Systematic analysis of Heat Shock Protein 70 (HSP70) gene family in radish and potential roles in stress tolerance.

The 70 kD heat shock proteins (HSP70s) represent a class of molecular chaperones that are widely distributed in all kingdoms of life, which play important biological roles in plant growth, development, and stress resistance. However, this family has not been systematically characterized in radish (Raphanus sativus L.). In this study, we identified 34 RsHSP70 genes unevenly distributed within nine chromosomes of R. sativus. Phylogenetic and multiple sequence alignment analyses classified the RsHSP70 proteins into six distinct groups (Group A-F). The characteristics of gene structures, motif distributions, and corresponding cellular compartments were more similar in closely linked groups. Duplication analysis revealed that segmental duplication was the major driving force for the expansion of RsHSP70s in radish, particularly in Group C. Synteny analysis identified eight paralogs (Rs-Rs) in the radish genome and 19 orthologs (Rs-At) between radish and Arabidopsis, and 23 orthologs (Rs-Br) between radish and Chinese cabbage. RNA-seq analysis showed that the expression change of some RsHSP70s were related to responses to heat, drought, cadmium, chilling, and salt stresses and Plasmodiophora brassicae infection, and the expression patterns of these RsHSP70s were significantly different among 14 tissues. Furthermore, we targeted a candidate gene, RsHSP70-23, the product of which is localized in the cytoplasm and involved in the responses to certain abiotic stresses and P. brassicae infection. These findings provide a reference for further molecular studies to improve yield and stress tolerance of radish.

Bioaccumulation, Trophic Transfer, and Biotransformation of Polychlorinated Diphenyl Ethers in a Simulated Aquatic Food Chain.

Polychlorinated diphenyl ethers (PCDEs) are detected in aquatic environments and demonstrate adverse effects in aquatic organisms. However, data regarding the environmental behavior of PCDEs in aquatic ecosystems are lacking. In the present study, a simulated aquatic food chain (Scenedesmus obliquus-Daphnia magna-Danio rerio) was constructed in a lab setting, and the bioaccumulation, trophic transfer, and biotransformation of 12 PCDE congeners were quantitatively investigated for the first time. The log-transformed bioaccumulation factors (BCFs) of PCDEs in S. obliquus, D. magna, and D. rerio were in the range of 2.94-3.77, 3.29-4.03, and 2.42-2.89 L/kg w.w., respectively, indicating the species-specific bioaccumulation of PCDE congeners. The BCF values increased significantly with the increasing number of substituted Cl atoms, with the exception of CDE 209. The number of Cl atoms at the para and meta positions were found to be the major positive contributing factors for BCFs in the case of the same number of substituted Cl. The lipid-normalized biomagnification factors (BMFs) of S. obliquus to D. magna, D. magna to D. rerio, and the whole food chain for the 12 PCDE congeners ranged at 1.08-2.27, 0.81-1.64, and 0.88-3.64, respectively, suggesting that some congeners had BMFs comparable to PBDEs and PCBs. Dechlorination was the only metabolic pathway observed for S. obliquus and D. magna. For D. rerio, dechlorination, methoxylation, and hydroxylation metabolic pathways were observed. 1H nuclear magnetic resonance (NMR) experiments and theoretical calculations confirmed that methoxylation and hydroxylation occurred at the ortho position of the benzene rings. In addition, reliable quantitative structure-property relationship (QSPR) models were constructed to qualitatively describe the relationships between molecular structure descriptors and BCFs for PCDEs. These findings provide insights into the movement and transformation of PCDEs in aquatic ecosystems.

Initial Studies on the Effect of the Rice-Duck-Crayfish Ecological Co-Culture System on Physical, Chemical, and Microbiological Properties of Soils: A Field Case Study in Chaohu Lake Basin, Southeast China.

Rice-duck and rice-crayfish co-culture patterns can increase soil productivity and sustainability and reduce the use of chemical pesticides and fertilizers, thereby reducing the resulting negative environmental impacts. However, most studies have focused on the rice-duck and rice-crayfish binary patterns and have ignored integrated systems (three or more), which may have unexpected synergistic effects. To test these effects, a paddy field experiment was carried out in the Chaohu Lake Basin, Hefei city, Southeast China. Four groups, including a rice-duck-crayfish ecological co-culture system (RDC), idle field (CK), single-season rice planting system (SSR), and double-season rice planting system (DSR), were established in this study. The results showed that the RDC improved the soil physical properties, fertility, humus content, and enzyme activity. In the RDC system, the soil total nitrogen content ranged from 8.54% to 28.37% higher than other systems in the 0-10 cm soil layer. Similar increases were found for soil total phosphorus (8.22-30.53%), available nitrogen (6.93-22.72%), organic matter (18.24-41.54%), urease activity (16.67-71.51%), and acid phosphatase activity (23.41-66.20%). Relative to the SSR treatment, the RDC treatment reduced the total losses of nitrogen and phosphorus runoff by 24.30% and 10.29%, respectively. The RDC also did not cause any harm to the soil in terms of heavy metal pollution. Furthermore, the RDC improved the yield and quality of rice, farmer incomes, and eco-environmental profits. In general, the RDC can serve as a valuable method for the management of agricultural nonpoint-source pollution in the Chaohu Lake area and the revitalization of the countryside.

Comparative studies of transformation behaviors and mechanisms of halophenols in multiple chemical oxidative systems.

Due to wide applications, halophenols (HPs), especially bromophenols, chlorophenols, and fluorophenols, are commonly detected but resistant to biological removal in wastewater treatment plants (WWTPs). This study investigated the overall transformation behaviors of three representative HPs (2,4-dichlorophenol: 24-DCP, 2,4-dibromophenol: 24-DBP, 2,4-difluorophenol: 24-DFP) in six chemical oxidative systems (KMnO4, K2FeO4, NaClO, O3, UV, and persulfate (PS)). The results revealed fast removal of selected HPs by O3, PS and K2FeO4, while a large discrepancy in their removal efficiencies occurred under UV irradiation, KMnO4 oxidation and particularly chlorination. Based on the analysis of the identified intermediates and products, coupling among the five routes was the general route, and dimers were the main intermediates for HP oxidation. The effect of the halogen atom on the transformation pathways of HPs was highly reaction type dependent. Among the six chemical treatments, PS could induce HPs to yield relatively low-molecular-weight polymers and obtain the highest coupling degree. Transition state (TS) calculations showed that the H atom linked to the phenoxy group of HPs was the most easily abstracted by hydroxyl radicals to form the coupling precursor, i.e., phenoxy radicals. This high coupling behavior further resulted in the increased toxicity to green algae. Characterization revealed that HP reaction solutions treated with PS had a severely negative effect on algae growth, photosynthetic pigment synthesis, and the antioxidant enzyme system. These findings can shed light on the reaction mechanisms of advanced oxidation technologies and some risk management and control of PS technique may be considered when treating phenolic pollutants.

An Insight into the Sorption Behavior of 2,3,7,8-Tetrachlorodibenzothiophene on the Sediments and Paddy Soil from Chaohu Lake Basin.

Considering the frequent detection of polychlorinated dibenzothiophenes (PCDTs) in various environmental matrices and the potential ecological health risks, the environmental behavior of such compounds needs to be elucidated further. In this work, the sorption behavior of 2,3,7,8-tetrachlorodibenzothiophene (2,3,7,8-TCDT) onto three sediments and paddy soil from Chaohu Lake were investigated via batch equilibration experiments. From the perspective of sorption kinetics and isotherms, the sorption characteristics and mechanism of 2,3,7,8-TCDT on the above four carriers were compared, and the relationship between their structural characteristics and soil sorption capacity was discussed. Results suggested that rapid sorption played the primary role during the sorption process of 2,3,7,8-TCDT and the corresponding sorption isotherms were well fitted using the Freundlich logarithmic model. Moreover, the effects of pH and dissolved organic matter (DOM) on the sorption of 2,3,7,8-TCDT were investigated. The maximum sorption capacity of 2,3,7,8-TCDT on sediment was under acidic pH condition (pH = 4.0). Meanwhile, DOM at a low level promoted the sorption capacity of sediment toward 2,3,7,8-TCDT, while the high concentration of DOM inhibited this effect. In addition, the values of logKoc were obtained using high-performance liquid chromatography (HPLC) and did not show any significant correlation with organic carbon (OC) contents, thereby indicating that the partition effect was the dominating influencing factor for the sorption of 2,3,7,8-TCDT both on sediments and soil. This work provides useful data to understand the sorption behavior of 2,3,7,8-TCDT on sediments and soil and assess its potential environmental risk.

Enhanced removal of Cd2+ from water by AHP-pretreated biochar: Adsorption performance and mechanism.

The sesame straw-derived biochar was successfully prepared via alkaline hydrogen peroxide (AHP) pretreatment in this study. Systematic experimental characterizations, 15 relevant batch and column adsorption models, combined with density functional theory (DFT) calculation were used to investigate the performances and micro-mechanisms of Cd2+ adsorption onto biochar. We found AHP-pretreatment could greatly improve the adsorption performance of biochar for Cd2+. The maximum Cd2+ adsorption capacity of AHP-pretreated biochar (87.13 mg g-1) was much larger than that of unpretreated biochar. Cd2+ adsorption was mainly dominated by the chemisorption of the homogeneous surface monolayer. The hydroxyl and carboxyl groups on the surface of biochar provided preferential adsorption sites, and liquid film diffusion and intra-particle diffusion were two dominant rate-controlling steps. Our results showed that ion exchange, co-precipitation, surface complexation, and Cd2+-π interaction were the dominant adsorption mechanisms. Especially, DFT calculations well-identified that lone-pair electrons during complexation and π electrons during coordination were provided by oxygen-containing functional groups and aromatic rings, respectively. The experimental breakthrough curves fitted better with the theoretical value of the BJP model, compared to Thomas, Yoon-Nelson, and EXY models. Overall, our study provides a promising method for Cd2+ removal from wastewater and resource utilization of agricultural wastes.

Experimental and theoretical study on Fe(VI) oxidative degradation of dichlorophen in water: Kinetics and reaction mechanisms.

Dichlorophenol (DCP), a commonly used fungicide and insecticide, is widely found in waters and wastewaters. Herein, the degradation of DCP by Ferrate (Fe(VI)) in different matrices was comprehensively investigated. In pure water, a complete removal of DCP was achieved in 300 s at [Fe(VI)]:[DCP] molar ratio of 2:1. The presence of HA (10 mg L-1) inhibited DCP degradation to a certain extent. A total of twenty degradation products were identified by HPLC/MS analysis. Based on these products, reaction pathways including the cleavage of C-C bridge bond, hydroxylation, and radical coupling were proposed. These reaction mechanisms were further rationalized by theoretical calculations. The analyses of Wiberg bond orders and transition state indicated that C7-C8 bond was the most vulnerable site for cleavage, and C12 site was the most likely site for hydroxyl addition. Mulliken atomic spin densities distribution suggested that self-coupling products was easily generated via C-O-C coupling ways. Finally, the feasibility of applying Fe(VI) to degrade DCP (20 µM) in a municipal wastewater effluent and a lake water was evaluated and verified. The findings in this study are of relevance in designing Fe(VI)-based treatment strategy for chlorine-containing persistent pesticides.

Ferrate(VI) oxidation of bisphenol E-Kinetics, removal performance, and dihydroxylation mechanism.

Bisphenol E (bis (4-hydroxyphenyl) ethane, BPE), as a typical endocrine disrupting chemical, is commonly detected in source water and drinking water, which poses potential risks to human health and ecological environment. This paper investigated the removal of BPE by ferrate(VI) (FeVIO42-, Fe(VI)) in water. Under the optimal condition of [Fe(VI)]0:[BPE]0 = 10:1 and pH = 8.0, a removal efficiency of 99% was achived in 180 s. Sixteen intermediates of BPE were detected, and four possible reaction pathways were proposed, which mainly involved the reaction modes of double-oxygen and single-oxygen transfer, bond breaking, carboxylation and polymerization. The double-oxygen transfer mechanism, different from traditional mechanisms, was newly proposed to illustrate the direct generation of di-hydroxylated products from parent BPE, which was demonstrated by theoretical calculations for its rationality. Significantly, NO2-, HCO3-, Cu2+, and humic acid, constituents of water promoted the removal of BPE. Additionally, samples from river, tap water, synthetic wastewater, and secondary effluent were tested to explore the feasibility of Fe(VI) oxidation for treating BPE in water. It was found that 99% of BPE was degraded within 300 s in these waters except for synthetic wastewater. The toxicity of BPE and its intermediates was evaluated by ECOSAR program, and the results showed that Fe(VI) oxidation decreased the toxicity of reaction solutions. These findings demonstrated that the Fe(VI) oxidation process was an efficient and green method for the treatment of BPE, and the new insights into the double-oxygen transfer mechanism aid to understand the reaction mechanisms of organic pollutants oxidized by Fe(VI).

Transcriptional and physiological data revealed cold tolerance in a photo-thermo sensitive genic male sterile line Yu17S.

BACKGROUND: Rice is highly sensitive to chilling stress during the seedling stage. However, the adaptable photo-thermo sensitive genic male sterile (PTGMS) rice line, Yu17S, exhibits tolerance to low temperatures. Currently, the molecular characteristics of Yu17S are unclear. RESULTS: To evaluate the molecular mechanisms behind cold responses in rice seedlings, a comparative transcriptome analysis was performed in Yu17S during seedling development under normal temperature and low temperature conditions. In total, 9317 differentially expressed genes were detected. Gene ontology and pathway analyses revealed that these genes were involved mostly in photosynthesis, carotenoid biosynthesis, carbohydrate metabolism and plant hormone signal transduction. An integrated analysis of specific pathways combined with physiological data indicated that rice seedlings improved the performance of photosystem II when exposed to cold conditions. Genes involved in starch degradation and sucrose metabolism were activated in rice plants exposed to cold stress treatments, which was accompanied by the accumulation of soluble sugar, trehalose, raffinose and galactinol. Furthermore, chilling stress induced the expression of phytoene desaturase, 15-cis-ζ-carotene isomerase, ζ-carotene desaturase, carotenoid isomerase and ß-carotene hydroxylase; this was coupled with the activation of carotenoid synthase activity and increases in abscisic acid (ABA) levels in rice seedlings. CONCLUSIONS: Our results suggest that Yu17S exhibited better tolerance to cold stress with the activation of carotenoid synthase activity and increasing of ABA levels, and as well as the expression of photosynthesis-related genes under cold condition in rice seedlings.

Identification, systematic evolution and expression analyses of the AAAP gene family in Capsicum annuum.

BACKGROUND: The amino acid/auxin permease (AAAP) family represents a class of proteins that transport amino acids across cell membranes. Members of this family are widely distributed in different organisms and participate in processes such as growth and development and the stress response in plants. However, a systematic comprehensive analysis of AAAP genes of the pepper (Capsicum annuum) genome has not been reported. RESULTS: In this study, we performed systematic bioinformatics analyses to identify AAAP family genes in the C. annuum 'Zunla-1' genome to determine gene number, distribution, structure, duplications and expression patterns in different tissues and stress. A total of 53 CaAAAP genes were identified in the 'Zunla-1' pepper genome and could be divided into eight subgroups. Significant differences in gene structure and protein conserved domains were observed among the subgroups. In addition to CaGAT1, CaATL4, and CaVAAT1, the remaining CaAAAP genes were unevenly distributed on 11 of 12 chromosomes. In total, 33.96% (18/53) of the CaAAAP genes were a result of duplication events, including three pairs of genes due to segmental duplication and 12 tandem duplication events. Analyses of evolutionary patterns showed that segmental duplication of AAAPs in pepper occurred before tandem duplication. The expression profiling of the CaAAAP by transcriptomic data analysis showed distinct expression patterns in various tissues and response to different stress treatment, which further suggest that the function of CaAAAP genes has been differentiated. CONCLUSIONS: This study of CaAAAP genes provides a theoretical basis for exploring the roles of AAAP family members in C. annuum.

Effective degradation of 2,4-dihydroxybenzophenone by zero-valent iron powder (Fe0)-activated persulfate in aqueous solution: Kinetic study, product identification and theoretical calculations.

2,4-Dihydroxybenzophenone (BP-1), a typically known derivative of the benzophenone-type UV filter, has been frequently detected in aqueous environments and poses a potential risk to human health and the entire ecosystem. In this study, an effective advanced oxidation technique using zero-valent iron powder (Fe0)-activated persulfate (PS) was used for the degradation of BP-1. The effects of several experimental parameters, including Fe0 dosages, PS dosages, pH, and common natural water constituents, were systematically investigated. The BP-1 degradation efficiency was enhanced by increasing the Fe0 and PS dosages and decreasing the solution pH. The presence of different concentrations of humic acid (HA) could inhibit BP-1 removal, while the addition of various cations and anions had different effects on the degradation. Moreover, the degradation of BP-1 in five water matrices was also compared, and the removal rates followed the order of ultrapure water > tap water > secondary clarifier effluent > river water > synthetic water. Thirteen oxidation products were identified by liquid chromatography-time-of-flight-mass spectrometry (LC-TOF-MS) analysis, and five possible degradation pathways were proposed. The addition reactions initiated by HO and SO4-, as well as single-electron coupling reactions and ring-closing reactions, were further supported by density functional theory (DFT) calculations. Assessment of toxicity of intermediates of the oxidation of BP-1 suggested decreased toxicity from the parent contaminant. The present work illustrates that BP-1 could be efficiently degraded in the Fe0/PS system, which may provide new insights into the removal of benzophenones in water and wastewater.

Products distribution and contribution of (de)chlorination, hydroxylation and coupling reactions to 2,4-dichlorophenol removal in seven oxidation systems.

We systemically investigated the transformation behavior of 2,4-dichlorophenol (24-DCP) in seven different reaction systems including KMnO4, heat/PS, O3, UV, Fenton, NaClO and K2FeO4 treatment. The results revealed that complete removal of 24-DCP could be reached in minutes, especially for Fe(VI), KMnO4, NaClO, Fenton and O3 system. A total of 41 products were identified by LC-MS, and 10 of them were validated using commercial and self-synthesized standards. Hydroxyl substitution and coupling reactions were commonly observed in the studied systems. Meanwhile, extra routes such as sulfate substitution, (de)chlorination and direct oxidation were also involved for certain oxidation methods. Comparisons showed that a high degree of chlorination (>90%) occurred for NaClO system, while coupling products accounted for ~45% of the removed 24-DCP under PS oxidation. Moreover, low mineralization degree together with high aquatic toxicity was attributed to the occurrence of coupling reaction, which was possibly related to the redox potential of the main oxidative species. Considering the low abundance of coupling products and the gentle reaction condition, UV irradiation is a better option for 24-DCP removal in water and wastewaters. These findings can deepen our understanding on the transformation process of 24-DCP and provide some useful information for the environmental elimination of substituted phenols.

Photodegradation of polychlorinated diphenyl sulfides (PCDPSs) under simulated solar light irradiation: Kinetics, mechanism, and density functional theory calculations.

The direct photolysis of 25 individual polychlorinated diphenyl sulfides (PCDPSs) substituted with 1-7 chlorine atoms was investigated using a 500-W Xe lamp. Photolysis of PCDPSs followed pseudo-first-order kinetics, with the higher chlorinated diphenyl sulfides generally degrading faster than the lower chlorinated congeners. A quantitative structure-activity relationship model to predict the photolysis rates of PCDPSs was developed using 16 fundamental quantum chemical descriptors. We found that the substitution pattern for chlorine atoms, the dipole moment, and ELUMO - EHOMO were major factors in the photolysis of PCPDSs. The reaction kinetics, products, and photodegradation pathways of 2,2',3',4,5-pentachlorodiphenyl sulfide (PeCDPS) suggest hydroxylation, direct photooxidation, the C-S bond cleavage reaction, and hydroxyl substitution were mainly involved in the photodegradation process, leading to the formation of 13 intermediates, detected by an electrospray time-of-flight mass spectrometer. The initial reaction sites of PCDPSs under photolysis were rationalized by density functional theory calculations. Anions (Cl-, SO42-, NO3-, and HCO3-) and Co2+ had no influence on the removal of PeCDPS, while Fe3+, Cu2+, and HA decreased the photolysis efficiency of PeCDPS. This report is the first to develop a logk quantitative structure-property relationships (QSPR) model of 25 PCDPSs and to describe mechanistic pathways for the photolysis of PeCDPS.

KMnO4-mediated reactions for hexachlorophene in aqueous solutions: Direct oxidation, self-coupling, and cross-coupling.

Hexachlorophene (HCP) is used in a range of general cleaning and disinfecting products and has received increased attention due to its damaging effect to the central nervous system in animals and its toxicity in humans. The chemical oxidation of HCP by KMnO4 was performed to systematically evaluate the effects of oxidant dose, pH, temperature, typical anions, humic acid (HA), and various matrices on HCP removal. The second-order rate constant for HCP was determined to be 4.83 × 104 M-1 s-1 at pH 7.0 and 25 °C. The presence of HA can inhibit the removal of HCP by KMnO4, while Cl-, NO3-, SO42-, PO43-, and CO32- have negligible effects. Degradation products analysis of the reaction, as well as theoretical calculations of HCP molecule and its phenoxy radical species, indicated that KMnO4 oxidation for HCP included a C-C bridge bond cleavage, hydroxylation, direct oxidation and self-coupling, and cross-coupling reactions. This study revealed that KMnO4 oxidation is an effective technique for eliminating HCP in real water and wastewater.

Alumina-mediated photocatalytic degradation of hexachlorobenzene in aqueous system: Kinetics and mechanism.

Five kinds of Al2O3 were characterized by SEM, TEM, FT-IR and BET surface area, and then used as carriers to investigate the photochemical removal of hexachlorobenzene (HCB) in aqueous system. The results showed that HCB coated on the surfaces of all Al2O3 could be photodegraded rapidly, and Neutral-Al2O3 presented the best performance. Meanwhile, the efficient removal of HCB in real water matrices, including tap water, river water and secondary clarifier effluent showed the potential practical application of Al2O3. EPR and theoretical calculation revealed the generation of hydroxyl radicals on Al2O3 surface under 500 W Xe lamp irradiation. Nine intermediates and a small amount of Cl- were identified by GC/MS, LC/MS and IC analysis, which was further verified by transition state calculations. These results can provide a new technique for HCB removal in water and wastewaters, and give more insights into the environmental ecological risk assessment of this pollutant.

A combined experimental and computational study on the oxidative degradation of bromophenols by Fe(VI) and the formation of self-coupling products.

In this study, the degradation of eight bromophenols (BPs), including monobromophenols (2-BP, 3-BP, and 4-BP), dibromophenols (2,4-DBP, 2,6-DBP, and 3,5-DBP), a tribromophenol (2,4,6-TBP) and a pentabromophenol (PBP), by a Fe(VI) reaction process at a pH of 8.0 was systematically studied. It was concluded that their degradation rates increased with increasing Fe(VI) concentrations in solution. The removal of 2,4,6-TBP, 2-BP, and 2,6-DBP was faster than that of the other five BPs, which could be attributed to the position of the substituting Br atom. Moreover, the direct oxidation and coupling reactions greatly influenced the reactivity of the bromophenols with Fe(VI). The electron paramagnetic resonance (EPR) analysis confirmed the presence of hydroxyl radicals in present system. The oxidation reaction products of PBP and 2-BP were recognized by an electrospray time-of-flight mass spectrometer; hydroxylation, hydroxyl substitution, the cleavage of the C-C bond, direct oxidation and polymerization via an end linking mechanism were noticeably found in the reaction process, resulting in the formation of polymerization products and causing hydroxylation to occur. Theoretical calculations further determined the possible oxidation sites of 2-BP and PBP. This study may provide comprehensive and important information on the remediation of BPs by Fe(VI).

Photochemical formation of hydroxylated polychlorinated biphenyls (OH-PCBs) from decachlorobiphenyl (PCB-209) on solids/air interface.

In this work, the photochemical transformation of decachlorobiphenyl (PCB-209) on the surface of several solid particles were systematically evaluated under simulated solar irradiation. The degradation kinetics of PCB-209 were first investigated using silica as a model aerosol particulate. It was found that PCB-209 photodegradation was enhanced at small silica particle size, low surface coverage and low humidity. Electron paramagnetic resonance (EPR) analysis and radicals quenching experiments demonstrated that hydroxyl radicals contributed to PCB-209 degradation. Stepwise hydrodechlorination, hydroxyl addition and cleavage of the CC bridge bond were mainly observed in the reaction process, leading to the formation of lower chlorinated PCBs, hydroxylated PCBs (OH-PCBs) and chlorophenols. Based on density functional theory (DFT) calculation, the dissociation energy of the CCl bond requires 354.81-359.79 kJ/mol energy that corresponds to a wavelength of less than 322 nm. And the minimum activation energy of OH radicals attack on PCB-209 is only 18.12 kJ/mol. Photochemical transformation of PCB-209 can also occur on the surface of natural particles, but the rates were inhibited as compared to silica. The hydroxylation and hydrodechlorination products of PCB-209 were detected in all natural particles. This study would make significant contribution to understanding the fate of PCBs in solids/air interface.

Mechanistic insights into the reactivity of Ferrate(VI) with phenolic compounds and the formation of coupling products.

In this paper, the removal of 2-benzylphenol (2-BP), phenol (Ph), chlorophene (CP), and 4-chlorophenol (4-CP) by Fe(VI) have been examined at pH 8.0. The second-order rate constant (k) for substrates degradation at a Fe(VI) concentration of 0.2 mM was in the order of kCP (353 M-1 s-1) > k4-CP (131 M-1 s-1) > k2-BP (102 M-1 s-1) > kPh (40 M-1 s-1), indicating that the presence of chlorine and benzyl groups in benzene ring can enhance the reactivity of the phenolic compounds with Fe(VI). Reaction products were identified by a liquid chromatography-quadrupole-time-of-flight-mass spectrometry (LC-Q-TOF-MS), and four reaction mechanisms, including hydroxylation of benzene ring, cleavage of C-C bridge bond, substitution of chlorine atom by hydroxyl group, and the single-electron coupling mechanism were proposed for phenols degradation by Fe(VI). The extracted peak areas of the degradation products showed that the single-electron coupling reaction is the main degradation mechanism in Fe(VI) oxidation processes. In addition to direct attack by Fe(VI), hydroxyl radical, as detected by electron paramagnetic resonance (EPR) spectra, also plays a role in phenols degradation. The •OH initiated reactions and single-electron coupling reactions were further explored by total charges distribution, transition state calculations and potential energy profiles. In addition, Fe(VI) could also work as a highly effective oxidant for substrates removal from real waters.

Formation of hydroxylated derivatives and coupling products from the photochemical transformation of polyfluorinated dibenzo-p-dioxins (PFDDs) on silica surfaces.

Polyfluorinated dibenzo-p-dioxins (PFDDs) are dioxin compounds that have been detected in industrial fluoroaromatic chemicals and can cause adverse effects to organisms. In this work, the photochemical behaviors of PFDDs congeners on silica was systematically investigated. The pseudo-first-order rate constants (k, h-1) of surface photolysis changed with the substitution number and position of fluorine atoms, and the tetra-fluorinated PFDDs tended to degrade more efficiently. Octafluorinated dibenzo-p-dioxin (OFDD) was selected as a representative to explore the reaction mechanisms. Product analysis showed that OFDD was decomposed into hydroxylated PFDDs (OH-PFDDs) and hydroxylated polyfluorinated diphenyl ethers (OH-PFDEs) via hydroxyl substitution and (OH radical mediated or direct) C-O bond cleavage. Coupling elimination reaction was also observed, resulting in the formation of three-membered and four-membered ring compounds. According to the extracted peak areas in mass spectra and the energy barrier in potential energy surface, direct homolysis of C-O bond occurs as the dominant reaction pathway. This work could provide some new insights into the environmental fate of dioxin compounds.

Photochemical degradation of polyhalogenated carbazoles in hexane by sunlight.

Polyhalogenated carbazoles (PHCZs) are a class of halogenated dibenzopyrrole, which have been increasingly detected in the environment and found to be bioaccumulative and potentially toxic. However, their environmental transformation potential is largely unknown. In this study, UV absorption spectra of carbazole (CZ) and 10 PHCZs were obtained with wavelength range 290-400 nm, and three peaks were identified in most cases with the highest occurring around 300 nm. Hexane solutions of CZ, 10 individual PHCZs, and a sediment extract containing nine other PHCZs were separately irradiated under natural sunlight in order to investigate their photodegradation kinetics and pathways. The pseudo-first-order reaction rate constants (k) of these PHCZs varied from 0.183 h-1 to 2.394 h-1, and increased exponentially with increasing numbers of chlorines and bromines in PHCZ molecules. Contribution to ln k from each bromine atom is more than doubling of that from each chlorine atom. Stepwise reduction debromination was confirmed to be one of the photodegradation mechanisms for both brominated and mixed halogenated (containing both bromine and chlorine) carbazoles. Only sporadic dechlorinated products were found during the photolysis of chlorinated carbazoles. By adopting a simplified kinetic approach, we estimated that dehalogenation contributed approximately 20% to 51% of the total loss of the parent PHCZs.