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.

Sulfur-aided aerobic biostabilization of swine manure and sawdust mixture: Humification and carbon loss.

To investigate how sulfur addition affects humification and carbon loss during swine manure (SM) biostabilisation, various proportions of sulfur, i.e., 0 (CK), 0.2%-0.8% (S1-S4) were added to SM in a 70-day pilot-scale test. Compared to CK (16.07%), sulfur addition resulted in the mineralization of 17.05%-24.27% of the total organic carbon. Sulfur addition also reduced CH4 emissions, which were 3.7%-29.3% lower than that of CK. The total global warming potential values were in the range of 913.1-968.2 g CO2 eq kg-1 for all treatments. Although the sulfur-added treatments showed lower HA/FA ratios than CK after 70 days, no significant impact on the maturity of the final products was observed. Sulfur addition impacted the microbial community, CH4, CO2, N2O emissions, and affected the variation of temperature in biowaste biostabilization. These discoveries provided an important basis for understanding the function of sulfur in regulating the aerobic bio-decomposition of organic waste.

P, N, and C-related functional genes in SBR system promoted antibiotics resistance gene transmission under polystyrene microplastics stress.

Wastewater treatment plants (WWTPs) are important sinks of microplastics (MPs) and antibiotics resistance genes (ARGs). Information regarding connections between functional modules of WWTPs and spread of ARGs under MPs stress is still lacking. In this study, correlations between P-, N-, and C-related functional genes and ARGs in a sequencing batch reactor (SBR) system were evaluated under polystyrene (PS) MPs stress. Total P and chemical oxygen demand (COD) in effluent showed no significant changes under 0.5-50 mg L-1 PS MPs stress within 32 cycle treatment periods of SBR, while 0.5 mg L-1 PS MPs affected the N cycling process. PS MPs (0.5-50 mg L-1) promoted the richness and diversity of microbial community in SBR, and the denitrification process was exuberant. PS MPs with a low dosage (0.5-5 mg L-1) enhanced secretion of extracellular polymeric substances and promoted expression levels of functional genes related to C fixation, C degradation, P cycling, and N cycling. Simultaneously, aac(3)-II, blaTEM-1, and tetW increased by 27.13%, 38.36%, and 9.57% under low dosages of PS MPs stress; more importantly, the total absolute abundance of intI1 nearly doubled. 78.4% of these P-, N-, and C-related functional genes were positively correlated with intI1, thus favoring transmission of ARGs. This study firstly disclosed the underlying correlations between functional modules of WWTPs and spread of ARGs under MPs stress.

Formation of emerging disinfection byproducts from agricultural biomass-derived DOM: Overlooked health risk source.

Carbon-derived dissolved organic matter (CDOM) are inevitably released to surface water during returning agricultural biomass carbon to farmland, which are potential precursors of disinfection byproducts (DBPs). In this study, CDOM was extracted from aerobic incineration ("OX") and anoxic pyrolysis ("PY") of three kinds of straw (wheat, corn, and rice), and the emerging DBPs from them were deciphered. The CDOM with molecular weight < 1 kDa in the OX and PY groups accounted for 53-87%, and it was higher in the PY group. A total 1343-2107 of CHO and 641-1761 of CHNO formulas were detected in the CDOM derived from the OX group, among which 74%-83% contained aromatic structures rich in oxygen containing groups. 1919-3289 of CHO and 785-1954 of CHNO formulas were observed in the PY group, and 77%-86% of them were lignins/CRAM-like compounds. Surprisingly, 765-2158 and 895-1648 of emerging DBPs were identified in the OX and PY groups, and the proportions of N-DBPs were 20.3-54.8% and 2.8-4.8%, respectively. Based on HOCl addition and Cl substitution mechanisms, the H/C ratios of the DBP precursors in the OX and PY groups were in the range of 0.2-1.5 and 0.6-2.0, respectively. The DBPs derived from the OX group exhibited higher cytotoxicity and genotoxicity due to the higher aromaticity and more N-DBPs. Thus, returning agricultural biomass carbon, particularly that produced by direct combustion, to farmland brought potential threat to drinking water safety.

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.

Photocatalytic reduction of Cr(VI) via surface modified g-C3N4 by acid-base regulation.

Cr(VI) is a class of highly toxic heavy metals. In this study, alkali-modified g-C3N4 (cOH-CN) and acid-modified g-C3N4 (cH-CN) materials were successfully synthesized, and their photocatalytic activities for Cr(VI) reduction under visible light irradiation were tested. Owing to defect structures by cH-CN and -OH group introduction by cOH-CN, the modified materials exhibited a larger surface area, more abundant pore structures, a wider visible light absorption range, higher energy gap values, and a stronger capacity for electron-hole pair separation. As a result, satisfactory Cr(VI) reduction performance was gained by these two photocatalysts. Almost all Cr(VI) was converted to Cr(III) after 60 min of treatment in the presence of these two catalysts, while it was only 30% for the pristine g-C3N4 materials. Relatively higher dosages of cH-CN and cOH-CN and acidic conditions both improved Cr(VI) reduction in the cH-CN and cOH-CN photocatalytic systems. Cr(VI) reduction was mainly initiated by free electrons in the photocatalytic system of the modified materials. Finally, Cr(VI) in the photocatalytic system was almost completely converted to Cr(III). Furthermore, the stability and recycling of the cH-CN and cOH-CN catalysts were evaluated.

Intrinsic mechanisms underlying the highly efficient removal of bacterial endotoxin and related risks in tailwater by dielectric barrier discharge plasma.

Endotoxin is widely present in aquatic environments and can induce adverse health effects. In this study, dielectric barrier discharge (DBD) plasma was used to remove bacterial endotoxin from the tailwater of a wastewater treatment plant. The removal efficiency of total endotoxin activity was up to 92% with low electrical energy consumption (0.43 J mL-1%-1) after 180 s of the DBD plasma treatment, which was better than other previously reported methods. In the early stage of DBD plasma oxidation, the expression of genes related to cell morphology and bacterial antioxidant enzyme synthesis was distinctly down-regulated, suggesting that cell integrity was destroyed, leading to endotoxin release into the solution. Additionally, endotoxin synthesis in the cells was suppressed. The endotoxin in the solution was effectively removed by ·OH, 1O2, and O2·-generated by the DBD plasma, with second-order reaction rates of 2.69 × 1010, 2.20 × 107, and 8.60 × 108 mol-1 L s-1, respectively. The core toxic component of endotoxin (lipid A) was attacked by these strong oxidative species, generating smaller molecular fragments with low toxicity. Consequently, the inflammatory factors IL-6, IL-ß, and TNF-α of endotoxin decreased by 3.4-4.8 folds after the DBD plasma treatment, implying that the health risks posed by endotoxin were greatly reduced. This study revealed the intrinsic mechanisms of the highly efficient removal of bacterial endotoxin by DBD plasma oxidation.

Underlying mechanisms of promoted formation of haloacetic acids disinfection byproducts after indometacin degradation by non-thermal discharge plasma.

Indometacin (IDM), as a kind of non-steroidal anti-inflammatory drugs, has ecological and health risks, which is the potential precursor of chlorination disinfection byproducts (DBPs). Non-thermal discharge plasma was attempted to eliminate IDM and control subsequent DBPs formation. Satisfactory removal performance for IDM was realized by the plasma oxidation; almost 100% of IDM was removed within 2 min. Relatively greater removal efficiency was gained at a higher plasma voltage and a lower pH level. Electron paramagnetic resonance spectrometer revealed that reactive species ·OH, O2·-, and 1O2 were responsible for IDM decomposition. Based on analyses of Fourier transform infrared spectroscopy, two-dimensional correlation spectroscopy, three-dimensional fluorescence spectrum, and gas chromatography-mass spectrometer, attacks of reactive species resulted in sequence breakages in functional groups of IDM, leading to production of small molecular alcohols, acids, and amines. Possible decomposition pathways of IDM were proposed. The produced acetamide and 1H-indol-5-ol were important precursors of DBPs. Formation and toxicity of nitrogen-containing DBPs were dramatically inhibited after IDM degradation; however, those of haloacetic acids were strengthened. The relevant roadmaps among DBPs and degradation intermediates were figured out. This study revealed the underlying mechanisms of IDM degradation by discharge plasma and its potential risks in chlorination disinfection.

FT-ICR/MS deciphers formation of unknown macromolecular disinfection byproducts from algal organic matters after plasma oxidation.

Algal organic matter (AOM) is a potential precursor of disinfection byproducts (DBPs) in water treatment. It is a major challenge to identify macromolecular DBPs due to the diversity of AOM. In this study, Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR/MS) was applied to diagnose the AOM diversity after algae removal by plasma oxidation and to recognize the macromolecular DBPs in subsequent chlorination. Significant removal of AOM released by M. aeruginosa, C. raciborskii, and A. spiroies was achieved by plasma oxidation, accompanied by decrease in the proportion of CHNO formulas and increase in CHO formulas. Without plasma treatment, chlorination generated approximately 2486 macromolecular carbonaceous DBPs (C-DBPs) and 1984 nitrogenous DBPs (N-DBPs), with C11HnOmClx and C18HnNmOzClx as the most abundant DBPs. The numbers of C-DBPs and N-DBPs decreased by 63.3% and 62.9%, respectively, if plasma treatment was applied prior to chlorination. Network computational analysis revealed that Cl substitution was the main formation pathway of AOM-derived DBP formation rather than HOCl addition. The precursors of macromolecular DBPs contained a characteristic atomic number of C and O (7 ≤ C ≤ 18; 3 ≤ O ≤ 11). This study firstly disclosed the relationship between AOM diversity and novel macromolecular DBPs during algae-laden water treatment.

Inactivation efficacy and mechanism of pulsed corona discharge plasma on virus in water.

The presence of viruses in water is a major risk for human and animal health due to their high resistance to disinfection. Pulsed corona discharge plasma (PCDP) efficiently inactivates bacteria by causing damage to biological macromolecules, but its effect on waterborne virus has not been reported. This study evaluated the inactivation efficacy of PCDP to viruses using spring viremia of carp virus (SVCV) as a model. The results showed that 4-log10 reduction of SVCV infectivity in cells was reached after 120 s treatment, and there was no significant difference in survival of fish infected with SVCV inactivated by PCDP for 240 s or more longer compared to the control fish without virus challenge, thus confirming the feasibility of PCDP to waterborne virus inactivation. Moreover, the high input energy density caused by voltage significantly improved the inactivation efficiency. The further research indicated that reactive species (RS) generated by pulsed corona discharge firstly reacted with phosphoprotein (P) and polymerase complex proteins (L) through penetration into the SVCV virions, and then caused the loss of viral infectivity by damage to genome and other structural proteins. This study has significant implications for waterborne virus removal and development of novel disinfection technologies.

Pyrene contaminated soil remediation using microwave/magnetite activated persulfate oxidation.

Polycyclic aromatic hydrocarbons (PAHs) are important mutagen prevalent in the contaminated sites, bringing potential risks to human health. Iron oxides are important natural components in soils. Pyrene removal in soil using persulfate (PS) oxidation activated by microwave (MW) and magnetite (Fe3O4) was investigated. Fe3O4 significantly promoted pyrene removal in the soil; 91.7 % of pyrene was degraded within 45 min treatment. Pyrene removal rate in the Fe3O4/MW/PS system was 5.18 and 3.00 times higher than that in the Fe3O4/PS and MW/PS systems. Increasing in Fe3O4 dosage, PS concentration, MW temperature, and soil moisture content in the selected range were conducive for pyrene degradation. SO4•-, •OH, O2•-, and 1O2 were responsible for pyrene degradation, and the conversion of Fe (Ⅱ) in the Fe3O4 to Fe (Ⅲ) contributed to the formation of O2•- and 1O2. Characteristic bands of pyrene were more obviously destroyed by the Fe3O4/MW/PS oxidation, in comparison with MW/PS oxidation. Ring hydroxylation and ring-opening reactions were the main degradation pathways of pyrene. The toxicities of the formed byproducts were significantly reduced after treatment. This study provided a promising option for pyrene contaminated soil remediation.

Elimination of Microcystis aeruginosa in water via dielectric barrier discharge plasma: Efficacy, mechanism and toxin release.

Microcystis aeruginosa (M. aeruginosa), as the representative hazardous algae in cyanobacteria blooms, has long posed a threat to aquatic ecosystems. Here, a self-cooling dielectric barrier discharge plasma (DBDP) reactor was used to eliminate M. aeruginosa in water. The removal efficiency and mechanism of DBDP for M. aeruginosa and its toxin release during the treatment process was investigated. The results showed that over 99% of M. aeruginosa cells were removed by DBDP over 60 min under optimal conditions, and treated M. aeruginosa lost their ability to reproduce entirely. Reactive species generated in the self-cooling DBDP reactor damaged the membrane of M. aeruginosa, leading to leakage and degradation of dissolved organic matter. Increased intracellular reactive oxygen species accelerated the breakdown of protein and enzyme, and causes cell cytolysis. Eventually, M. aeruginosa was mineralized and lost its activity. The ·OH, 1O2 and ·O2- were crucial for inactivating M. aeruginosa. During the treatment process, the toxin microcystin-LR increased in the first 20 min, but declined over time: its concentration fell below 1 µg·mL-1 after 60 min. This study provides insight into M. aeruginosa' s elimination in water by DBDP and has significant implications for developing a plasma technique to curtail cyanobacteria bloom.

Zirconium hydroxide nanoparticle encapsulated magnetic biochar composite derived from rice residue: Application for As(III) and As(V) polluted water purification.

Finding a low-cost and suitable adsorbent is still in urgent need for efficient decontamination of As(III) and As(V) elements from the polluted waters. A novel zirconium hydroxide nanoparticle encapsulated magnetic biochar composite (ZBC) derived from rice residue was synthesized for the adsorptive capture of As(III) and As(V) from aqueous solutions. The results revealed that ZBC showed an acceptable magnet separation ability and its surface was encapsulated with lots of hydrous zirconium oxide nanoparticles. Compared to As(III), the adsorption of As(V) onto ZBC was mainly dependent on the pH of the solution. The intraparticle diffusion model described the adsorption process. ZBC showed satisfactory adsorption performances to As(III) and As(V) with the highest adsorption quantity of 107.6 mg/g and 40.8 mg/g at pH 6.5 and 8.5, respectively. The adsorption of As(III) and As(V) on ZBC was almost impervious with the ionic strength while the presence of coexisting ions, especially phosphate, significantly affected the adsorption process. The processes of complexation reaction and electrostatic attraction contributed to the adsorption of As(III) and As(V) onto ZBC. ZBC prepared from kitchen rice residue was found to be a low cost environmentally friendly promising adsorbent with high removal capacity for As(III) and As(V) and could be recycled easily from contaminated waters.

Plasma induced efficient removal of antibiotic-resistant Escherichia coli and antibiotic resistance genes, and inhibition of gene transfer by conjugation.

Antibiotic-resistant bacteria (ARB) and their resistance genes (ARGs) are emerging environmental pollutants that pose great threats to human health. In this study, a novel strategy using plasma was developed to simultaneously remove antibiotic-resistant Escherichia coli (AR bio-56954 E. coli) and its ARGs, aiming to inhibit gene transfer by conjugation. Approximately 6.6 log AR bio-56954 E. coli was inactivated within 10 min plasma treatment, and the antibiotic resistance to tested antibiotics (tetracycline, gentamicin, and amoxicillin) significantly decreased. Reactive oxygen and nitrogen species (RONS) including •OH, 1O2, O2•-, NO2-, and NO3- contributed to ARB and ARGs elimination; their attacks led to destruction of cell membrane, accumulation of excessive intracellular reactive oxygen substances, deterioration of conformational structures of proteins, and destroy of nucleotide bases of DNA. As a result, the ARGs (tet(C), tet(W), blaTEM-1, aac(3)-II), and integron gene intI1), and conjugative transfer frequency of ARGs significantly decreased after plasma treatment. The results demonstrated that plasma has great prospective application in removing ARB and ARGs in water, inhibiting gene transfer by conjugation.

Insights into the underlying mechanisms for integrated inactivation of A. spiroides and depression of disinfection byproducts by plasma oxidation.

Cyanobacteria blooms threaten water supply and are potential sources for disinfection byproducts (DBPs) formation. In this study, the underlying mechanisms for effective removal of A. spiroides and the following depression on the formation of DBPs were disclosed. Highly efficient inactivation (more than 99.99%) of A. spiroides was realized by the plasma treatment within 12 min, and 93.4% of Anatoxin-a was also removed within 12 min, with no signals of resurrection after 7 days' re-cultivation. Transcriptomic analysis demonstrated that the expressions of the genes related to cell walls and peripherals, thylakoid membranes, photosynthetic membranes, and detoxification of toxins were distinctly altered. The generated reactive oxidative species (ROS), including ·OH, O2·-, and 1O2, attacked A. spiroides and resulted in membrane damage and algae organic matter (AOM) release. EEM-PARAFAC analysis illustrated that the AOM compositions were subsequently decomposed by the ROS. As a result, the formation potentials of the C-DBPs and N-DBPs were significantly inhibited, due to the effectively removal of AOM and Anatoxin-a. This study disclosed the underneath mechanisms for the effective inactivation of A. spiroides and inhibition of the following formation of the DBPs, and supplied a prospective technique for integrated pollutant control of cyanobacterial containing drinking water.

Enhanced removal of acid orange II from aqueous solution by V and N co-doping TiO2-MWCNTs/γ-Al2O3 composite photocatalyst induced by pulsed discharge plasma.

This paper presents a study of V and N co-doping TiO2 embedding multi-walled carbon nanotubes (MWCNTs) supported on γ-Al2O3 pellet (V/N-TiO2-MWCNTs/γ-Al2O3) composite photocatalyst induced by pulsed discharge plasma to enhance the removal of acid orange II (AO7) from aqueous solution. The photocatalytic activity of the V/N-TiO2-MWCNTs/γ-Al2O3 composite to AO7 removal induced by the pulsed discharge plasma was evaluated. The results indicate that the V/N-TiO2-MWCNTs/γ-Al2O3 composite possesses enhanced photocatalytic activity that facilitates the removal of AO7 compared with the TiO2-MWCNTs/γ-Al2O3 and TiO2/γ-Al2O3 composites. Almost 100% of AO7 is removed after 10 min under optimal conditions. The V0.10/N0.05-TiO2-MWCNTs/γ-Al2O3 photocatalyst exhibits the best removal effect for AO7. Analysis of the removal mechanism indicates that the enhancement of the removal of AO7 resulting from V and N co-doping causes TiO2 lattice distortion and introduces a new impurity energy level, which not only reduces the band gap of TiO2 but also inhibits the recombination of the ecb-/hvb+ pairs.

Remediation of organophosphorus pesticide polluted soil using persulfate oxidation activated by microwave.

Contaminated sites from pesticide industry have attracted global concern due to the characteristics of organic pollution with high concentrations and complete loss of habitat conditions. Remediation of organophosphorus pesticide polluted soil using microwave-activated persulfate (MW/PS) oxidation was investigated in this study, with parathion as the representative pesticide. Approximately 90 % of parathion was degraded after 90 min of MW/PS oxidation treatment, which was superior to those by single PS or MW treatment. Relatively greater performances for parathion degradation were obtained in a relatively larger PS dosage, higher microwave temperature, and lower organic matter content. Appropriate soil moisture favored parathion degradation in soil. SO4-, OH, O2-, and 1O2 generated in the MW/PS system all contributed to parathion degradation. Multiple spectroscopy analyses indicated that PO and PS bonds in parathion were destroyed after MW/PS oxidation, accompanied by generation of hydroxylated and carbonylated byproducts. The soil safety after parathion degradation was assessed via model prediction. Furthermore, MW/PS oxidation also exhibited great performance for degradation of other organophosphorus pesticides, including ethion, phorate, and terbufos.

Simultaneous removal of chromium(VI) and tetracycline hydrochloride from simulated wastewater by nanoscale zero-valent iron/copper-activated persulfate.

In this paper, metallic copper (Cu) was supported on nanoscale zero-valent iron (nZVI) to form a nanoscale bimetallic composite (nZVI-Cu), which was used to activate persulfate (PS) to simultaneously remove the compound contaminants Cr(VI) and tetracycline hydrochloride (TCH) in simulated wastewater. nZVI, nZVI-Cu, and nZVI-Cu-activated PS (nZVI-Cu/PS) were characterized by SEM, TEM, XRD, and XPS. The effects of the bimetallic composite on Cr(VI) and TCH removal were compared in the nZVI, nZVI-activated PS (nZVI/PS), nZVI-Cu, and nZVI-Cu/PS systems. The results showed that nZVI and Cu can form a nanobimetallic system, which can create galvanic cells; thus, the galvanic corrosion of nZVI and the transfer of electrons are accelerated. For a single contaminant, the removal efficiency of Cr(VI) and TCH is the highest when nZVI is loaded with 3 wt% and 1 wt% Cu, respectively. The ratio of nZVI-Cu with 3 wt% Cu to PS is 7:1, and the removal efficiency of Cr(VI) and TCH compound contaminants is ~ 100% after 60 min under acidic conditions, which indicates that the Cr(VI) reduction and TCH oxidation were complete in the nZVI-Cu/PS system. The mechanisms of simultaneous removal of Cr(VI) and TCH in the nZVI-Cu/PS system are proposed. The removal of Cr is because of the adsorption-reduction effects of the nZVI-Cu bimetallic material. The degradation of TCH is mainly due to the action of oxidative free radicals generated by Fe2+-activated PS. The free radical capture experiments showed that SO- 4· plays a major role in the process of TCH degradation.

Probing the aging processes and mechanisms of microplastic under simulated multiple actions generated by discharge plasma.

Microplastics (MPs) are becoming one class of pollutants with high global concerns. Information regarding aging behaviors of MPs in complicated natural conditions is still lacking due to the very slow aging processes. In this study, discharge plasma oxidation was applied to simulate the various radical oxidation and physical effects naturally occurring in the environment to shed light on the aging behaviors and mechanisms of MPs, with polyvinyl chloride microplastic (PVC-MP) as a model. The surface morphology, particle size, specific surface area, crystallinity, and chemical compositions of PVC-MP were comprehensively characterized as a result of aging. The aging degree indicated by carbonyl index and oxygen-to-carbon ratio increased with the plasma oxidation intensity and duration. The aged PVC-MP was characterized as more O-containing functional groups, smaller particle size, larger specific surface area, higher hydrophilicity, and higher crystallinity. Consequently, the aged PVC-MP provided more sites for adsorption of tetrabromobisphenol (TBBPA) in solutions by forming hydrogen-bonds, and electrostatic force. The changes in the properties of the aged PVC-MP, and the strong adsorption with TBBPA led to unexpected synergistic toxic effects to Scenedesmus obliquus. The results provide direct evidences of aging processes of MPs and the potential environmental risks due to aging in the environment.