A Comparative Study on the Oxidation Mechanisms of Substituted Phenolic Pollutants by Ferrate(VI) through Experiments and Density Functional Theory Calculations.

In this work, the oxidation of five phenolic contaminants by ferrate(VI) was comparatively investigated to explore the possible reaction mechanisms by combined experimental results and theoretical calculations. The second-order rate constants were positively correlated with the energy of the highest occupied molecular orbital. Considering electronic effects of different substituents, the easy oxidation of phenols by ferrate(VI) could be ranked as the electron-donating group (-R) > weak electron-withdrawing group (-X) > strong electron-withdrawing group (-(C═O)-). The contributions of reactive species (Fe(VI), Fe(V)/(IV), and •OH) were determined, and Fe(VI) was found to dominate the reaction process. Four main reaction mechanisms including single-oxygen transfer (SOT), double-oxygen transfer (DOT), •OH attack, and electron-transfer-mediated coupling reaction were proposed for the ferrate(VI) oxidation process. According to density functional theory calculation results, the presence of -(C═O)- was more conducive for the occurrence of DOT and •OH attack reactions than -R and -X, while the tendency of SOT for different substituents was -R > -(C═O)- > -X and that of e--transfer reaction was -R > -X > -(C═O)-. Moreover, the DOT pathway was found in the oxidation of all four substituted phenols, indicating that it may be a common reaction mechanism during the ferrate(VI) oxidation of phenolic compounds.

Promoting Effect of Silver Oxide Nanoparticles on the Oxidation of Bisphenol B by Ferrate(VI).

Bisphenol B (BPB, 2,2-bis(4-hydroxyphenyl) butane), as a substitute for bisphenol A, has been widely detected in the environment and become a potential threat to environmental health. This work found that silver oxide nanoparticles (Ag2O) could greatly promote the removal of BPB by ferrate (Fe(VI)). With the presence of 463 mg/L Ag2O, the amount of Fe(VI) required for the complete removal of 10 µM BPB will be reduced by 70%. Meanwhile, the recyclability and stability of Ag2O have been verified by recycling experiments. The characterization results and in situ electrochemical analyses showed that Ag(II) was produced from Ag(I) in the Fe(VI)-Ag2O system, which has a higher electrode potential to oxidize BPB to enhance its removal. A total of 13 intermediates were identified by high-resolution mass spectrometry, and three main reaction pathways were proposed, including oxygen transfer, bond breaking, and polymerization. Based on the toxicity assessment through the ECOSAR program, it is considered that the presence of Ag2O reduced the toxicity of BPB oxidation intermediates to aquatic organisms. These results would deepen our understanding of the interaction between Fe(VI) and Ag2O, which may provide an efficient and environmentally friendly method for water and wastewater treatment.

New Findings of Ferrate(VI) Oxidation Mechanism from Its Degradation of Alkene Imidazole Ionic Liquids.

Chemical reactivity, kinetics, degradation pathways and mechanisms, and ecotoxicity of the oxidation of 1-vinyl-3-ethylimidazolium bromide ([VEIm]Br), the most common alternative to organic solvents, by Fe(VI) (HFeO4-) were studied by lab experiments and theoretical calculations. Results show that Fe(VI) can efficiently remove VEIm through the dioxygen transfer-hydrolysis mechanism, which has not been reported yet. The reactivity of VEIm toward Fe(VI) mainly depends on the double bonds in the side chain of VEIm. The second-order rate constant for VEIm was 629.45 M-1 s-1 at pH 7.0 and 25 °C. Typical water constituents, except for SO32-, Cl-, and Cu2+, had no obvious effects on the oxidation. The oxidation products were determined by high-performance liquid chromatography hybrid quadrupole time-of-flight mass spectrometry, which proves that there were interactions between the oxidation intermediates of the anion and cation parts of [VEIm]Br during the degradation process. The structures of related products and oxidation mechanisms were further rationalized by theoretical calculations. The ecotoxicity of products from the three oxidation pathways all showed a trend of increase after the initial decrease. We hope that the findings of this work can give researchers some new inspirations on Fe(VI) degradation of other alkene-containing contaminants.

Oxidative Oligomerization of Phenolic Endocrine Disrupting Chemicals Mediated by Mn(III)-L Complexes and the Role of Phenoxyl Radicals in the Enhanced Removal: Experimental and Theoretical Studies.

Soluble manganese(III), stabilized by ligands as Mn(III)-L complexes, are ubiquitous in natural waters and wastewaters and can potentially serve as both the oxidant and reductant in one-electron transfer reactions with organic contaminants. In this study, the oxidative transformations of 14 phenolic endocrine disrupting chemicals (EDCs) by in situ-formed Mn(III)-L complexes, generated from irradiated water containing Mn(II) and humic acid, were investigated. The pseudo-first-order rate constants (kobs, h-1) of these phenols varied from 1.0 × 10-4 to 5.9 × 10-2. A quantitative structure-activity relationship model was developed, which suggests that the electron-donating ability (EHOMO) of phenolic chemicals was the most important molecular characteristic for the Mn(III)-L-mediated oxidative transformation. Phenol transformation was initiated by the generation of a phenoxyl radical through electron transfer to Mn(III)-L. Subsequent self-coupling reactions between phenoxyl radicals resulted in the formation of self-coupling dimers and trimers. With the addition of simple phenol as a cosubstrate, enhanced transformations of these phenolic EDCs were clearly observed, and cross-coupling products of simple phenol and the substrates were also detected. In addition, a reaction activation energy calculation based on the transition-state theory indicated that the cross-coupling reaction was more likely than the self-coupling reaction to occur in the presence of phenol. This work provides new insights into the environmental fate of phenolic compounds.

Fe-Activated Peroxymonosulfate Enhances the Degradation of Dibutyl Phthalate on Ground Quartz Sand.

Soil contamination by organic compounds has received worldwide concern for decades. Here, we found that dibutyl phthalate (DBP) could be degraded on moist quartz sand (QS, crystal, a typical soil constituent) during stirring, and the removal rate reached 57.2 ± 3.1% after 8 h of reaction. The introduction of peroxymonosulfate (PMS) and zerovalent iron (Fe0) substantially improved the decomposition of DBP to 94.2 ± 1.6% in 8 h, suggesting they have great contributions. DBP decomposition was caused by multiple reactive species, such as surface silicon-based radicals (like ≡SiO•) and other reactive species like superoxide radical (O2•-), hydroxyl radical (•OH), and sulfate radical (SO4•-). In the QS/ultrapure water system, DBP was mainly attacked by O2•- or ≡SiO•, with the formation of hydrolysis products. In the iron@QS/PMS system, due to the activation of PMS by Fe0, SO4•- and •OH were produced while the latter led to DBP degradation, and thus hydroxyl substitution products of DBP were ubiquitous. DBP was hardly removed on amorphous supporters like silica gel, alumina, and red soil even with the presence of PMS and Fe0, indicating the indispensable role of surface radicals on crystals like QS. This work presents a new remediation technology for polluted soil, especially aquifer.

Enhanced Removal of Chlorophene and 17ß-estradiol by Mn(III) in a Mixture Solution with Humic Acid: Investigation of Reaction Kinetics and Formation of Co-oligomerization Products.

Reaction with soluble Mn(II) has been considered as a main decay pathway for superoxide in natural waters, accompanied by an important Mn redox cycling. In this study, the interaction of Mn(II) and humic acid (HA) was investigated in visible light irradiated water. Our results indicate that HA may play a dual role to act as a photosensitizer to produce superoxide anions (O2-) and as a strong ligand to stabilize the Mn(III), forming soluble Mn(III)L species for substrate transformation. Furthermore, the reaction kinetics, products, and mechanisms of chlorophene (CP) and estradiol (E2) mixture in the Mn(II)/HA/visible light reaction systems were assessed. The removal of CP and E2 was enhanced by 24.3% and 13.2%, respectively, in mixture solution at initial concentration of 1.0 µM for each target contaminant, as compared to the case of single-compound degradation. Product identification and density functional theory calculations indicated that cross-coupling reaction of CP and E2 radicals was more likely to occur than the self-coupling reaction in mixture solution. In addition, estrogenic activities of initial reaction solution were also effectively decreased during the transformation process. These findings provide new insights into Mn(III)-mediated reactions to better understand the environmental fate of organic contaminant mixture in waters.

Fe(VI)-Mediated Single-Electron Coupling Processes for the Removal of Chlorophene: A Combined Experimental and Computational Study.

Potassium ferrate [Fe(VI)] is a promising oxidant widely used in water treatment for the elimination of organic pollutants. In this work, the reaction kinetics, products, and mechanisms of the antimicrobial agent chlorophene (CP) undergoing Fe(VI) oxidation in aqueous solutions were investigated. CP is very readily degraded by Fe(VI), with the apparent second-order rate constant, k, being 423.2 M-1 s-1 at pH 8.0. A total of 22 oxidation products were identified using liquid chromatography-quadrupole time-of-flight-mass spectrometry , and their structures were further elucidated using tandem mass spectrometry. According to the extracted peak areas in mass spectra, the main reaction products were the coupling products (dimers, trimers, and tetramers) that formed via single-electron coupling. Theoretical calculations demonstrated that hydrogen abstraction should easily occur at the hydroxyl group to produce reactive CP· radicals for subsequent polymerization. Cleavage of the C-C bridge bond, electrophilic substitution, hydroxylation, ring opening, and decarboxylation were also observed during the Fe(VI) oxidation process. In addition, the degradation of CP by Fe(VI) was also effective in real waters, which provides a basis for potential applications.

Hydroxyl Radical Based Photocatalytic Degradation of Halogenated Organic Contaminants and Paraffin on Silica Gel.

Photochemical materials are of scientific and practical importance in the field of photocatalysis. In this study, the photochemistry of several organic contaminants, including decabromodiphenyl ether (BDE-209), halogenated phenols (C6 X5OH, X = F, Cl, Br) and paraffin, on silica gel (SG) surface was investigated under simulated solar irradiation conditions. Photolysis of these compounds at the solid/air interface proceeds with different rates yielding various hydroxylation products, and hydroxyl radical was determined as the major reactive species. According to density functional theory (DFT) calculations, the reaction of physically adsorbed water with reactive silanone sites (>Si═O) on silica was indispensable for the generation of •OH radical, where the required energy matches well with the irradiation energy of visible light. Then, the BDE-209 was selected as a representative compound to evaluate the photocatalytic performance of SG under different conditions. The SG material showed good stability in the photodegradation process, and was able to effectively eliminate BDE-209 under natural sunlight. These findings provide new insights into the potential application of SG as a solid surface photocatalyst for contaminants removal.

Photodegradation of Polyfluorinated Dibenzo-p-Dioxins in Organic Solvents: Experimental and Theoretical Studies.

Eighteen polyfluorinated dibenzo-p-dioxins (PFDDs) were synthesized by pyrolysis of fluorophenols. Using a 500 W Xe lamp as the light source, the PFDDs photodegradation kinetics in n-hexane were investigated. The photolysis reactions obeyed the pseudo-first-order rate equation, and higher fluorinated PFDDs tended to photolyze more slowly. Theoretically calculated parameters reflecting the molecular structural properties were used to develop a new model of PFDDs photolysis rates. The results indicated that the substitution pattern for fluorine atoms and the C-O bond length were major factors in the photolysis of PFDDs. We selected octafluorinated dibenzo-p-dioxin (OFDD) as a representative PFDDs to explore the influence of solvent on the photolysis rate of PFDDs, and the results indicated that neither the polarity nor donor hydrogen of organic solvents are independent influencing factors. Mechanistic pathways for the photolysis of OFDD in n-hexane were first studied. The results indicated that photodegradation of OFDD produces octafluorinated dihydroxybiphenyls, octafluorinated phenoxyphenols, and fluorinated phenols. The major pathway for photodegradation of OFDD was C-O bond cleavage. Defluorination reactions did not occur during the photolysis process.

Responses of antioxidant defense system to polyfluorinated dibenzo-p-dioxins (PFDDs) exposure in liver of freshwater fish Carassius auratus.

In this study, we evaluated the toxicity of ten polyfluorinated dibenzo-p-dioxins (PFDDs) congeners to freshwater fish Carassius auratus, by determining the antioxidative responses and lipid peroxidation in the liver after the fish were injected with two different concentrations (10 and 100 µmol/kg) of individual PFDDs for 3 and 14 days. The results showed that oxidative stress was obviously induced in some PFDDs-treated groups, as implied by the significantly inhibited antioxidants levels (superoxide dismutase, catalase, reduced glutathione, and glutathione S-transferase) and elevated malondialdehyde content. In addition, the oxidative stress inducing ability was variable for different PFDDs congeners, which was related with the substitution number and position of fluorine atom. Based on the calculated integrated biomarker response (IBR) values, the toxicity was ranked as 2,3,7,8-FDD>Octa-FDD>1,2,3,4,7-FDD>1,3,6,8-FDD>1,2,3,4,6,7-FDD>1,2,6,7-FDD>1,2,7-FDD>DD>2,7-FDD>2-FDD. This study can enhance the general understanding of the PFDDs induced oxidative stress in aquatic organisms.

Effects of in vivo exposure to polyfluorinated dibenzo-p-dioxins on organo-somatic indices and ethoxyresorufin-O-deethylase activity in mice (Mus musculus).

In this study, five different congeners of polyfluorinated dibenzo-P-dioxins (PFDDs) (1,8-di-FDD, 1,3,8-tri-FDD, 1,3,6,8-tetra-FDD, 2,3,7,8-tetra-FDD and 1,2,3,4,5,6,7,8-octa-FDD), representing different numbers and positions of fluorine substituents of all 75 PFDD congeners, were synthesized and purified to evaluate their potential environmental impact on living organisms. Their toxicity was evaluated by determining the impact on the organo-somatic indices (OSI) and ethoxyresorufin-O-deethylase (EROD) activity in mice (Mus musculus) after intragastric administration with different doses (0.5-100 µg/kg body weight) for 3 days. The results showed that these PFDDs significantly inhibited the growth and changed the OSI in mouse tissues. Notably, hepatic EROD activity was markedly induced in mice after exposure to these PFDDs, probably indicating a high affinity of binding to the aryl hydrocarbon receptor. Overall, these findings provided some preliminary but alarming toxicity data of PFDDs, and filled information gaps in the toxicological databases for living organisms.

Oxidative degradation of decabromodiphenyl ether (BDE 209) by potassium permanganate: reaction pathways, kinetics, and mechanisms assisted by density functional theory calculations.

This study found that decabromodiphenyl ether (BDE 209) could be oxidized effectively by potassium permanganate (KMnO4) in sulfuric acid medium. A total of 15 intermediate oxidative products were detected. The reaction pathways were proposed, which primarily included cleavage of the ether bond to form pentabromophenol. Direct oxidation on the benzene ring also played an important role because hydroxylated polybrominated diphenyl ethers (PBDEs) were produced during the oxidation process. The degradation occurred dramatically in the first few minutes and fitted pseudo-first-order kinetics. Increasing the water content decelerated the reaction rate, whereas increasing the temperature facilitated the reaction. In addition, density functional theory (DFT) was employed to determine the frontier molecular orbital (FMO) and frontier electron density (FED) of BDE 209 and the oxidative products. The theoretical calculation results confirmed the proposed reaction pathways.

A comparative study on antioxidant status combined with integrated biomarker response in Carassius auratus fish exposed to nine phthalates.

Laboratory experiments were performed to determine the antioxidant responses to nine phthalates (PAEs) in the liver of the goldfish Carassius auratus. The fish were injected with 10 mg/kg body weight of each PAE for 1 day and 4, 8, and 15 days. The potential biotoxicity of the PAEs were examined using the antioxidase and lipid peroxide indices. We determined that the superoxide dismutase (SOD), catalase (CAT), glutathione peroxidase (GPx), and malondialdehyde (MDA) levels displayed different trends following prolonged treatment, suggesting that metabolism generated either less toxic or more active substances. Based on the intensity of enzymes inhibition, MDA content, and the calculated integrated biomarker response (IBR), the toxicity order was determined as follows: dibutyl phthalate (DBP) > diethyl phthalate (DEP) > diisodecyl phthalate (DIDP) > diphenyl phthalate (DPP) > butyl benzyl phthalate (BBP) > diallyl phthalate (DAP) > dicyclohexyl phthalate (DCHP) > dimethyl phthalate (DMP) > di(2-ethylhexyl) phthalate (DEHP). In particular, DBP, which exhibited significant inhibition of enzyme activity and the greatest decrease in MDA content, may be a highly toxic contaminant. Furthermore, our results suggest that the IBR may be a general marker of pollution.

Occurrence of polychlorinated diphenyl sulfides (PCDPSs) in surface sediments and surface water from the Nanjing section of the Yangtze River.

Polychlorinated diphenyl sulfides (PCDPSs) are dioxin-like compounds that could induce various adverse effects to organisms. However, little is known about the occurrence of PCDPSs in the riverine environment. In the present study, the concentrations of twenty-one types of PCDPSs in the surface sediments and in surface water from the Nanjing section of the Yangtze River were examined. A total of 19 types of PCDPSs were detected and ∑PCDPSs concentrations in surface sediment and surface water ranged from 0.10 to 6.90 ng/g and 0.18 to 2.03 ng/L, respectively. The 2,2',4,4',5-penta-CDPS was the dominant congener in sediment (19.9%) and 2,2',3,3'-tetra-CDPS was the most abundant congener in water (12.2%). The tetra-CDPSs were the dominant congeners both in sediment and in water. Compared with sediment, the percentage of lower chlorinated PCDPSs in water increased distinctly. Source analysis revealed that the PCDPSs in the sediment and in the water mainly came from chemical wastewater rather than domestic sewage. There was a significant linear correlation between ∑PCDPS concentrations and sediment TOC contents, while no linear correlation existed between ∑PCDPS concentrations and water DOC contents. This study demonstrated the prevalent contamination by PCDPSs in sediments and in water from the Nanjing section of the Yangtze River.

Activation of avian aryl hydrocarbon receptor and inter-species sensitivity variations by polychlorinated diphenylsulfides.

It was hypothesized that polychlorinated diphenyl sulfides (PCDPSs) can potentially interact with an aryl hydrocarbon receptor (AHR) and thereby cause adverse effects in wildlife like birds. A recently developed avian AHR1-luciferase report gene (LRG) assay was used to assess the interaction between avian AHR1 and 18 PCDPSs and to compare the interspecies sensitivity among chicken, ring-necked pheasant, and Japanese quail by PCDPSs. Most of the tested PCDPSs could activate the AHR1-mediated pathways in avian species, and the relative potency (ReP) of the PCDPSs increased with the increasing number of substituted Cl atoms. The rank orders of PCDPSs potency were generally similar among birds, although the ReP varied. In addition, not all the sensitivity rank orders of avian AHR1 constructs for PCDPSs were consistent with that of TCDD. ReP values of PCDPSs suggested that some PCDPSs like 2,3,3',4,5,6-hexa-CDPS and 2,2',3,3',4,5,6-hepta-CDPS are higher than the avian WHO-TEFs of OctaCDD, OctaCDF, and most of the coplanar PCBs. Our results report for the first time the activation of an AHR1-mediated molecular toxicological mechanism by PCDPSs, and provide the ranking of ReP and relative sensitivity values of different congeners, which could guide the further toxicity test of this group of potential high priority environmental pollutants.

Effect of water quality on mercury toxicity to Photobacterium phosphoreum: Model development and its application in natural waters.

Mercury (Hg) compounds are widely distributed toxic environmental and industrial pollutants and they may bring danger to growth and development of aquatic organisms. The distribution of Hg species in the 3 percent NaCl solution was calculated using the chemical equilibrium model Visual MINTEQ, which demonstrated that Hg was mainly complexed by chlorides in the pH range 5.0-9.0 and the proportions of HgCl4(2-), HgCl3(-) and HgCl2(aq) reached to 95 percent of total Hg. Then the effects of cations (Ca(2+), Mg(2+), K(+) and H(+)), anions (HCO3(-), NO3(-), SO4(2-) and HPO4(2-)) and complexing agents (ethylene diamine tetraacetic acid (EDTA) and dissolved organic matter (DOM)) on Hg toxicity to Photobacterium phosphoreum were evaluated in standardized 15min acute toxicity tests. The significant increase of 6.3-fold in EC50 data with increasing pH was observed over the tested pH range of 5.0-8.0, which suggested the possible competition between hydroxyl and the negatively charged chloro-complex. By contrast, it was found that major cations (Ca(2+), Mg(2+) and K(+)) have little effect on Hg toxicity to P. phosphoreum. An interesting finding was that the addition of HPO4(2-) significantly increased Hg toxicity, which may imply that the addition of phosphate increased the soluble Hg-chloro complex species. Additions of complexing agents (EDTA and DOM) into the exposure water increased Hg bioavailability via complexation of Hg. Finally, a model which incorporated the effect of pH, HPO4(2-), HCO3(-), SO4(2-) and DOM on Hg toxicity was developed to predict acute Hg toxicity for P. phosphoreum, which may be a useful tool in setting realistic water quality criteria for different types of water.

Biochemical biomarkers in liver and gill tissues of freshwater fish Carassius auratus following in vivo exposure to hexabromobenzene.

Hexabromobenzene (HBB) is a novel brominated flame retardant (BFR) with ample evidence of its ubiquitous existence in the aquatic ecosystems. However, to date, the toxicological effects of this BFR on fish have been inadequately researched. The present study was conducted, based on an in vivo model, to investigate HBB-induced biochemical changes in liver and gill tissues of Carassius auratus after medium-term exposure to different concentrations (10, 150, and 300 mg/kg) for 7, 14, and 25 days. Oxidative stress was evoked evidently for the prolonged exposure, demonstrated by significant inhibition in antioxidant enzymes activities including superoxide dismutase, catalase, glutathione reductase, glutathione peroxidase, and glutathione S-transferase, and a decrease in reduced glutathione level, as well as simultaneous elevation in malondialdehyde content. Moreover, Na(+) , K(+) -ATPase activity, and protein level were remarkably reduced in fish tissues. Based on the integrated biomarker response, the toxic potency in each treatment was distinguished, and the more severe stress was mainly noted with the increasing concentrations and the extending durations. It was also observed that liver exhibited more pronounced alterations in biochemical parameters than gill, probably indicating the vulnerability of liver to HBB-triggered oxidative stress. Taken together, the results of this study clearly showed that HBB was capable of inducing oxidative stress and inhibiting Na(+) , K(+) -ATPase activity in different tissues of C. auratus after medium-term exposure.

Insights into enhanced oxidation of benzophenone-type UV filters (BPs) by ferrate(VI)/ferrihydrite: Increased conversion of Fe(VI) to Fe(V)/Fe(IV).

In this work, the oxidation performance of a new ferrate(VI)/ferrihydrite (Fe(VI)/Fh) system was systematically explored to degrade efficiently six kinds of benzophenone-type UV filters (BPs). Fe(VI)/Fh system not only had a superior degradation capacity towards different BPs, but also exhibited higher reactivity over a pH range of 6.0-9.0. The second-order kinetic model successfully described the process of BP-4 degradation by heterogeneous Fh catalyzed Fe(VI) system (R2 = 0.93), and the presence of Fh could increase the BP-4 degradation rate by Fe(VI) by an order of magnitude (198 M-1·s-1 v.s. 14.2 M-1·s-1). Remarkably, there are higher utilization efficiency and potential of Fe(VI) in Fe(VI)/Fh system than in Fe(VI) alone system. Moreover, characterization and recycling experiments demonstrated that Fh achieved certain long-term running performance, and the residual Fe content of solution after clarifying process meet World Health Organization (WHO) guidelines for drinking water. The contributions of reactive species could be ranked as Fe(V)/Fe(IV) > Fe(VI) > â€¢OH. Fe(IV)/Fe(V) were the dominant species for the enhanced removal in the Fe(VI)/Fh system, whose percentage contribution (72 %-36 %) were much higher than those in Fe(VI) alone system (5 %-17 %). However, the contribution of Fe(VI) in oxidizing BP-4 should not be underestimated (20 %-56 %). These findings reasonably exploit available Fh resources to reduce the relatively high cost of Fe(VI), which offers a proper strategies for efficient utilization of high-valent iron species and may be used as a highly-efficient and cost-effective BPs purification method.

Investigation of the photolysis process of benzo(a)anthracene (BaA) on polyvinyl chloride (PVC) and polystyrene (PS) microplastics: Plastics aging effect, transformation products and toxicity assessment.

Microplastics (MPs) and persistent pollutants (POPs) are new pollutants that are extensively studied worldwide. To fill the gaps that the degradation processes and mechanisms of polycyclic aromatic hydrocarbons (PAHs) on the surface of most MPs are still unclear, the photochemical transformation of benzo(a)anthracene (BaA) on polyvinyl chloride (PVC) MPs and polystyrene (PS) MPs in water were investigated and compared. The photolysis of BaA on the surface of PS in water proceeded easier than that on PVC within the 48 h irradiation period, with the pseudo-first-order rate constant of 0.0489 min-1 and 0.0181 min-1, respectively, which can be ascribed to the smaller particle size and more OH production of PS MPs. Due to the light competition between the chromophore and BaA as well as the light-shielding effect, aged MPs showed an inhibitory effect on the degradation of BaA compared with pristine MPs. For BaA/PVC MPs system, the degradation of BaA in real water was not significantly affected by coexisting ions and humic acid (HA) (p < 0.05), while slight inhibitory effect on the degradation of BaA appeared for PS MPs in different water matrices (UP: 86.97 %, YR: 84.47 %, PR: 81.42 % and HR: 83.21 %). According to the electron paramagnetic resonance (EPR) test, quenching experiment and probe experiment, the relative contribution of direct photolysis (PVC: 82.02 %; PS: 69.54 %) and indirect photolysis (PVC: 17.98 %; PS: 30.46 %) was confirmed. A total of 14 products were identified, and the product types were not affected by plastics aging. The results of the toxicity assessment indicated that although some intermediate products remained toxic to aquatic organisms, the toxicity of most products was lower than that of BaA. This study provides new insights into the environmental fate of PAHs and the role of MPs in the photolysis process of contaminants in surface water.

Insights into the photocatalytic degradation of hydrophobic organic contaminants on the surface of nitrogen doped silica: New findings of the formation of silicon-based substitution products.

In this work, nitrogen-doped SiO2 (N-SiO2) was successfully synthesized to develop an "adsorption-photocatalytic degradation" water purification technology to remove hydrophobic organic contaminants (HOCs). As a representative of HOCs, decabromodiphenylethane (DBDPE) could be efficiently degraded under simulated sunlight after adsorption on the surface of N-SiO2. Due to the generation of reactive oxygen species (ROS) and silicon-based radicals, the photodegradation rate of DBDPE on water-SiO2 interface was 1.5-fold higher than that in water. Furthermore, the transformation pathways of DBDPE on N-SiO2 surface were compared with that in water. Bond breaking and debromination reactions were the common pathways, while hydroxylation and silicon-based substitution reactions were the specific transformation pathways for DBDPE on the surface of N-SiO2. Density functional theory (DFT) calculation was used to reveal the generation mechanism of silicon-based radicals and determine the rationality of the involvement of silicon-based radicals in DBDPE transformation. The energy barriers of silicon-based substitution reaction were comparable to that of hydroxylation and debromination reactions, which confirmed the plausibility of the generation of silicon-based substitution products. This study provides an efficient method for the disposal of HOCs, which also gives some new insights into the conversion mechanism of organic pollutants mediated by silicon-based radicals.