Ecological and human health hazards of soil heavy metals after wildfire: A case study of Liangshan Yi autonomous prefecture, China.

Soil samples were collected in at different depths from the conflagration area in Liangshan Yi Autonomous Region, China, to investigate the distribution characteristics and ecological and human health risks of heavy metals after a wildfire. The samples collected comprise wildfire ash (WA) above the soil surface, ash soil (AS) 0-5 cm, and plain soil (PS) 5-15 cm below the soil surface. Additionally, reference soil (RS) was collected from a nearby unburned area at the same latitude as the conflagration area. The results showed that the concentrations of zinc (Zn), copper (Cu), lead (Pb), and cadmium (Cd) in the WA and AS were significantly higher than in reference soil (RS) (p < 0.05). Concentrations of Pb in the PS were 2.52 times higher than that in RS (17.9 mg kg-1) (p < 0.05). The AS and WA had the highest Index of potential ecological risks (RI > 600). In addition, The Cd in AS and WA contributed the most to the highest Improved nemerow index (INI) and RI with a contribution of more than 80%. The concentration of heavy metals was used to establish non-carcinogenic effects and cancer risks in humans via three exposure pathways: accident ingestion of soil, dermal contact with soil, and inhalation of soil particles. Hazard index (HI) values of each sample were all less than 1, indicating the non-carcinogenic risk was within the acceptable range and would not adversely affect the local population's health. The Cancer risk (CR) values of Cr, As, Cd, and Ni were all below 1 × 10-6, indicating that heavy metal pollution from this wildfire did not pose a cancer risk to residents.

Enhanced simultaneous removal of phosphate and ammonium from swine wastewater using magnetic magnesium-loaded Chinese herbal medicine residues: Performance, mechanism, and resource utilization.

Magnetic magnesium (Mg)-loaded Chinese herbal medicine residues (MM-TCMRs) were fabricated to simultaneously remove and recover phosphate and ammonium from wastewater. The MM-TCMRs exhibited larger specific surfaces and rougher structures with massive spherical particles than those of original residues. They could be separated by adjusting the magnetic field. The phosphate and ammonium adsorption by MM-TCMRs were matched with the pseudo-second-order model, while the Langmuir model yielded the maximum adsorption capacities of 635.35 and 615.57 mg g-1, respectively. Struvite precipitation on the MM-TCMRs surface was the primary removal mechanism with electrostatic attraction, ligand exchange, intra-particle diffusion, and ion exchange also involved. The recyclability of MM-TCMRs confirmed their good structural stability. More importantly, the nutrient-loaded MM-TCMRs enhanced alfalfa growth and improved soil fertility in planting experiments. Collectively, the MM-TCMRs are promising candidates for nutrient removal and recovery from wastewater.

Green remediation of Ni, Zn, and Cu in an electroplating contaminated site by wood vinegar with optimization and risk assessment.

Wood vinegar (WV) is a renewable organic compound, possessing characteristics such as high oxygenated compound content and low negative impact on soil. Based on its weak acid properties and complexing ability to potentially toxic elements (PTEs), WV was used to leach Ni, Zn, and Cu contaminated soil in electroplating sites. In addition, the response surface methodology (RSM) based on the Box-Behnken design (BBD) was established to clarify the interaction between each single factor, and finally completed the risk assessment of the soil. The amounts of PTEs leached from the soil climbed with the increase of WV concentration, liquid-solid ratio, and leaching time, while they surged with the decrease of pH. Under optimal leaching circumstances (the concentration of WV= 100 %; washing time= 919 min; pH= 1.00), the removal rates of Ni, Zn, and Cu could reach 91.7 %, 57.8 %, and 65.0 %, respectively, and the WV-extracted PTEs were mainly from the Fe-Mn oxides fraction. After leaching, the Nemerow integrated pollution index (NIPI) decreased from an initial value of 7.08 (indicating severe pollution) to 0.450 (indicating no pollution). The potential ecological risk index (RI) dropped from 274 (medium level) to 39.1 (low level). Additionally, the potential carcinogenic risk (CR) values reduced by 93.9 % for both adults and children. The results revealed that the washing process significantly reduced the pollution level, potential ecological risk, and health risk. Coupled with FTIR and SEM-EDS analysis, the mechanism of WV removal of PTEs could be explained from three aspects: acid activation, H+ ion exchange, and functional group complexation. In summary, WV is an eco-friendly and high-efficiency leaching material for the remediation of PTEs polluted sites, which will maintain soil function and protect human health.

Activation and tolerance of Siegesbeckia Orientalis L. rhizosphere to Cd stress.

This experiment investigated the changes of rhizosphere soil microenvironment for hyperaccumulation-soil system under Cd stress in order to reveal the mechanism of hyperaccumulation and tolerance. Thus, Cd fractions, chemical compositions, and biochemical characteristics in rhizosphere soil of Siegesbeckia orientalis L. under Cd stress conditions of 0, 5, 10, 25, 50, 100, and 150 mg kg-1 were investigated through a root bag experiment, respectively. As a result, Cd induced the acidification of S. orientalis rhizosphere soil, and promoted the accumulation of dissolved organic carbon (DOC) and readily oxidizable organic carbon (ROC), which increased by 28.39% and 6.98% at the maximum compared with control. The percentage of labile Cd (acid-soluble and reducible Cd) in soil solution increased significantly (P < 0.05) from 31.87% to 64.60% and from 26.00% to 34.49%, respectively. In addition, rhizosphere microenvironment can alleviate the inhibition of Cd on soil microorganisms and enzymes compare with bulk soils. Under medium and low concentrations of Cd, the rhizosphere soil microbial biomass carbon (MBC), basal respiration, ammonification and nitrification were significantly increased (P < 0.05), and the activities of key enzymes were not significantly inhibited. This suggests that pH reduction and organic carbon (DOC and ROC) accumulation increase the bioavailability of Cd and may have contributed to Cd accumulation in S. orientalis. Moreover, microorganisms and enzymes in rhizosphere soils can enhance S. orientalis tolerance to Cd, alleviating the nutrient imbalance and toxicity caused by Cd pollution. This study revealed the changes of physicochemical and biochemical properties of rhizosphere soil under Cd stress. Rhizosphere soil acidification and organic carbon accumulation are key factors promoting Cd activation, and microorganisms and enzymes are the responses of Cd tolerance.

Dual Superlyophobic Materials for Under-Liquid Microfluid Manipulation, Immiscible Solvent Separation, and CO2 Blockage.

Oily water purification, immiscible solvent separation, sensitive microreaction, and CO2 blockage are of great interest because of their importance for the environment and demands of controllable microreactions. However, one specific material that can meet all the requirements has yet to be reported. Herein, we developed a simple environment-benign method to prepare specific dual superlyophobic materials to solve the problems mentioned earlier. The dual superlyophobic materials can maintain their dual superoleophobicity in various oil/water systems, and no additional surface modifications were required when the oil/water system was changed. Moreover, the materials can be used to separate oil/water mixtures with separation efficiencies greater than 99.50% even after 40 separation cycles and separate immiscible organic solvents with efficiencies over than 99.25% after 20 cycles. Separations of meal waste oily water at 60 °C and crude oil/water were also successfully performed. The materials can be further applied to manipulate and block CO2 bubbles under liquid. The materials can also act as a platform for microdrop manipulation/microreaction under liquid.

Characterization of ionic liquids removing heavy metals from electroplating sludge: Influencing factors, optimisation strategies and reaction mechanisms.

The disposal of electroplating sludge (ES) is a common concern of researchers. Currently, it is difficult to achieve effective fixation of heavy metals (HMs) using traditional ES treatment. As green and effective HMs removal agents, ionic liquids can be used for the disposal of ES. In this study, 1-butyl-3-methyl-imidazole hydrogen sulphate ([Bmim]HSO4) and 1-propyl sulphonic acid-3-methyl imidazole hydrogen sulphate ([PrSO3Hmim]HSO4) were used as washing solvents for the removal of Cr, Ni, and Cu from ES. In reaction with increased agent concentration, solid-liquid ratio, and duration, the amount of HMs eliminated from ES rises, whereas opposite patterns were shown in response to rising pH. The quadratic orthogonal regression optimisation analysis also revealed that the ideal washing specifications for [Bmim]HSO4 were 60 g L-1, 1:40, and 60 min, respectively, for agent concentration, solid-liquid ratio, and washing time, while those for [PrSO3Hmim]HSO4 were 60 g L-1, 1:35, and 60 min, respectively. Under the optimal experimental conditions, the Cr, Ni, and Cu removal efficiencies for [Bmim]HSO4 were 84.3, 78.6, and 89.7%, respectively, and those values for [PrSO3Hmim]HSO4 were 99.8, 90.1, and 91.3%, respectively. This was mainly attributed to that ionic liquids enhance metal desorption through acid solubilisation, chelation, and electrostatic attraction. Overall, ionic liquids are reliable washing reagents for ES contaminated by HMs.

Carbon Quantum Dots-Functionalized UiO-66-NH2 Enabling Efficient Infrared Light Conversion of 5-Hydroxymethylfurfuryl with Waste Ethanol into 5-Ethoxymethylfurfural.

The catalytic etherification of 5-hydroxymethylfurfural (HMF) with the waste ethanol into high-energy-density 5-ethoxymethylfurfural (EMF) has been considered as a promising way to simultaneously alleviate the energy crisis and environmental pollution. However, the energy consumption is rather high as the synthesis of EMF requires a high temperature to open the etherification reaction. Herein, we demonstrate a clever design and construction of acidified biomass-derived carbon quantum dots (BCQDs)-modified UiO-66-NH2 that is immobilized on cermasite (H+/BCQDs/UiO-66-NH2@ceramsite), which can use the IR light as driven energy and wasted ethanol to trigger the catalytic conversion of HMF into EMF. The temperature on the surface of the immobilized catalyst could reach as high as 139 °C within 15 min IR irradiation. Due to the aforementioned advantages, the as-prepared catalyst exhibited excellent IR-triggered catalytic performance toward EMF production, where the EMF yields and selectivity were as high as 45% and 65%, respectively. The high catalytic performance originates from the outstanding photo-to-thermal conversion by the introduction of BCQDs, as well as the strong interactions between BCQDs and UiO-66-NH2 that boosts the etherification reactions. The immobilization of catalyst on cermasite not only benefits catalyst recycling, but more importantly reduces catalyst loss during practical applications. The conceptual study shown here provides new viewpoints in designing energy-effective materials for the conversion of wastes into high-value-added resources.

The molecular-level understanding of the uptake of PFOS and its alternatives (6:2 Cl-PFESA and OBS) into phospholipid bilayers.

Bioaccumulation of perfluoroalkyl and polyfluoroalkyl substances (PFASs) is an important indicator of their hazard. Partitioning to membrane phospholipids is one of the pathways for their bioaccumulation. However, the molecular mechanism on PFASs uptake into membrane phospholipids is not yet to be fully understood. In this work, we used molecular dynamics (MD) simulations to study the uptake processes of PFOS and its alternatives (6:2 Cl-PFESA and OBS) into DPPC bilayers, and to evaluate their interaction with DPPC bilayers and their effect on properties of DPPC bilayers. The result of free energy changes shows that a barrier of 2-3 kcal mol-1 exists when these adsorbed PFASs on the surface are absorbed into DPPC bilayers. After incorporating into DPPC bilayers, three DPPC molecules interact with and thus stabilize a PFOS (or 6:2 Cl-PFESA or OBS) molecule. And another role of the three DPPC molecules is to shield these PFASs from exposure to water environment. These PFASs have the similar condensing effect on the model membrane. The molecular-level study is beneficial for understanding the bioaccumulation and toxicity of PFOS and its alternatives.

Potential environmental fate and risk based on the hydroxyl radical-initiated transformation of atmospheric 1,2-dibromo-4-(1,2dibromoethyl)cyclohexane stereoisomers.

1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH), as an emerging brominated flame retardant (EBFR) pollutant, has been often observed in the air, and to comprehend its fate in the environment is still challenging due to the diversity of its stereoisomers. In this work, the environmental transformation behavior and potential toxicological implications of TBECH stereoisomers under the oxidation of OH· in the gas phase were investigated by computational chemistry. Our results indicate the complexity of the TBECH transformation reactions and the diversity of its transformation products in the atmosphere. Although the reactions of TBECH enantiomers with OH· exhibit highly consistency, it is obvious that the reactions of the four diastereoisomers of TBECH with OH· and their subsequent reactions have both specificity and similarity. The dehydrogenation intermediates produced by H-abstraction of OH· in the initial reactions may undergo oxidative debromination, hydroxylation and decomposition reactions, leading to the transformation into low bromine and monohydroxy substituted compounds, as well as debrominated or unbrominated unsaturated fatty ketones. The toxicity assessments show that all transformation products are less toxic to aquatic organisms than TBECH, but some of them are still classified at toxic or harmful levels. More importantly, some transformation products still exhibit carcinogenic and teratogenic activity. To our knowledge, this study provides, for the first time, a deep insight into the transformation mechanism, kinetics, and environmental impacts of atmospheric TBECH by theoretical calculations.

Mechanism of secondary organic aerosol formation from the reaction of isoprene with sulfoxy radicals.

Isoprene can react with sulfoxy radicals (SO4•- and SO3•-) to form organosulfur compounds in aqueous phase, and the organosulfur compounds are important compositions of secondary organic aerosols (SOAs). To make sure the specific configurations of the products and the role of SO4•- and SO3•- in the formation of organosulfur compounds, the reaction mechanisms are studied by theoretical calculations. The lowest Gibbs free energy barrier of addition of SO3•- onto isoprene is 24.06 kcal mol-1 at C4 site, and its rate constant is 1.30 × 10-11 M-1 s-1 at 298 K and 1 atm. And the Gibbs free energy barriers of addition of SO4•- onto isoprene at C1 and C4 sites are barrierless and 0.92 kcal mol-1; the rate constants of these two addition processes are 6.85 × 109 and 1.17 × 105 M-1 s-1 at 298 K and 1 atm. It elucidates that organosulfates are easier to be formed. As for the products P1 (with alcohol group) and P2 (with aldehyde group), the lowest Gibbs free energy barrier of the formation of P1 is 3.17 kcal mol-1, and that of the formation of P2 is 15.84 kcal mol-1, which means that the product with alcohol group is easier to be formed than that with aldehyde group. This work provides a reference for the formation of organosulfur compounds in aqueous phase, and it may help to understand the SOA formation.

New insight into photodegradation mechanisms, kinetics and health effects of p-nitrophenol by ozonation in polluted water.

P-nitrophenol (p-NP) is a recalcitrant organic compound attracted great environmental attention, but its degradation mechanism is indeterminacy, which challenges its treatment, migration, transformation and ecological impact in the environment. In the present study, the aqueous-phase decomposition process of p-NP initiated by O3 has been investigated by a theoretical calculation method. The detailed possible reaction pathways for the oxidative degradation of p-NP by ozone have been proposed. The chemical reaction thermodynamics results show that the reaction barriers of all ozone-initiated pathways are below 15 kcal·mol-1, indicating that ozone can completely initiate the oxidation of p-NP under natural conditions. However, the kinetic results show that the initiation reaction of p-NP by ozone alone is relatively slow compared to the reaction by OH. Interestingly, under ultraviolet (UV) radiation, the dissolved ozone interacts with water and produces two active radicals: OH and HO2. The reaction rate of p-NP initiated with OH is much higher than that with ozone, implying that the OH produced in the photochemical process can improve the removal efficiency of p-NP. The intermediates generated in the ozone-initiated reaction have been found to decompose into small molecule organic acids, aldehydes and ketones. The potential carcinogenicities and teratogenicities of the transformation products have also been studied, and some of them still have carcinogenic activity, which deserve further attention. In addition, to our knowledge, this may be the first computational chemistry study on the degradation of p-NP initiated by HO2. All the results provide a new fundamental understanding for the migration and transformation of p-NP in water environment, and indicate that further assessment is needed for the impact of p-NP and especially its transformation products on the ecological environment in a significant way.

Mechanisms, kinetics and eco-toxicity assessment of singlet oxygen, sulfate and hydroxyl radicals-initiated degradation of fenpiclonil in aquatic environments.

Fenpiclonil is an agricultural phenylpyrrole fungicide, which raise the concern about its ecotoxicological effects. In this paper, we investigate the indirect photochemical transformation mechanisms, environmental persistence and eco-toxicity of fenpiclonil initiated by various active oxidants (1O2, •OH and SO4•‾) in aquatic environments. The results shown that 1O2 can react with pyrrole ring by cycloaddition pathways to form the endo-peroxides. In addition, •OH and SO4•‾ initial mechanisms are calculated, suggesting that •OH-initiated mechanisms play a dominant role in the degradation process of fenpiclonil at high rate constants (2.26 ×109 M-1 s-1, at 298 K). The kinetic calculation results indicate that high temperature is more favorable for the degradation of fenpiclonil. To better understand the adverse effects of the transformation products formed during the subsequent reaction of •OH-adduct IM10, the computational toxicology has been used for the toxicity estimation. The results show that aquatic toxicity of these products decrease with degradation process, especially the decomposition products (TP3 and TP4). However, TP1 and TP2 are still toxic and developmental toxicant. The study provides guidance for further experimental research and industrial application of fungicide degradation from the perspective of theoretical calculation.

Experimental and theoretical insights into the RCS-Involved electro-catalytic transformation of 4-nitrophenol.

The important role of reactive chlorine species (RCS) in electrochemical system has been widely concerned for water disinfection recently. In this study, we built an electrochemical system using carbon nanotube as cathode and oxide precursor (Ti/SnO2-Sb2O5-IrO2) as anode, where RCS was produced from Cl-. This system was used to degrade nitrogen contaminants, i.e. NO3- and 4-nitrophenol. Optimization of the reaction conditions was carried out by a treatment of inorganic nitrogen contaminant NO3- and the optimal condition of the electrochemical system was determined at U = 5.5 V, and pH = 10 with a Cl- concentration of 2000 mg L-1, and the removal efficiency of NO3- can reach up to 60.6% in 150 min. Under the optimal condition, a common nitrogenous organic pollutant, 4-nitrophenol was treated and a removal efficiency of nearly 100% in 90 min. To investigate the detailed degradation mechanism in the applied electrochemical system, a combined method of products identification and density functional theory (DFT) calculation was employed. It concluded that Cl radicals' generation was stimulated was stimulated by the OH radicals after adding Cl- into the electrochemical system. These two radicals jointly promoted the transformation of 4-nitrophenol resulting in the formation of more toxic organic and inorganic substances. In addition, a conversion of organic nitro group to amino group leading to the formation of 4-aminophenol was found and explained by the indirect reduction theory.

Indirect Photodegradation of Sulfamethoxazole and Trimethoprim by Hydroxyl Radicals in Aquatic Environment: Mechanisms, Transformation Products and Eco-Toxicity Evaluation.

The bacteriostatic antibiotics, sulfamethoxazole (SMX) and trimethoprim (TMP), have frequently been found in wastewater and surface water, which raises the concerns about their ecotoxicological effects. The indirect photochemical transformation has been proven to be an efficient way to degrade SMX and TMP. In this study, the reaction mechanisms of the degradation by SMX and TMF by OH radicals were investigated by theoretical calculations. Corresponding rate constants were determined and the eco-toxicity of SMX and TMP and its degradations products were predicted using theoretical models. The results indicate that the most favorable pathways for the transformation of SMX and TMP are both •OH-addition reaction of benzene ring site with lowest Gibbs free energy barriers (6.86 and 6.21 kcal mol-1). It was found that the overall reaction rate constants of •OH-initial reaction of SMX and TMP are 1.28 × 108 M-1 s-1 and 6.21 × 108 M-1 s-1 at 298 K, respectively. When comparing the eco-toxicity of transformation products with parent SMX and TMP, it can be concluded that the acute and chronic toxicities of the degraded products are reduced, but some products remain harmful for organisms, especially for daphnid (toxic or very toxic level). This study can give greater insight into the degradation of SMX and TMP by •OH through theoretical calculations in aquatic environment.

Complexation of Fe(III)/Catechols in atmospheric aqueous phase and the consequent cytotoxicity assessment in human bronchial epithelial cells (BEAS-2B).

Recent research has shown that the complexation of metals-organics plays an important role in atmospheric particulate matter, whose health effects should be taken into account. This work investigates the interactions between catechols (CAs), i.e., 4-nitrocatechol (4NC) and 4-methylcatechol (4MC), and transition metals (i.e., Fe) in the aqueous phase dark reaction. The formation of Fe/CAs complexes and secondary organics products are analyzed by UV-Vis spectroscopy, stopped-flow spectroscopy, high-resolution mass spectrometry and Raman spectroscopy, while the insoluble particulate matter formed from the CAs/Fe mixtures are characterized by the FTIR, X-ray photoelectron spectroscopy (XPS) and thermogravimetric-quadrupole-mass spectrometry (TG-Q-MS). On the basis of the density functional theory (DFT) calculation and experimental results, the possible formation pathways for the complexes of Fe(III) with 4NC (a proxy for organics) are proposed. The Fe/CAs complexes and organics products perhaps have significant sources of light absorption which play an important role in influencing the intensity of atmospheric radiation and particulate phase photochemistry. Besides, the cytotoxicity is tested as a function of concentrations for CAs/Fe mixtures in BEAS-2B cells. Our results show that CAs/Fe mixtures have strong association with cytotoxicity, indicating the mixtures have potential influence to human health.

Indirect photodegradation of fludioxonil by hydroxyl radical and singlet oxygen in aquatic environment: Mechanism, photoproducts formation and eco-toxicity assessment.

Fludioxonil has been proven valuable as a broad-spectrum fungicide. However, there are concerns about its risk posed to non-target organisms in aquatic environments. In this paper, the mechanism, photoproducts transformation and eco-toxicity of fludioxonil during •OH/1O2-initiated process were systematically studied using quantum chemistry and computational toxicology. The results indicate that the two favorable pathways of •OH/1O2-initiated reactions are both occurred in pyrrole ring. It can conclude that the rate constants of •OH and 1O2 are 1.23 × 1010 and 3.69 × 107 M-1 s-1 at 298K, respectively, which results in half-lives of <2 days in surface waters under sunlit near-surface conditions. Based on toxicity assessments, these photoproducts showed a decreased aquatic toxicity but the majority products are still toxic. This study gives more insight into the chemical transformation mechanism of fludioxonil in aquatic environments.

Determination of reactions between Criegee intermediates and methanesulfonic acid at the air-water interface.

In recent years, Criegee chemistry has become an important research focus due to its relevance in regulating concentrations of tropospheric OH radicals, hydroperoxides, sulfates, nitrates, and aerosols. However, to date, its interface behavior remains poorly understood. Thus, in this study, we used the Born-Oppenheimer molecular dynamics (BOMD) simulation method to explore the reaction mechanisms between Criegee intermediates (CIs) and methylsulfonic acid (MSA) at the air-water interface, then compared the observed behaviors with those in the gas phase. The addition of Criegee intermediates to MSA is nearly a barrierless reaction and follows a loop-structure mechanism in the gas phase. The high rate constants indicate that the Criegee intermediates and MSA reactions are the main acid removal channels. At the water's surface, the interaction of Criegee intermediates with MSA includes three main channels: 1) direct addition reaction, 2) H2O-mediated hydroperoxide formation, and 3) MSA-mediated Criegee hydration. These reaction channels follow a loop-structure or a stepwise mechanism and proceed at the picosecond time-scale. The results of this work broaden our understanding of Criegee atmospheric behaviors in polluted urban and marine areas, which in turn will aid in developing more effective pollution control measures.

Distribution, transformation and toxicity evaluation of 2,6-Di-tert-butyl-hydroxytotulene in aquatic environment.

2,6-Di-tert-butyl-hydroxytotulene (BHT), as a significant synthetic phenolic antioxidant (SPA), has received increasing attention in the environmental field. In the present study, the BHT is confirmed to be mainly distributed in the liquid phase in the environment base on the Aspen PLUS simulation results. The mechanism and kinetics of BHT transformation initiated by OH radicals were conducted in aquatic environment using density functional theory (DFT) method. Briefly, seven initiation reactions and three detailed transformation pathways of BHT were reported. The H atoms in the t-butyl and methyl group were found more favorable to be abstracted. The C1 site of the BHT was susceptible to addition by OH radicals. Rate constants of different initial reactions were calculated and they were inhibited by temperature rise. Meanwhile, the acute and chronic toxicities of BHT and its metabolites were evaluated at three different trophic levels using the ECOSAR program. During the degradation process, the toxicities of these metabolites gradually decreased, but the toxicities of the final product 2,6-di-tert-butyl-2,5-cyclohexadien-1,4-dione (BHT-Q) were significantly increased. These results could help to reveal the transformation mechanism and risk assessment of BHT in aquatic environment, and further design the experimental and industrial applications of SPAs.

Theoretical study on the reaction of anthracene with sulfate radical and hydroxyl radical in aqueous solution.

Sulfate radical (SO4-) and hydroxyl radical (OH) generated from persulfate or peroxymonosulfate in AOPs have been widely used in contaminant degradation. Anthracene (ANT) can be decomposed by SO4- and OH. The processes of ANT decomposition were investigated using theoretical calculations in this paper. The initiation reactions of ANT, anthrone, anthraquinone (ATQ) and 1-hydroxylanthraquinone (1-hATQ) by two radicals are studied. The highest free energy barriers of initiation reactions are 22.30 kcal mol-1 in ATQ + SO4- reaction and 6.84 kcal mol-1 in ATQ + OH reaction. Comparing the rate constants of initiation reaction through the two radicals at 273-373 K, it can be concluded that SO4- and OH both play important roles on the initiation of ANT and anthrone at lower pH. For ATQ and 1-hATQ, OH is more important than SO4- in the initiation process, which indicates that the indirect influence of SO4- are more significant in the degradation processes of ATQ and 1-hATQ. This study provides theoretical confirmations for the mechanisms of reactions of ANT with SO4- and OH, and evaluates the importance of SO4- and OH according to the reaction rates. The work can give more insight into the degradation of PAHs by radicals.

Synergistic Reaction of SO2 with NO2 in Presence of H2O and NH3: A Potential Source of Sulfate Aerosol.

Effect of H2O and NH3 on the synergistic oxidation reaction of SO2 and NO2 is investigated by theoretical calculation using the molecule system SO2-2NO2-nH2O (n = 0, 1, 2, 3) and SO2-2NO2-nH2O-mNH3 (n = 0, 1, 2; m = 1, 2). Calculated results show that SO2 is oxidized to SO3 by N2O4 intermediate. The additional H2O in the systems can reduce the energy barrier of oxidation step. The increasing number of H2O molecules in the systems enhances the effect and promotes the production of HONO. When the proportion of H2O to NH3 is 1:1, with NH3 included in the system, the energy barrier is lower than two pure H2O molecules in the oxidation step. The present study indicates that the H2O and NH3 have thermodynamic effects on promoting the oxidation reaction of SO2 and NO2, and NH3 has a more significant role in stabilizing product complexes. In these hydrolysis reactions, nethermost barrier energy (0.29 kcal/mol) can be found in the system SO2-2NO2-H2O. It is obvious that the production of HONO is energetically favorable. A new reaction mechanism about SO2 oxidation in the atmosphere is proposed, which can provide guidance for the further study of aerosol surface reactions.