Updating vehicle VOCs emissions characteristics under clean air actions in a tropical city of China.

In the context of clean air actions in China, vehicle emission limits have been continuously tightened, which has facilitated the reduction of volatile organic compounds (VOCs) emissions. However, the characteristics of VOC emissions from vehicles with strict emission limits are poorly understood. This study investigated the VOC emission characteristics from vehicles under the latest standards based on tunnel measurements, and identified future control strategies for vehicle emissions. The results showed that the highest percentage of VOCs from vehicle consisted of alkanes (80.9 %), followed by aromatics (15.8 %) and alkenes (3.1 %). Alkanes had the most significant ozone formation potential due to their high concentrations, in contrast to the aromatics that have been dominant in previous studies. The measured fleet-average VOC emission factor was 71.3 mg·km-1, including tailpipe emissions of 39.6 mg·km-1 and evaporative emissions of 31.7 mg·km-1. The VOC emission factors of the subgroups were obtained. The emission of evaporated VOCs accounted for 44.5 % of the total vehicle VOC emissions, which have increased substantially from previous studies. In addition, the emission characteristics of vehicles that are under the latest emission threshold values have changed significantly, and the mixing ratio of toluene/benzene (T/B) has been updated to 3:1. This study updates the VOCs emission factors of vehicles under clean air actions and highlights the future mitigation policies should focus on reducing evaporative VOC emissions.

New solution for predicting the removal efficiency of organic contaminants by UV/ H2O2: From a case study of 1H-benzotriazole.

Rapid prediction of the removal efficiency and energy consumption of organic contaminants under various operating conditions is crucial for advanced oxidation processes (AOPs) in industrial application. In this study, 1H-Benzotriazole (BTZ, CAS: 95-14-7) is selected as a model micropollutant, a validated incorporated Computational Fluid Dynamics (CFD) model is employed to comprehensively investigate the impacts of initial concentrations of H2O2, BTZ and dissolved organic carbon (DOC) (i.e., [DOC]0, [BTZ]0 and [DOC]0), as well as the effective UV lamp power P and volumetric flow rate Qv. Generally, the operation performance depends on [DOC]0 and [BTZ]0 in similar trends, but with quantitatively different ways. The increase in [H2O2]0 and P/Qv can promote •OH generation, leading to the elimination of BTZ. It is worth noting that P/Qv is found to be linearly correlated with the removal order of BTZ (ROBTZ) under specific conditions. Based on this finding, the degradation of other potential organic contaminants with a wide range of rate constants by UV/H2O2 is further investigated. A model for predicting energy consumption for target removal rates of organic pollutants is established from massive simulation data for the first time. Additionally, a handy Matlab app is first developed for convenient application in water treatment. This work proposes a new operable solution for fast predicting operation performance and energy consumption for the removal of organic contaminants in industrial applications of advanced oxidation processes.

[Ozone Pollution Characteristics and Formation Mechanism in a Typical Tropical Seaside City].

To investigate the pollution characteristics and formation mechanism of ambient air ozone(O3) in a typical tropical seaside city, we conducted an observational experiment on O3 and its precursors at an urban site in Haikou, Hainan Province, from June to October 2019. The O3 pollution characteristics were analyzed comprehensively; the O3-NOx-VOCs sensitivities and key precursors were determined, and the control strategies for O3 pollution were carried out. The results were as follows:1 O3 pollution in Haikou mainly occurred in September and October, with daily maximum 8-h O3 concentrations in the range of 39-190 µg·m-3, and the daily variation in O3 was unimodal, peaking at approximately 14:00. 2 The concentrations of NO2 and VOCs were higher during O3 pollution episodes than their respective mean values in Haikou City. The increased O3 precursor concentrations were an important factor leading to O3 pollution, whereas O3 pollution was also influenced by regional transport, with pollutants mainly transported from the northeastern part of Haikou City. 3 O3-NOx-VOCs sensitivity in Haikou City was in the VOCs and NOx transitional regime, and the most sensitive precursors in various months were different. O3 formation in September was sensitive to anthropogenic VOCs the most; however, in October it was sensitive to NOx. 4 In the future, the reduction ratio of VOCs to NOx should be 1:1-4:1 to control O3 pollution effectively in Haikou.

New insight into the removal process of benzotriazole UV stabilizers by UV/H2O2: Integrating quantum chemical calculation with CFD simulation.

Benzotriazole UV stabilizers (BT-UVs) are important UV absorbers. As high-production chemicals and potential hazards, their ubiquitous presence in aquatic environments is of greatly pressing concern. Herein, the removal of six typical BT-UVs by UV/H2O2 was comprehensively investigated by quantum chemistry calculation integrated with CFD simulation. Utilizing such a micro and macro incorporated model in treating contaminants is the first report. From the micro-view, degradation mechanisms of BT-UVs by •OH oxidation were determined, and corresponding rate constants were obtained with values of 109∼1010 M-1s-1. In a macroscopic aspect, combining the established kinetic model and CFD simulation, the effects of UV lamp power (P), volumetric flow rate (Qv), and H2O2 dosage ([H2O2]0) on removal yields of BT-UVs were expounded, increasing P or [H2O2]0 or decreasing Qv are effective in improving removal yields of BT-UVs, but the enhancement was abated when P or [H2O2]0 increased to a certain level. When [H2O2]0 is 5 mg/L and Qv is decreased from 0.1 to 0.05 m3/h, the removal yields of BT-UVs could achieve more than 95% (P = 150 W) and 99% (P = 250 W), respectively. This work provides a new interdisciplinary insight for investigating organic contaminant removal in potential industrial applications of UV/H2O2 systems.

Mechanistic insight into the degradation of 1H-benzotriazole and 4-methyl-1H-benzotriazole by •OH-based advanced oxidation process and toxicity assessment.

Benzotriazoles (BTs) are highly produced chemicals that are commonly used in the manufacture of aircraft de-icing/antifreeze fluids (ADAFs), coolants, etc. BTs have been detected in a variety of water environments, causing health hazards to aquatic species and humans. In this study, 1H-benzotriazole (BTri) and 4-methyl-1H-benzotriazole (4-TTri) were selected to investigate their degradation mechanisms in the aqueous phase initiated by ·OH using a theoretical calculation method. Addition reactions are the main type of reactions of ·OH with BTri and 4-TTri. The total rate constants for the reactions of BTri and 4-TTri with ·OH at 298 K are 8.26 × 109 M-1 s-1 and 1.81 × 1010 M-1 s-1, respectively. The reaction rate constants increase as the temperature rises, indicating that rising temperatures promote the degradation of BTri and 4-TTri. 7-hydroxy-1H-benzotriazole (1-P1) and 4-hydroxy-benzotriazoles (1-P2) produced via multiple reaction pathways are important transformation products of BTri. After successive reactions with ·OH, 1-P1 and 1-P2 can be successively converted to 4,7-dihydroxy-1H-benzotriazole (1-P7), 4,7-dione-1H-benzotriazole (1-P8), and 1,2,3-triazole-4,5-dicarboxylic acid (1-P9), which is consistent with the product compositions detected in the experiments. The toxicity assessment indicated that the acute toxicity and chronic toxicity of the resulting transformation products are significantly reduced compared to BTri as the degradation process progressed, and ultimately showed no harm to all three aquatic organisms (fish, daphnia, and green algae). Hence, advanced oxidation processes (AOPs) can not only effectively remove BTs from water, but also reduce their toxic effects on aquatic organisms.

A Comprehensive Investigation on Potential Risk Factors for NSCL/P in a Rural District of Hebei Province, China.

Non syndromic cleft lip with or without palate (NSCL/P), one of the most common birth defects, is closely related to various risk factors. However, information regarding risk factors for NSCL/P in rural districts in China is very limited thus far. The objective of this study was designed to identify the potential risk factors for NSCL/P in rural districts.A comprehensive retrospective investigation including 435 NSCL/P patients and 402 healthy children was carried out in Hebei Province, China. Multiple logistic regression analysis and transmission disequilibrium test (TDT) were respectively used to identify non-genetic and genetic risk factors for NSCL/P, and then PLINK was used to explore the relationship between non-genetic and genetic risk factors.The results showed that maternal periconceptional exposure to pesticides and herbicides, as well as low parental education level were involved in the increased risk of NSCL/P, whereas maternal folic acid and multivitamin supplementation use during preconception period were associated with the reduced risk of NSCL/P. TDT analysis identified 2 single nucleotide polymorphisms (SNPs) (rs7078160 and rs4752028) in VAX1 and one SNP (rs17563) in BMP4 as the genetic risk factors for NSCL/P. Further analysis showed that the genetic risk factors were closely related with the negative non-genetic risk factors.Our study identified the potential risk factors for NSCL/P in rural districts, thus providing a theoretical basis for the prevention of NSCL/P occurrence.

Wall Effects for Spheroidal Particle in Confined Bingham Plastic Fluids.

The wall effects on the sedimentation motion of a single spheroidal particle in cylindrical tubes filled with Bingham plastic fluid are investigated with the fixed computational domain using the Computational Fluid Dynamic (CFD) model in steady-state mode. The CFD model is validated with literature in both bounded and unbounded mediums. The rheological model of the Bingham plastic fluid is regularized with a smoothly varying viscosity. The retardation effects of the tube wall are presented in functions of Reynolds number Re, radius ratio λ (the radius of the tube to the semiaxis of the particle normal to the flow λ = R/r), aspect ratio E (the ratio of the semiaxis of the particle along the flow to r, E = b/r), and Bingham number Bn. The simulation results demonstrate that the drag coefficient C D declines with the rise in Reynolds number. The relative contribution to drag coefficient from the pressure force increases with larger Bingham number comparing with that from the friction force. The formation and size of the recirculation wake is suppressed by the yield stress. While Bn is approaching infinity, the limiting behavior is observed in the location of yield surface and the value of yield-gravity parameter. The values of critical yield-gravity parameter are explicitly given at different values of E, showing independence with Re and λ. For the flow with Bn ≥ 100, the influence of wall can be even ignored while λ is larger than 5.

Influence of SO3 on the MnOx/TiO2 SCR catalyst for elemental mercury removal and the function of Fe modification.

Elemental mercury (Hg0) is a highly hazardous pollutant of coal combustion. The low-temperature SCR catalyst of MnOx/TiO2 can efficiently remove Hg0 in coal-burning flue gas. Considering its sulfur sensitivity, the effect of SO3 on the catalytic efficiency of MnOx/TiO2 and Fe modified MnOx/TiO2 for Hg0 removal was investigated comprehensively for the first time. Characterizations of Hg-TPD and XPS were conducted to explore the catalytic mechanisms of Hg0 removal processes under different conditions. Hg0 removal efficiency of MnOx/TiO2 was inhibited irreversibly from 92% to approximately 60% with the addition of 50 ppm SO3 at 150 â„ƒ, which resulted from the transformation of Mn4+ and chemisorbed oxygen to MnSO4. The existence of H2O would intensify the inhibitory effect. The inhibition almost disappeared and even converted to promotion as the temperature increased to 250 â„ƒ and above. Fe modification on MnOx/TiO2 improved the Hg0 removal performance in the presence of SO3. The addition of SO3 caused only a slight inhibition of 1.9% on Hg0 removal efficiency of Fe modified MnOx/TiO2 in simulated coal-fired flue gas, and the efficiency maintained good stability during a 12 h experimental period. This work would be conducive to the future application of MnOx/TiO2 for synergistic Hg0 removal.

New mechanistic understanding for atmospheric oxidation of isoprene initiated by atomic chlorine.

Isoprene is the most abundant non-methane VOC and a significant SOA contributor. The atmospheric oxidation initiated by atomic chlorine is an important sink for isoprene, especially in certain regions with high Cl concentration, while its detailed oxidation mechanism remains unclear. In this work, we comprehensively investigated the reaction mechanism of isoprene with Cl using quantum chemistry calculation, and first elaborated the specific reaction mechanisms of chloroalkenyl peroxy radicals with HO2/NO and the formation of 2-methylbut-3-enal, highlighting their important roles in the SOA formation. For the initial reactions, Cl additions to terminal carbons and H abstraction from CH3 moiety of isoprene are the predominant reactions, which is consistent with previous research. Following the initial reactions, their subsequent reactions with O2 and HO2 (or NO) under different atmospheric conditions could lead to the formation of 17 highly oxidized molecules (HOMs), of which P10, P12, P16, P17, P19 and P33 generated by the subsequent reactions of the major first-generation products (MVK, CMBO, CMBA and MBO) have been detected in the reaction process of isoprene with Cl in the chamber experiment. In addition to auto-oxidation process, the reaction of chloroalkenyl peroxy radicals with HO2/NO and their subsequent reactions are all easy to occur under atmospheric conditions, which could be crucial contributors to the formation of HOMs and SOA arising from the Cl initiated oxidation of isoprene. This study would be conducive to clarifying the atmospheric oxidation process of isoprene initiated by Cl and providing a new understanding of its SOA formation.

The expression of STAT3 inhibited the NF-ΚB signalling pathway and reduced inflammatory responses in mice with viral myocarditis.

BACKGROUND: The aim of this study was to investigate the mechanism of STAT3 in reducing the inflammatory responses in mice with viral myocarditis (VMC). METHODS: Induce and generate viral myocarditis by using coxsackievirus B3 (CVB3) infected cardiomyocyte-specific STAT3 conditional knockout (STAT3cKO) mice and BALB/c mice. Use RT-PCR and western blot techniques to detect the expression of related cytokines in the uninfected wild-type mice group (Control group), myocarditis wild-type mice group (Model group) and STAT3cKO group, as well as the differentiation of spleen T cells in each group. Eukaryotic expression plasmid pcDNA3-STAT3 can reduce the expression of inflammatory factors the in vitro cultured cardiomyocytes of the STAT3cKO group. RESULTS: RT-PCR showed that compared with the Control group, the expression levels of VMC-related genes (NF-κB, TNF­α, IL-1ß and IL-1) and anti-inflammation-related cytokines (IL-10 and TGF-ß) in the Model group went up (*p < 0.05, **p < 0.01, ***p < 0.001); and also compared with the Control group, the rise in the expression levels of the above VMC-related genes in the STAT3cKO group was particularly significant (***p < 0.001, ****p < 0.0001) but there was no significant difference in the expression of IL-10 and TGF-ß. After 4 weeks, a second RT-PCR showed that the expression of inflammation-related genes in the STAT3cKO group continued to be activated (***p < 0.001, ****p < 0.0001). Western blotting was performed to detect the expression of p65, a key protein of the NF-κB signalling pathway. The results showed that the p65 protein content was increased and the IL-10 protein content was decreased in the STAT3cKO group; the results of the T cell differentiation test showed that the T cell differentiation rate increased in the STAT3cKO group (**p < 0.01). Eukaryotic expression plasmid pcDNA3-STAT3 could reduce the expression of NF-κB, TNF-α, IL-1ß and IL-17 (**p < 0.01). CONCLUSION: The expression of STAT3 gene in VMC could to a certain extent inhibit the NF-κB signalling pathway and reduce the inflammatory responses of VMC.

Decellularized adipose matrix provides an inductive microenvironment for stem cells in tissue regeneration.

Stem cells play a key role in tissue regeneration due to their self-renewal and multidirectional differentiation, which are continuously regulated by signals from the extracellular matrix (ECM) microenvironment. Therefore, the unique biological and physical characteristics of the ECM are important determinants of stem cell behavior. Although the acellular ECM of specific tissues and organs (such as the skin, heart, cartilage, and lung) can mimic the natural microenvironment required for stem cell differentiation, the lack of donor sources restricts their development. With the rapid development of adipose tissue engineering, decellularized adipose matrix (DAM) has attracted much attention due to its wide range of sources and good regeneration capacity. Protocols for DAM preparation involve various physical, chemical, and biological methods. Different combinations of these methods may have different impacts on the structure and composition of DAM, which in turn interfere with the growth and differentiation of stem cells. This is a narrative review about DAM. We summarize the methods for decellularizing and sterilizing adipose tissue, and the impact of these methods on the biological and physical properties of DAM. In addition, we also analyze the application of different forms of DAM with or without stem cells in tissue regeneration (such as adipose tissue), repair (such as wounds, cartilage, bone, and nerves), in vitro bionic systems, clinical trials, and other disease research.

Hazardous volatile organic compounds in ambient air of China.

Volatile organic compounds (VOCs) are ubiquitous in the atmosphere and the majority of them have been proved to be detrimental to human health. The hazardous VOCs were studied very insufficiently in China, despite the enormous emissions of VOCs. In this study, the concentrations and sources of 17 hazardous VOCs reported in literature were reviewed, based on which the health effects were assessed. In-depth survey indicated that benzene and toluene had the highest concentrations in eastern China (confined to the study regions reviewed, same for the other geographic generalization), which however showed significant declines. The southern China featured high levels of trichloroethylene. Dichloromethane and chloroform were observed to be concentrated in northern China. The distributions of 1,2-dichloropropane and tetrachloroethylene were homogeneous across the country. Basically consistent with the spatial patterns of ozone, the summertime formaldehyde exhibited higher levels in eastern and northern China, and increased continuously. While transportation served as the largest source of benzene and toluene, industrial emissions and secondary formation were the predominant contributors of halogenated hydrocarbons and aldehydes (formaldehyde and acetaldehyde), respectively. The chronic non-cancer effects of inhalation exposure to the hazardous VOCs were insignificant, however the probabilities of developing cancers by inhaling the hazardous VOCs in ambient air of China were quite high. Formaldehyde was identified as the primary carcinogenic VOC in the atmosphere of most regions. The striking results, especially the high inhalation cancer risks, alerted us that the emission controls of hazardous VOCs were urgent in China, which must be grounded upon full understanding of their occurrence, presence and health effects.

Correction to: Gas-phase reaction of benzo[a]anthracene with hydroxyl radical in the atmosphere: products, oxidation mechanism, and kinetics.

The original version of this article unfortunately contained a mistake. The sequence of the author affiliations was incorrect. The correct information is given below.

Mechanism and kinetics studies of the atmospheric oxidation of p,p'-Dicofol by OH and NO3 radicals.

As an effective organochlorine pesticide, Dicofol has been extensively applied in more than 30 countries for protecting over 60 different crops. Considering its large consumption and potential adverse effect on human health (endocrine disrupting and carcinogenicity), the fate of Dicofol sprayed into the air is of public concern. In this study, we conducted a comprehensive study on the reaction mechanisms of p,p'-Dicofol with OH and NO3 radicals using DFT method. Comparing the abstrations by OH and NO3 radical, OH and NO3 radical addition reactions are predominant due to the lower potential barriers and stronger heat release. The phenolic substances (P1P5), epoxides (P11 and P15), dialdehyde (P13) and other species (P8, P9, P10 and P14) are generated by OH additions and their subsequent reactions while OH abstraction reactions produce DCBP, P7 and chlorphenyl radical. Particularly, NO3 additions and their subsequent reactions yield dialdehydes (P16 and P17) and 2,8-DCDD, which is the first report of the generation of dioxin from atmospheric oxidation of p,p'-Dicofol. Additionally, based on the structure optimization and energy calculation, rate constants and Arrhenius formulas of the elementary reactions of p,p'-Dicofol with OH and NO3 radicals were obtained over the temperature range of 280-380 K and at 1 atm. The rate constants for the reactions of p,p'-Dicofol with OH and NO3 radicals are 1.51 × 10-12 and 8.88 × 10-14 cm3 molecule-1 s-1, respectively. The lifetime (τTotal) of p,p'-Dicofol determined by the reactions of OH and NO3 radical is 5.86 h, indicating a potential long-range transport in the atmosphere.

Gas-phase reaction of benzo[a]anthracene with hydroxyl radical in the atmosphere: products, oxidation mechanism, and kinetics.

Polycyclic aromatic hydrocarbons (PAHs) have induced large-scale and long-term environmental contamination due to heavy emissions, toxicity, and persistence. The investigation of the ultimate sink of PAHs in the atmosphere is very important. In this work, using quantum chemistry methods, the reaction mechanism of hydroxyl radical-initiated oxidation of benzo[a]anthracene (BaA) in the atmosphere was studied. The products resulted from the gas-phase reaction of BaA with hydroxyl radical include benzo[a]anthracenols, dialdehydes, ketones, epoxides, etc. Applying Rice-Ramsperger-Kassel-Marcus (RRKM) theory, the overall rate constant for reactions of •OH addition to BaA was estimated to be 4.82 × 10-11 cm3 molecule-1 s-1 at 298 K and 1 atm. The lifetime of BaA in the atmosphere with respect to hydroxyl radical was calculated to be 5.92 h.

Relationship of polycyclic aromatic hydrocarbons with oxy(quinone) and nitro derivatives during air mass transport.

Airborne concentrations of Polycyclic Aromatic Hydrocarbons (PAH), quinone and nitro derivatives have been measured at three sites on the coast of Saudi Arabia to the north of the city of Jeddah. The PAH show a general reduction in concentrations from northwest to southeast, consistent with a source from a petrochemical works to the northwest of the sampling sites. In comparison, the concentrations of quinones show little variation between the sampling sites consistent with these being predominantly longer lived secondary pollutants formed from PAH oxidation. The nitro-PAH show a gradient in concentrations similar to but smaller than that for the PAH suggesting a balance between atmospheric formation and removal by photolysis. The 2-nitrofluoranthene:1-nitropyrene ratio increases from north to south, consistent with atmospheric chemical formation of the former compound, while the ratio of 2-nitrofluoranthene:2-nitropyrene is consistent with hydroxyl radical as the dominant reactant. An investigation of the changes in PAH congener ratios during air mass transport along the Red Sea coast shows consistency with reaction with a relatively low concentration of hydroxyl radical only for the day with the highest concentrations. It is concluded that while PAH degradation is occurring by chemical reaction, emissions from other locations along the air mass trajectory are most probably also leading to changes in congener ratios.

Mechanism and thermal rate constant for the gas-phase ozonolysis of acenaphthylene in the atmosphere.

Due to its prevalent presence, it is critical to clarify the atmospheric fate of acenaphthylene (Ary). In this paper, the reaction mechanism of the gas-phase ozonolysis of Ary was investigated by using quantum chemistry methods. Possible reaction pathways were discussed, and the theoretical results were compared with the available experimental data. The rate constants of the crucial elementary reactions were determined by the Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The main products include secondary ozonide, naphthalene-1,8-dicarbaldehyde, 1,8-naphthalic anhydride, oxaacenaphthylene-2-one, 1-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, and α-hydroxyhydroperoxide. The reaction of the unsaturated cyclo-pentafused ring with O3 is the dominant pathway. The overall rate constant of the O3 addition reaction is 5.31×10(-16)cm(3)molecule(-1)s(-1) at 298 K and 1 atm. The atmospheric lifetime of Ary determined by O3 is about 0.75 h. This work provides a comprehensive investigation of the ozonolysis of Ary and should help to understand its atmospheric fate.

Theoretical perspectives on the mechanism and kinetics of the OH radical-initiated gas-phase oxidation of PCB126 in the atmosphere.

Polychlorinated biphenyls (PCBs) primarily exist in the gas phase in air and may undergo atmospheric oxidation degradations, particularly the oxidation reaction initiated by OH radicals. In this work, the mechanism of the OH radical-initiated atmospheric oxidation of the most toxic PCB congener 3,3',4,4',5-pentachlorobiphenyl (PCB126) was investigated by using quantum chemistry methods. The rate constants of the crucial elementary reactions were estimated by the Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The oxidation products of the reaction of PCB126 with OH radicals include 3,3',4,4',5-pentachlorobiphenyl-ols, chlorophenols, 2,3,4,7,8-pentachlorodibenzofuran, 2,3,4,6,7-pentachlorodibenzofuran, dialdehydes, 3,3',4,4',5-pentachloro-5'-nitro-biphenyl, and 4,5-dichloro-2-nitrophenol. Particularly, the formation of polychlorinated dibenzofurans (PCDFs) from the atmospheric oxidation of PCBs is revealed for the first time. The overall rate constant of the OH addition reaction is 2.52×10(-13)cm(3)molecule(-1)s(-1) at 298K and 1atm. The atmospheric lifetime of PCB126 determined by OH radicals is about 47.08days which indicates that PCB126 can be transported long distances from local to global scales.

Mechanistic and kinetic studies on OH-initiated atmospheric oxidation degradation of benzo[α]pyrene in the presence of O2 and NO(x).

The degradation of polycyclic aromatic hydrocarbons (PAHs) in the atmosphere can lead to toxic derivatives which contribute to the carcinogenic potential of particulate organic matter. This paper aimed to investigate the mechanism of the OH-initiated oxidation degradation of benzo[α]pyrene (BaP), a cancer risk indicator. High-accuracy molecular orbital calculations were carried out, and all of the possible degradation pathways were discussed. The theoretical results were compared with the available experimental observation. The possible secondary reactions were also investigated. The rate constants of the crucial elementary steps were evaluated by using the Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The dominant degradation products involve benzo[α]pyren-ol, nitro-benzo[α]pyrene, benzo[α]pyrene-7,10-dione as well as several ring-opened products such as alkyl substituted benzanthraldehyde et al. In particular, water plays an important role in the degradation pathways leading to the formation of nitro-benzo[α]pyrene. This work provides a comprehensive investigation of the OH-initiated degradation of BaP and should help to clarify its potential risk.

Mechanism and kinetic properties for the OH-initiated atmospheric oxidation degradation of 9,10-Dichlorophenanthrene.

Chlorinated polycyclic aromatic hydrocarbons (ClPAHs) have become a serious environmental concern due to their widespread occurrence and dioxin-like toxicities. In this work, the mechanism of the OH-initiated atmospheric oxidation degradation of 9,10-dichlorophenanthrene (9,10-Cl2Phe) was investigated by using high-accuracy quantum chemistry calculations. The rate constants of the crucial elementary reactions were determined by the Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The theoretical results were compared with the available experimental data. The main oxidation products are a group of ring-retaining and ring-opening compounds including chlorophenanthrols, 9,10-dichlorophenanthrene-3,4-dione, dialdehydes, chlorophenanthrenequinones, nitro-9,10-Cl2Phe and epoxides et al. The overall rate constant of the OH addition reaction is 2.35 × 10(-12)cm(3) molecule(-1)s(-1) at 298 K and 1 atm. The atmospheric lifetime of 9,10-Cl2Phe determined by OH radicals is about 5.05 days. This study provides a comprehensive investigation of the OH-initiated oxidation degradation of 9,10-Cl2Phe and should contribute to clarifying its atmospheric fate.