Transformation Of Organic Pollutants Research Articles

Insights into sunlight-driven transformation of tetracycline by iron (hydr)oxides: The dominating role of self-generated hydrogen peroxide

Iron (hydr)oxides are abundant in surface environment, and actively participate in the transformation of organic pollutants due to their large specific surface areas and redox activity. This work investigated the transformation of tetracycline (TC) in the presence of three common iron (hydr)oxides, hematite (Hem), goethite (Goe), and ferrihydrite (Fh), under simulated sunlight irradiation. These iron (hydr)oxides exhibited photoactivity and facilitated the transformation of TC with the initial phototransformation rates decreased in the order of: Hem > Fh > Goe. The linear correlation between TC removal efficiency and the yield of HO• suggests that HO• dominated TC transformation. The HO• was produced by UV-induced decomposition of self-generated H2O2 and surface Fe2+-triggered photo-Fenton reaction. The experimental results indicate that the generation of HO• was controlled by H2O2, while surface Fe2+ was in excess. Sunlight-driven H2O2 production in the presence of the highly crystalline Hem and Goe occurred through a one-step two-electron reduction pathway, while the process was contributed by both O2-induced Fe2+ oxidation and direct reduction of O2 by electrons on the conduction band in the presence of the poorly crystalline Fh. These findings demonstrate that sunlight may significantly accelerate the degradation of organic pollutants in the presence of iron (hydr)oxides.

Electron beam radiation coupled to flocculation for advanced treatment of coking and dyeing wastewater: Performance and synergistic effect

Advanced treatment of industrial wastewater is a tough problem in the field of wastewater treatment. In this study, the electron beam radiation coupled to flocculation process was firstly developed and investigated for the advanced treatment of coking and dyeing wastewater. Three different coupled processes were studied, i.e. electron beam radiation followed by flocculation process (EBF), flocculation followed by electron beam radiation process (FEB), and simultaneous electron beam radiation and flocculation process (SEBF). It was found that different processes had various performances in the removal of targeted organic pollutants. For humic acid, FEB with poly aluminum ferric chloride (PAFC) as flocculants showed the best synergistic effect at 10 kGy, in which the removal of humic acid was 95.2%, while SEBF exhibited the inhibition effect under all the conditions. For Rhodamine B, EBF with PAFC had the highest synergistic effect at 10 kGy, in which the removal of Rhodamine B was 87.4%. For phenol, SEBF with PAFC as flocculants showed the highest synergistic effect at 10 kGy, in which the phenol removal was 64.2%. The transformation of organic pollutants, such as the polymerization was the main reason for the synergistic effect of EBF, while the dissolved iron ions and the enhanced oxidation made major contribution to the synergistic effect of FEB, and the structural change of flocculants and the transformation of organic pollutants during the process of electron beam radiation was mainly responsible for the synergistic effect of SEBF. EBF showed better performance in COD removal for actual coking and dyeing wastewater than FEB, indicating that electron beam radiation could promote the flocculation effect. Considering the operation procedure and treatment cost comprehensively, EBF with PAFC is recommended for the advanced treatment of actual coking and dyeing wastewater. This study could provide a novel and effective method for the advanced treatment of industrial wastewater.

Wavelength-dependent direct and indirect photochemical transformations of organic pollutants

Sunlight-induced photochemical transformations greatly affect the persistence of organic pollutants in natural environment. Whereas sunlight intensity is well-known to affect pollutant phototransformation rates, the reliance of pollutant phototransformation kinetics on sunlight spectrum remains poorly understood, which may greatly vary under different spatial-temporal, water matrix, and climatic conditions. Here, we systematically assessed the wavelength-dependent direct and indirect phototransformations of 12 organic pollutants. Their phototransformation rates dramatically decreased with light wavelength increasing from 375 to 632 nm, with direct photolysis displaying higher wavelength-dependence than indirect photolysis. Remarkably, UV light dominated both direct (90.4–99.5 %) and indirect (64.6–98.7 %) photochemical transformations of all investigated organic pollutants, despite its minor portion in sunlight spectrum (e.g., 6.5 % on March 20 at the equator). Based on wavelength-dependent rate constant spectrum, the predicted phototransformation rate of chloramphenicol (4.5 ± 0.7 × 10−4 s−1) agreed well with the observed rate under outdoor sunlight irradiation (4.3 ± 0.0 × 10−4 s−1), and there is no significant difference between the predicted rate and the observed rate (p-value = 0.132). Moreover, rate constant and quantum yield coefficient (QYC) spectrum could be applied for facilely investigate the influence of spectral changes on the phototransformation of pollutants under varying spatial-temporal (e.g., season, latitude) and climatic conditions (e.g., cloud cover). Our study highlights the wavelength-dependence of both direct and indirect phototransformation of pollutants, and the UV part of natural sunlight plays a decisive role in the phototransformation of pollutants.

Differential photodegradation processes of adsorbed polychlorinated biphenyls on biochar colloids with various pyrolysis temperatures

Despite the crucial role of photodegradation in the environmental transformation of organic pollutants, the photodegradation process of organic pollutants irreversibly absorbed on biochar colloids (BCCs) remains poorly understood. This study investigated the photodegradation processes and mechanisms of 2,4,4′-trichlorobiphenyl (PCB28) adsorbed on BCCs released from bulk biochars derived from bamboo chips at pyrolysis temperatures of 300, 500, and 700 °C. Results show that BCCs-adsorbed PCB28 could be degraded under simulated solar illumination (95–105 mW·cm−2) but at decreased photodegradation rates compared to the dissolved PCB28. The inhibition effect of BCCs on the PCB28 photodegradation increased with increasing pyrolysis temperature. After adsorptive binding to BCCs, the half-life of PCB28 (0.1 mg/L) was prolonged from 2.65 h for the dissolved PCB28 alone in deionized water to 7.48, 40.67, and 81.82 h in the presence of BCC300, BCC500, and BCC700 (5.0 mg/L), respectively. Mechanistically, the photodegradation of adsorbed pollutants was regulated by the photogenerated free radicals and surface functional groups of the low-temperature BCCs, as well as the defects and direct electron transfer capabilities of the high-temperature BCCs; PCB28 adsorbed on the low-temperature BCCs accepted electrons from persistent free radicals under light illumination, which led to PCB28 dechlorination, followed by ring-opening oxidation through hydroxyl radical attack, ultimately resulting in progressive mineralization; singlet oxygen caused preferential ring opening of adsorbed PCB28 on the high-temperature BCCs, preceding dechlorination. The photodegradation of BCCs-adsorbed PCB28 remained significant though more or less being inhibited under the effects of water pH, ionic strength, dissolved organic matters (humic acid and fulvic acid), and in natural water samples. These findings contribute to a better understanding of the structural properties of BCCs that impact phototransformation processes of adsorbed pollutants and facilitate an accurate assessment of the environmental risk associated with biochar application.

Modulating the photooxidation selectivity on graphitic carbon nitride by tuning edge functional groups

Selective photooxidation reactions offer a promising route for transformation of organic pollutants into high-value products under mild conditions. In this work, we demonstrate that the edge functional groups in polymer carbon nitride (PCN) were key to the selectivity of methyl mercaptan (CH3SH) photocatalytic oxidation. The amino-decorated PCN favors the oxidation of the -SH group of CH3SH to forming CH3SO3H with selectivity up to 84.0%, while cyanamide-enriched PCN prefers to breaking the -CH3 end of CH3SH and produce H2SO4 with selectivity of 82.0%. The totally difference in reaction sites is ascribed to the functional-group-modulated electronic structure of PCN, which determines activity of photoinduced carriers and the molecular oxygen activation pathway. The amino- and cyanamide-decorated PCN leads to preferential generation of 1O2 and·O2-, respectively. This study highlights the significant role of edge groups engineering in modulation of the excitonic effects in PCN and the resultant selectivity control during photocatalytic reaction.

First-principles study on the heterogeneous formation of environmentally persistent free radicals (EPFRs) over α-Fe2O3(0001) surface: Effect of oxygen vacancy

Metal oxides with oxygen vacancies have a significant impact on catalytic activity for the transformation of organic pollutants in waste-to-energy (WtE) incineration processes. This study aims to investigate the influence of hematite surface oxygen point defects on the formation of environmentally persistent free radicals (EPFRs) from phenolic compounds based on the first-principles calculations. Two oxygen-deficient conditions were considered: oxygen vacancies at the top surface and on the subsurface. Our simulations indicate that the adsorption strength of phenol on the α-Fe2O3(0001) surface is enhanced by the presence of oxygen vacancies. However, the presence of oxygen vacancies has a negative impact on the dissociation of the phenol molecule, particularly for the surface with a defective point at the top layer. Thermo-kinetic parameters were established over a temperature range of 300–1000 K, and lower reaction rate constants were observed for the scission of phenolic O-H bonds over the oxygen-deficient surfaces compared to the pristine surface. The negative effects caused by the oxygen-deficient conditions could be attributed to the local reduction of FeIII to FeII, which lower the oxidizing ability of surface reaction sites. The findings of this study provide us a promising approach to regulate the formation of EPFRs.

Machine learning strategy on activation energy of environmental heterogeneous reactions and its application to atmospheric formation of typical montmorillonite-bound phenoxy radicals

Heterogeneous transformation of organic pollutants into more toxic chemicals poses substantial health risks to humans. Activation energy is an important indicator that help us to understand transformation efficacy of environmental interfacial reactions. However, the determination of activation energies for large numbers of pollutants using either the experimental or high-accuracy theoretical methods is expensive and time-consuming. Alternatively, the machine learning (ML) method shows the strength in predictive performance. In this study, using the formation of a typical montmorillonite-bound phenoxy radical as an example, a generalized ML framework RAPID was proposed for activation energy prediction of environmental interfacial reactions. Accordingly, an explainable ML model was developed to predict the activation energy via easily accessible properties of the cations and organics. The model developed by decision tree (DT) performed best with the lowest root-mean-squared error (RMSE = 0.22) and the highest coefficient of determination values (R2 score = 0.93), the underlying logic of which was well understood by combining model visualization and SHapley Additive exPlanations (SHAP) analysis. The performance and interpretability of the established model suggest that activation energies can be predicted by the well-designed ML strategy, and this would allow us to predict more heterogeneous transformation reactions in the environmental field.

Cobalt-loaded carbon nanotubes boosted aerobic ciprofloxacin transformation driven by sulfide: A comprehensive mechanism investigation

Sulfide oxidation under aerobic conditions can produce active oxygen for the transformation of organic pollutants in aquatic environments. However, the catalytic performance of transition metal-supported carbon material on this process is poor understood. This study found that Co-loaded carbon nanotubes (CNTs) was able to realize the efficient aerobic transformation of antibiotic ciprofloxacin (CIP) by sulfide, with the pseudo-first order reaction rate constant improved from 0.013 h−1 without catalyst to 0.44–0.71 h−1 with 100 mg/L Co-loaded CNTs. Singlet oxygen (1O2) was the main active specie playing key roles in the process of CIP aerobic transformation with presence of Co-loaded CNTs. Mechanism studies indicated that the excellent electron transfer ability of Co-loaded CNTs might play an important role to promote the electron transfer and facilitate the formation of intermediate H2O2 and 1O2. Additionally, the Co-loaded CNTs/sulfide system effectively reduced the acute toxicity of organic pollutant, and Co-loaded CNTs showed remarkable cycling stability and negligible leaching. This study gives a better understanding for the Co-loaded CNTs mediated aerobic antibiotics transformation by sulfide, and provide a reference for the application of Co-loaded carbon materials on organics aerobic transformation by sulfide.

Dissolved organic matter accelerates microbial degradation of 17 alpha-ethinylestradiol in the presence of iron mineral

Dissolved organic matter (DOM) and iron minerals widely existing in the natural aquatic environment can mediate the migration and transformation of organic pollutants. However, the mechanism of interaction between DOM and iron minerals in the microbial degradation of pollutants deserves further investigation. In this study, the mechanism of 17 alpha-ethinylestradiol (EE2) biodegradation mediated by humic acid (HA) and three kinds of iron minerals (goethite, magnetite, and pyrite) was investigated. The results found that HA and iron minerals significantly accelerated the biodegradation process of EE2, and the highest degradation efficiency of EE2 (48%) was observed in the HA-mediated microbial system with pyrite under aerobic conditions. Furthermore, it had been demonstrated that hydroxyl radicals (HO•) was the main active substance responsible for the microbial degradation of EE2. HO• is primarily generated through the reaction between hydrogen peroxide secreted by microorganisms and Fe(II), with aerobic conditions being more conducive. The presence of iron minerals and HA could change the microbial communities in the EE2 biodegradation system. These findings provide new information for exploring the migration and transformation of pollutants by microorganisms in iron-rich environments.

Water Vapor Condensation on Iron Minerals Spontaneously Produces Hydroxyl Radical.

The hydroxyl radical (•OH) is a potent oxidant and key reactive species in mediating element cycles and pollutant dynamics in the natural environment. The natural source of •OH is historically linked to photochemical processes (e.g., photoactivation of natural organic matter or iron minerals) or redox chemical processes (e.g., reaction of microbe-excreted or reduced iron/natural organic matter/sulfide-released electrons with O2 in soils and sediments). This study revealed a ubiquitous source of •OH production via water vapor condensation on iron mineral surfaces. Distinct •OH productions (15-478 nM via water vapor condensation) were observed on all investigated iron minerals of abundant natural occurrence (i.e., goethite, hematite, and magnetite). The spontaneous •OH productions were triggered by contact electrification and Fenton-like activation of hydrogen peroxide (H2O2) at the water-iron mineral interface. Those •OH drove efficient transformation of organic pollutants associated on iron mineral surfaces. After 240 cycles of water vapor condensation and evaporation, bisphenol A and carbamazepine degraded by 25%-100% and 16%-51%, respectively, forming •OH-mediated arene/alkene hydroxylation products. Our findings largely broaden the natural source of •OH. Given the ubiquitous existence of iron minerals on Earth's surface, those newly discovered •OH could play a role in the transformation of pollutants and organic carbon associated with iron mineral surfaces.

Mechanism of visible light enhances microbial degradation of Bisphenol A.

Bisphenol A (BPA) is a toxic endocrine disruptor detected in various environments. Microbial metabolic/enzymatic degradation has been thought to be the main pathway for BPA attenuation in natural environments. In this study, we found that under visible light conditions, superoxide produced by bacteria was the main reason for the rapid removal of BPA, accounting for 57% of the total removal rate. With visible light, the bacteria degraded BPA at a rate of 0.22mg/L/d, and the total removal within 8 days reached 85%, which is 4.7 times compared with that of dark culture. The intermediate product 4-iso-propenylphenol, which was considered as an end-product of microbial degradation of BPA in previous reports, was detected in large quantities at 24h in culture but gradually decreased in our experiment. Community analysis suggested bacteria with aromatic hydrocarbon degradation ability were more enriched under light incubation. Moreover, the bacteria showed well degradation ability to various pharmaceutically active but nonbiodegradable compounds including diclofenac and fluoxetine, with a removal rate of 88 % and 20%, respectively. Our study revealed the organic pollutant transformation pathway under the combined action of light and microorganisms, providing new insights into the microbial treatment of aromatic hydrocarbon pollutants.

Determination of organophosphate diesters in facility vegetable soils using ultra-high performance liquid chromatography-electrostatic field orbitrap high resolution mass spectrometry

Organophosphate diesters (Di-OPEs) are biotic or abiotic degradation products of organophosphate esters (OPEs). Current analytical methods focus on detecting Di-OPEs in human urine. Human exposure to Di-OPEs in environmental matrices has not been systematically studied. Soil plays an important role in the environmental migration and transformation of organic pollutants. Previous studies found that OPEs are ubiquitous in soil. However, few studies reported OPEs metabolite pollution in soil, especially in facility vegetable soil. In this study, an ultra-high performance liquid chromatography-electrostatic field orbitrap high resolution mass spectrometry (UPHLC-Orbitrap HRMS) method was developed for the determination of five Di-OPEs (bis(2-chloroethyl) phosphate (BCEP), bis(1,3-dichloro-2-propyl) phosphate (BDCP), di-n-butyl phosphate (DnBP), diphenyl phosphate (DPhP), and bis(2-ethylhexyl) phosphate (DEHP)) in the facility vegetable soil. The pretreatment process and chromatographic and mass spectrometric conditions were optimized in the present study. Comparative study of the purification effects of different solid-phase extraction columns showed that Oasis WAX cartridge had best purification efficiency for the five Di-OPEs. The cartridge was first activated using 3 mL methanol, 3 mL methanol containing 5% (v/v) ammonia, and 3 mL 0.1 mol/L sodium acetate-acetic acid buffer solution. Then, the cartridge was rinsed with 3 mL of 30% (v/v) methanol aqueous solution, and finally eluted using 8 mL methanol containing 5% (v/v) ammonia. The effects of mobile phase (with respect to solvent composition and flow rate) and column temperature on the shape and intensity of chromatographic peaks were studied. The optimized UHPLC conditions were as follows: chromatographic column, Thermo Accucore RP-MS; column temperature, 30 ℃; mobile phase, 0.2 mmol/L ammonium acetate aqueous solution and methanol; flow rate, 0.2 mL/min. In the UHPLC-Orbitrap HRMS experiment, the five Di-OPEs were analyzed in full MS mode with negative ionization. Instrumental parameters, such as sheath gas and auxiliary gas, were optimized to determine the MS conditions. The optimized Orbitrap HRMS conditions were as follows: heating electrospray ionization source (HESI), full MS mode with negative ionization; scan range, m/z 100-500; ion transfer tube temperature, 320 ℃; automatic gain control of target particle count, 1×106; sheath gas flow rate, 8.58 L/min; auxiliary gas flow rate, 17.40 L/min; spray voltage, 3.2 kV; and S-lens voltage, 50 V. The limits of detection and quantification were 0.001-0.047 ng/g and 0.004-0.156 ng/g, respectively. The correlation coefficients of the calibration curve were 0.9985-0.9999. At three spiked levels, 5.0, 25.0, and 50.0 ng/g, the recoveries of the five Di-OPEs ranged from 56.9% to 133.0% with relative standard deviations of 4.4%-18.9%. The established method was applied to the analysis of the five Di-OPEs in 16 facility vegetable soils. The detection frequencies of the five Di-OPEs exceeded 60% in all soil samples, indicating that the Di-OPEs were ubiquitous in the facility vegetable soil. The contents of the five Di-OPEs in the facility vegetable soil samples ranged from 2.53-6.94 ng/g. DnBP (1.37-3.20 ng/g) and DPhP (0.47-2.44 ng/g) were the predominant congeners in the facility vegetable soil samples, accounting for 23.4%-68.8% and 16.3%-35.9% of the five Di-OPEs, respectively. The developed method is simple, sensitive, and reproducible and can be used effectively for the determination of Di-OPEs in soil. The results of this study will be helpful for understanding the environmental behavior of Di-OPEs and their human exposure in facility vegetable soils.

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.

Visualizing the Distribution of Phthalate Esters and Plant Metabolites in Carrot by Matrix-Assisted Laser Desorption/Ionization Imaging Mass Spectrometry.

The accumulation of organic pollutants in vegetables is a major global food safety issue. The concentrations of pollutants in vegetables usually differ across different tissues because of different transport and accumulation pathways. However, owing to the limitations of conventional methods, in situ localization of typical organic pollutants such as phthalate esters (PAEs) in plant tissues has not yet been studied. Here, we developed a quick and efficient method for in situ detection and imaging of the spatial distribution of PAEs in a typical root vegetable, carrot, using matrix-assisted laser desorption/ionization imaging mass spectrometry (MALDI-IMS). The use of a 2,5-dihydroxybenzoic acid matrix with a spray-sublimation coating method led to the successful identification of PAEs ion signals. The IMS results showed that a typical PAE-di-(2-ethylhexyl)phthalate (DEHP) was broadly distributed in the cortex, phloem, and metaxylem, but was barely detectable in the cambium and protoxylem. Interestingly, MALDI-IMS data also revealed for the first time the spatial distribution of sugars and β-carotene in carrots. In summary, the developed method offers a new and practical methodology for the in situ analysis of PAEs and plant metabolites in plant tissues. As a result, it could provide a more intuitive understanding of the movement and transformation of organic pollutants in soil-plant systems.

The Roles of Different Fractions in Freshwater Biofilms in the Photodegradation of Methyl Orange and Bisphenol A in Aqueous Solutions.

Freshwater biofilms play an important role in the migration and transformation of organic pollutants, especially under illumination conditions. Nonetheless, the roles of variable fractions in freshwater biofilms, e.g., extracellular polymeric substances (EPS), microbial cells and original biofilms, in promoting the photodegradation of trace organic pollutants remain largely unclear. In this study, two contaminants, i.e., methyl orange (MO) and bisphenol A (BPA), were selected, and the roles of different fractions in freshwater biofilms in their photodegradation performances were investigated. After dosing 696 mg/L SS biofilm harvested from an effluent-receiving river, the direct photodegradation rate of MO and BPA was increased 8.7 times and 5.6 times, respectively. River biofilm EPS contained more aromatic fractions, chromogenic groups and conjugated structures than biofilm harvested from a less eutrophic pond, which might be responsible for the enhanced photodegradation process. The quenching experiments suggested that when EPS fractions derived from river biofilm were dosed, 3EPS* was the major reactive oxygen species during the photodegradation of MO and BPA. Meanwhile, for EPS derived from the pond biofilm, ·OH/1O2 was predominantly responsible for the enhanced photodegradation. Batch experimental results suggested that the cells and EPS in river biofilms could collaboratively interact with each other to enhance the preservation of reactive species and protection of microbes, thus facilitating the photoactivity of biofilms. Our results might suggest that biofilms generated from eutrophic waterbodies, such as effluent-receiving rivers, could play a more important role in the photodegradation processes of contaminants.

Highly Efficient Degradation of Tetracycline Hydrochloride in Water by Oxygenation of Carboxymethyl Cellulose-Stabilized FeS Nanofluids.

The transformation of organic pollutants by stabilized nano-FeS in oxic conditions is far less understood than in anoxic states. Herein, carboxymethyl cellulose-stabilized FeS (CMC-FeS) nanofluids are prepared at a CMC-to-FeS mass ratio of 1/2 and their performance of tetracycline hydrochloride (TC) degradation under oxic conditions was investigated. Here, we showed that TC could be efficiently removed by oxygenation of CMC-FeS nanofluids at neutral initial pH. We found that CMC-FeS dosages as low as 15 mg/L can achieve the TC removal efficiency as high as 99.1% at an initial TC concentration of 50 mg/L. Oxidative degradation plays a predominated role in TC removal (accounting for 58.0%), adsorption has the second importance (accounting for 37.0%), and reduction has minor impact (accounting for 4.1%) toward TC removal. Electron spin resonance assays, fluorescent detection using coumarin as a probe, and radical scavenging experiments confirm that hydroxy radicals (•OH), both in free and surface-bound forms, contribute to oxidation of TC. Humic acids brought detrimental effects on TC removal and therefore should be biologically degraded in advance. This work offers a facile and cost-effective solution to decontaminate TC in natural and engineered water bodies.

High-pressure modified mesoporous Zr-BTB nanosheets with enhanced photocatalyst activity

In this paper, a porous two-dimensional CdSNPs@Zr-BTB composite photocatalyst driven by visible light was successfully synthesized by CO2 expansion liquid in supercritical system, which can degrade methylene blue rapidly and stably compared with ordinary CdSNPs@Zr-BTB composite photocatalyst. The structure and morphology analysis show that the modified Zr-BTB nanosheet can form an optimal nanosheet with 17.8 nm aperture and 1.6 nm thickness. The XRD and Raman spectra showed that CdS was loaded on the nanosheets. The photocurrent, EIS, UV–vis DRS and PL spectra illustrate that CdSNPs@Zr-BTB(7 MPa) has a strong photoelectric effect. The degradation rate of two-dimensional CdSNPs@Zr-BTB composite photocatalyst can reach 98% under light, and the photocatalytic efficiency remains at 82.15% after 5 photocatalytic cycles. The density functional theory analysis shows that the electron cloud distribution between CdSNPs and Zr-BTB is beneficial to the transformation of organic pollutants under visible light irradiation.

Facet-dependent Fe(II) redox chemistry on iron oxide for organic pollutant transformation and mechanisms

Fe(II) redox chemistry is a pivotal process of biogeochemical Fe cycle and the transformation of organic pollutants in subsurface aquifers, while its interfacial reactivity on iron oxides with varying surface chemistries remains largely unexplored. In this study, the redox processes of Fe(II) on two hematite with highly exposed {001} and {110} facets and their impacts on the transformation of nitrobenzene were investigated. Results suggest that Fe(II) adsorption is the rate-limiting step of the redox chain reactions, controlling the reduction potential (EH). Nitrobenzene activates the facet electron transfer on hematite, leading to nitrobenzene reduction and Fe(II) oxidation. Moreover, {001} facet exhibits a higher reactivity and electron transport efficiency than {110} facet, which is attributed to a lower site density (0.809 #Fe/nm2) and a lower EH of hematite {001} facet than that of {110} facet. It is worth noting that the facet-dependent reduction activity is more intense at low pH or high Fe(II) activity. A slight dissolution of {110} facet was observed, indicating hematite {001} facet exhibits higher thermodynamic stability than {110} facet. This study confirms the facet-dependent reducing activity of surface bound Fe(II) on hematite, providing a new perspective for in-depth understanding of the interfacial reactions on hematite. The findings of this work broaden the biogeochemical process of Fe cycle in subsurface environments and its impact on the fate of organic pollutants in groundwater.

Effect of freeze-thaw cycle aging and high-temperature oxidation aging on the sorption of atrazine by microplastics

This study aims to better understand the aging characteristics of microplastics in the environment and the influence of aging microplastics on the migration and transformation of organic pollutants. In this study, polyvinyl chloride (PVC) and polyethylene (PE) were chosen as research objects, and the effects of two aging methods (freeze-thaw cycle aging and high-temperature oxidation aging) on their surface properties and atrazine (ATZ) sorption were investigated. The crystallinity of PE increased after freeze-thaw cycling and decreased after high-temperature oxidation. The freeze-thaw cycle destroys the amorphous region of PE, reducing the micropores on the PE surface and decreasing the ATZ adsorbed by PE. Although aging had no significant effect on the surface structure of PVC, it caused new oxygen-containing functional groups to be produced on the PVC surface, which reduced the ATZ adsorption capacity. These results show that the two aging modes change the surface properties of PVC and PE, thus affecting the sorption mechanism of ATZ, and provide a theoretical premise for the natural behavior and ecological chance assessment of ATZ in the presence of microplastics.

Transformation of phenol and nitrobenzene by superoxide radicals: Kinetics and mechanisms

In this study, the kinetics and mechanisms of superoxide radical (O2·-)-mediated transformation of two monosubstituted aromatic contaminants with diametrically opposed electronic effect, namely phenol (PhOH) and nitrobenzene (NB), were investigated through combined experimental and theoretical approaches. The reaction rate constant between O2·- and PhOH was determined to be 269 M−1 s−1via competition kinetic method. Such weak role of O2·- was confirmed by density functional theory (DFT) calculations at SMD/CAM-B3LYP/6-311++G(2d,2p)//CAM-B3LYP/6-31+G(d,p) level of theory. However, NB exhibited a higher reactivity towards O2·- than PhOH, demonstrating the selectivity of O2·- to electron withdrawing group. Despite the difference in reactivity, O2·- shows very limited removal capacity for PhOH and NB. These results were also in reasonably good agreement with an indication from a quantitative structure–property relationship model. With these quantitative and mechanistic results, we provided a more comprehensive understanding on the O2·--mediated transformation of organic pollutants bearing different electron donating/withdrawing groups.