO3•-. This study provides valuable insights into the understanding of photo-transformation of MPs in natural aquatic environments.

The photodegradation processes and mechanisms of polyvinyl chloride and polyethylene terephthalate microplastic in aquatic environments: Important role of clay minerals.

It is well known that microplastics (MPs) may experience weathering and aging under ultraviolet light (UV) irradiation, but it remains unclear if these processes are impacted by natural components, such as clay minerals. In this study, we systematically investigated the photodegradation behaviors of polyvinyl chloride (PVC) and poly (ethylene terephthalate) (PET), two utmost used plastics, in the presence of clay minerals (kaolinite and montmorillonite). The results demonstrated that the clay minerals, particularly kaolinite, significantly promoted the MPs photodegradation, and the aging of PET was more prominent. The photodegradation was the most distinct at pH 7.0, regardless of the presence or absence of the clay minerals. The results of electron paramagnetic resonance and inhibition experiments of reactive oxygen species indicated that the minerals, particularly kaolinite, remarkably facilitated production of •OH, which was the key species contributing to the photodegradation of MPs. Specifically, UV irradiation facilitated the photo-ionization of MPs, producing hydrated electrons and MP radical cations (MP+). The Lewis base sites prevalent on the clay siloxane surfaces could stabilize the MP radical cations and prevent their recombination with hydrated electrons, which promoted the generation of •OH under aerobic conditions, and facilitated the degradation of MP. Two-dimensional (2D) Fourier transformation infrared (FTIR) correlation spectroscopy (COS) analysis and ultra-high-performance liquid chromatography coupled to a Q Exactive Orbitrap HF mass spectrometer were used to identify the sequential changes of functional groups, and the degradation products of the MPs. This study improves our understanding on the aging of MPs in the complex natural environment.

Degradation of polyethylene plastic in soil and effects on microbial community composition.

Plastics pollution in global soil systems is becoming a severely global issue and potential threat to terrestrial ecosystem serves and human health. Herein, in order to determine the degradability and ecological effects of polyethylene (PE) films, we measured the weight loss and characterization of PE films and analyzed variation in microbial community. The results of weight loss, SEM and FTIR spectra exhibited that PE films had unique degradation performance under different conditions. Simultaneously, we investigated the effects of PE films on the microbial community, and the microbiota colonizing on plastics. PE films may change the soil microbial community composition in soil, and hold the post of unique matrix for microbial colonization. These results indicate that the degradation of PE films and microbial community composition in soil can be affected by different conditions (soil layer, time and plants). By assessing the alteration of microbial community composition and PE films in soil, this work will contribute to enhance our understanding on the potential risks of plastics on soil ecosystems and provide a scientific basis for understanding the ecological effect of plastics on soil functions.