Effect of Dissolved Organic Matter on the Photodegradation of Decachlorobiphenyl (PCB-209) in Heterogeneous Systems: Experimental Analysis and Excited-State Theory Calculations.

Dissolved organic matter (DOM) can affect the transformation of pollutants through photosensitization, but most current research focuses on hydrophilic pollutants, making it such that less attention is paid to hydrophobic pollutants. In this paper, the effect and action mechanism of coexisting DOM on the photodegradation of decachlorobiphenyl (PCB-209) on suspended particles collected from the Yellow River were systematically investigated in a heterogeneous system using DOM standards and model compounds. Through molecular probe experiments, mass spectrometry analysis and theoretical calculations, we found that the excited triplet state of DOM (3DOM*) could excite PCB-209 to undergo dechlorination reaction. Due to the different modes of electron transition, the presence of carbonyl groups decreased the energy of 3DOM*, whereas the electron-donating groups made the energy of 3DOM* higher. DOM containing phenolic hydroxyl groups led to a higher steady-state concentration of •OH, and DOM containing phenyl ketone structures had a stronger ability to produce •O2-. Compared with aqueous •OH, •O2- produced from hydrophobic microregions could react more readily with PCB-209. This study deepens the understanding of the role of different functional groups of DOM in the photosensitized transformation of hydrophobic compounds.

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.

Photodegradation of polychlorinated biphenyls in water/nitrogen-doped silica and air/nitrogen-doped silica systems: Kinetics, mechanism and quantitative structure activity relationship (QSAR) analysis.

Developing efficient and low-cost photocatalytic materials is essential for removing polychlorinated biphenyls (PCBs). In this work, the photodegradation process of fourteen representative polychlorinated biphenyls (PCBs) in both water/nitrogen-doped SiO2 (N-SiO2) and air/N-SiO2 systems was studied. The photodegradation kinetics of PCBs is consistent with the pseudo-first-order kinetic equation. The variation in the degradation effects of different PCBs in the two systems is primarily related to the position of the Cl substituent and the effective absorption wavelength range of PCBs. A total of fourteen intermediates for 4'-Dichlorobiphenyl (PCB-15), 2,2',4,4',6,6'-Hexachlorobiphenyl (PCB-155), and 2,2',3,3',4,4',5,5',6,6'-Decachlorobiphenyl (PCB-209) generated from four reaction pathways were identified based on both mass spectrometry analysis and theoretical calculations. Using the values of lnk (k denotes pseudo-first-order kinetic constants) for the 11 PCBs in the training set and the calculated molecular and structural parameters, quantitative structure-activity relationship (QSAR) models for the two systems were constructed by using multiple linear regression (MLR) method to better understand the factors affecting the photodegradation rate of PCBs. The QSAR equations were obtained with Cl atom substitution at position 3 (N3) as the main parameter, which were lnk = -1.98 - 0.19 N3 for the water/N-SiO2 system and lnk = -1.56 - 0.34 N3 for the air/N-SiO2 system, with the correlation coefficient (R2) of 0.66 and 0.73, leave-one-out cross-validation (Q2LOO) of 0.51 and 0.59, respectively, and bootstrapping validation coefficients (Q2BOOT) values of both 0.74, confirming that the models were well fitted and showed high robustness and prediction ability. This study provides valuable insights into photocatalytic degradation studies of PCBs.

Photodegradation of 2-chlorodibenzo-p-dioxin (2-CDD) on the surface of municipal solid waste incineration fly ash: Kinetics and product analysis.

Considering that waste incineration fly ash is the main carrier of dioxins and can migrate over long distances in the atmosphere, it is of great significance to study the photochemical transformation behavior of dioxins on the surface of fly ash. In this work, 2-chlorodibenzo-p-dioxin (2-CDD) was selected to conduct a systematic photochemical study. The influence of various factors on the photodegradation of 2-CDD were first explored, and the results showed that small particle size of fly ash, low concentration of 2-CDD and appropriate level of humidity were more conducive to photodegradation, with the highest degradation percentage reaching 76%-84%. The components of fly ash (Zn (Ⅱ), Al (Ⅲ), Cu (Ⅱ) and SiO2) also had a certain promoting effect on the degradation of 2-CDD, which increases the degradation efficiency by 10%-20%, because they could act as effective photocatalysts to produce free radicals for reaction. With a higher total light exposure intensity, natural light environments led to a more complete degradation of 2-CDD than laboratory Xe lamp irradiation (90% degradation Vs. 79% degradation). Based on chemical probe and radical quenching experiment, hydroxyl radical also contributed to 2-CDD photodegradation on fly ash. A total of 16 intermediate products were detected by mass spectrometry analysis, and four initial reaction pathways of 2-CDD were speculated in the process, including dechlorination, ether bond cleavage, hydroxyl substitution, and hydroxyl addition. According to the results of density functional theory calculation, the reaction channels of ether bond cleavage and •OH attack were determined. The toxicity assessment software tool (TEST) was used to assess the toxicity and bioconcentration coefficient of reaction products, and it was found that the overall toxicity of the photodegradation products was reduced. This study would provide new insights into the environmental fate of dioxins during long-range atmospheric migration process.

Photodegradation of polycyclic aromatic hydrocarbons on soil surface: Kinetics and quantitative structure-activity relationship (QSAR) model development.

Polycyclic aromatic hydrocarbons (PAHs) have attracted much attention because of their widespread existence and toxicity. Photodegradation is the main natural decay process of PAHs in soil. The photodegradation kinetics of benzopyrene (BaP) on 16 kinds of soils and 10 kinds of PAHs on Hebei (HE) soil were studied. The results showed that BaP had the highest degradation rate in Shaanxi (SN) soil (kobs = 0.11 min-1), and anthracene (Ant) was almost completely degraded after 16 h of irradiation in HE soil. Two quantitative structure-activity relationship (QSAR) models were established by the multiple linear regression (MLR) method. The developed QSAR models have good stability, robustness and predictability. The model revealed that the main factors affecting the photodegradation of PAHs are soil organic matter (SOM) and the energy gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital (Egap). SOM can function as a photosensitizer to induce the production of active species for photodegradation, thus favoring the photodegradation of PAHs. In addition, compounds with lower Egap are less stable and more reactive, and thus are more prone to photodegradation. Finally, the QSAR model was optimized using machine learning approach. The results of this study provide basic information on the photodegradation of PAHs and have important significance for predicting the environmental behavior of PAHs in soil.

Environmental transformation and hazards of decachlorobiphenyl on suspended particles under sunlight irradiation.

Decachlorobiphenyl (PCB-209) can be widely detected in suspended particles and sediments due to its large hydrophobicity, and some of its transformation products may potentially threaten organisms through the food chain. Here we investigate the photochemical transformation of PCB-209 on suspended particles from the Yellow River. It was found that the suspended particles had an obvious shielding effect to largely inhibit the photodegradation of PCB-209. Meanwhile, the presence of inorganic ions (e.g. Mg2+ and NO3-) and organic matters (e.g. humic acid, HA) in the Yellow River water inhibited the reaction. The main transformation products of PCB-209 were lower-chlorinated and hydroxylated polychlorinated biphenyls (OH-PCBs), and small amounts of pentachlorophenol (PCP) and polychlorinated dibenzofurans (PCDFs) were also observed. The mechanisms of PCP formation by double •OH attacking carbon bridge and PCDFs formation by elimination reaction of ionic state OH-PCBs were proposed using theoretical calculations, which provided some new insights into the inter-transformations between persistent organic pollutants. In combination with VEGA and EPI Suite software, some intermediates such as PCDFs were more toxic to organisms than PCB-209. This study deepens the understanding of the transformation behavior of PCB-209 on suspended particles under sunlight.

Enhanced removal of bisphenol S in ozone/peroxymonosulfate system: Kinetics, intermediates and reaction mechanism.

The degradation process of bisphenol S (BPS) in ozone/peroxymonosulfate (O3/PMS) system was systematically explored. The results showed that the removal efficiency of BPS by O3 could be significantly improved with addition of PMS. Compared with ozonation alone, the pseudo-first-order constant (kobs) was increased by 2-5 times after adding 400 µM PMS. In O3/PMS system, accelerated removal of BPS was observed under neutral and alkaline conditions. The removal efficiency of BPS reached 100% after 40 s of reaction at pH 7.0, with the kobs of 0.098 s-1. Moreover, Cu2+ had a catalytic effect on the O3/PMS system, because it could catalyze the decomposition of ozone and PMS to produce •OH and SO4•-, respectively. Electron paramagnetic resonance illustrated that •OH and SO4•- were the reactive species in O3/PMS system. Twelve intermediates were identified by mass spectrometry, and the degradation reactions in O3/PMS system mainly included hydroxylation, sulfate addition, polymerization and ß-scission. Finally, the toxicity of the products was evaluated by the EOCSAR program. Our results introduce an efficient method for BPS removal and would provide some guidance for the development of O3-based advanced oxidation technology.

Adsorption and migration behaviors of heavy metals (As, Cd, and Cr) in single and binary systems in typical Chinese soils.

In this study, the competitive adsorption and migration behaviors of arsenic (As), cadmium (Cd), and chromium (Cr) in typical Chinese soils were investigated. It was observed that Hainan, Shanxi, and Zhejiang Mengjiadai soils exhibited the highest adsorption capacities for As (563 µg/g), Cd (653 µg/g), and Cr (383 µg/g), respectively. Heavy metals (HMs) adsorption capacities were predicted by Extreme gradient boosting (XGBoost) models, and the Shapley additive explanation (SHAP) was employed to elucidate the effect of soil physicochemical properties on target values. Due to redox and complexation reaction, the primary factor affecting adsorption has changed from free state manganese (Mn) in single As system to antimony (Sb) in As/Cd and As/Cr systems. Furthermore, the maximum adsorption capacity (Qm) of As increased by 49.4 % with the addition of Cd into Heilongjiang soil. Finally, the migration process of HMs in Heilongjiang, Hebei, and Hainan soils was simulated by column experiments. With a relatively large dispersion coefficient (D = 29.630 cm2/h) and small retardation factor (Rh = 0.030), Cr penetrated fastest in Heilongjiang soil. This research demonstrates that both the types and coexistence of HMs may affect the HMs behaviors in soil.

Transformation and Degradation of PAH Mixture in Contaminated Sites: Clarifying Their Interactions with Native Soil Organisms.

Soil contamination of polycyclic aromatic hydrocarbons (PAHs), especially caused by the mixture of two or more PAHs, raised great environmental concerns. However, research on the migration and transformation processes of PAHs in soils and their interactions with native communities is limited. In this work, soil samples from uncontaminated sites around the industrial parks in Handan, Hengshui, and Shanghai were artificially supplemented with three concentrations of anthracene (Ant), 9-chloroanthracene (9-ClAnt), benzopyrene (BaP), and chrysene (Chr). Ryegrass was planted to investigate the degradation of PAHs and its interaction with native soil organisms in the constructed ryegrass-microbe-soil microcosmic system. The bacterial and fungal communities in soil were affected by PAHs; their species diversity and relative abundance changed after exposure to different concentrations of PAHs, among which Lysobacter, Bacillus, Pseudomonas, and Massilia bacteria were correlated to the degradation of PAHs. On the 56th day, the contents of BaP, Chr, and Ant decreased with the degradation process, while the degradation of 9-ClAnt was limited. Nineteen intermediates, including hydroxylation and carboxylated compounds, were identified. The present research would help clarify the potential interactions between PAHs and native organisms in contaminated sites, providing fundamental information for evaluating the transformation risks of PAHs in the natural environment.

Experimental insights and modeling innovations: Deciphering Fe(VI) oxidation in imidazole ionic liquids through QSAR and RFR.

In this investigation, we conducted a detailed analysis of the oxidation of 16 imidazole ionic liquid variants by Fe(VI) under uniform experimental setups, thereby securing a dataset of second-order reaction rate constants (kobs). This methodology ensures superior data consistency and comparability over traditional methods that amalgamate disparate data from varied studies. Utilizing 16 chemical structural parameters obtained via Density Functional Theory (DFT) as descriptors, we developed a Quantitative Structure Activity Relationship (QSAR) model. Through rigorous correlation analysis, Principal Component Analysis (PCA), Multiple Linear Regression (MLR), and Applicability Domain (AD) evaluation, we identified a pronounced negative correlation between the molecular orbital gap energy (Egap) and kobs. MLR analysis further underscored Egap as a pivotal predictive variable, with its lower values indicating heightened oxidative reactivity towards Fe(VI) in the ionic liquids, leading the QSAR model to achieve a predictive accuracy of 0.95. Furthermore, we integrated an advanced machine learning approach - Random Forest Regression (RFR), which adeptly highlighted the critical factors influencing the oxidation efficiency of imidazole ionic liquids by Fe(VI) through elaborate decision trees, feature importance assessment, Recursive Feature Elimination (RFE), and cross-validation strategies. The RFR model demonstrated a remarkable predictive performance of 0.98. Both QSAR and RFR models pinpointed Egap as a key descriptor significantly affecting oxidation efficiency, with the RFR model presenting lower root mean square errors, establishing it as a more reliable predictive tool. The application of the RFR model in this study significantly improved the model's stability and the intuitive display of key influencing factors, introducing promising advanced analytical tools to the field of environmental chemistry.

Enhanced permanganate oxidation of phenolic pollutants by alumina and potential industrial application.

In this study, we found that alumina (Al2O3) may improve the degradation of phenolic pollutants by KMnO4 oxidation. In KMnO4/Al2O3 system, the removal efficiency of 2,4-Dibromophenol (2,4-DBP) was increased by 26.5%, and the apparent activation energy was decreased from 44.5 kJ/mol to 30.9 kJ/mol. The mechanism of Al2O3-catalytic was elucidated by electrochemical processes, X-ray photoelectron spectroscopy (XPS) characterization and theoretical analysis that the oxidation potential of MnO4- was improved from 0.46 V to 0.49 V. The improvement was attributed to the formation of coordination bonds between the O atoms in MnO4- and the empty P orbitals of the Al atoms in Al2O3 crystal leading to the even-more electron deficient state of MnO4-. The excellent reusability of Al2O3, the good performance on degradation of 2,4-DBP in real water, the satisfactory degradation of fixed-bed reactor, and the enhanced removal of 6 other phenolic pollutants demonstrated that the KMnO4/Al2O3 system has satisfactory potential industrial application value. This study offers evidence for the improvement of highly-efficient MnO4- oxidation systems.

Degradation of Butylated Hydroxyanisole by the Combined Use of Peroxymonosulfate and Ferrate(VI): Reaction Kinetics, Mechanism and Toxicity Evaluation.

Butylated hydroxyanisole (BHA), a synthetic phenolic antioxidant (SPA), is now widely present in natural waters. To improve the degradation efficiency of BHA and reduce product toxicity, a combination of peroxymonosulfate (PMS) and Ferrate(VI) (Fe(VI)) was used in this study. We systematically investigated the reaction kinetics, mechanism and product toxicity in the degradation of BHA through the combined use of PMS and Fe(VI). The results showed that PMS and Fe(VI) have synergistic effects on the degradation of BHA. The effects of operational factors, including PMS dosage, pH and coexisting ions (Cl-, SO42-, HCO3-, K+, NH4+ and Mg2+), and different water matrices were investigated through a series of kinetic experiments. When T = 25 °C, the initial pH was 8.0, the initial BHA concentration was 100 µM, the initial concentration ratio of [PMS]0:[Fe(VI)]0:[BHA]0 was 100:1:1 and the degradation rate could reach 92.4% within 30 min. Through liquid chromatography time-of-flight mass spectrometry (LC-TOF-MS) identification, it was determined that the oxidation pathway of BHA caused by PMS/Fe(VI) mainly includes hydroxylation, ring-opening and coupling reactions. Density functional theory (DFT) calculations indicated that •OH was most likely to attack BHA and generate hydroxylated products. The comprehensive comparison of product toxicity results showed that the PMS/Fe(VI) system can effectively reduce the environmental risk of a reaction. This study contributes to the development of PMS/Fe(VI) for water treatment applications.