Photodegradation of hexachlorobenzene and theoretical prediction of its degradation pathways using quantum chemical calculation

Experimentally determined photodegradation pathways of hexachlorobenzene (HCB), a chlorinated aromatic compound, in hexane, 2-propanol (IPA), and methanol were compared with those predicted by quantum chemical calculation based on density functional theory (DFT), and the adequacy of the prediction method was evaluated. The experimental main degradation pathways of HCB were virtually the same for the three solvents and also agreed with the predicted main degradation pathways. In the DFT method, the main degradation product was the dechlorinated benzene at the position where the C-Cl bond was predicted to have the lowest bond dissociation energy. This result suggested that the photodechlorination pathways of chlorinated aromatic compounds could be predicted by comparing the bond dissociation energies calculated with the DFT method.     

Photodechlorination of octachlorodibenzothiophene and octachlorodibenzofuran: comparison of experimental degradation pathways with degradation pathways predicted by DFT

Polychlorodibenzothiophenes (PCDTs) are sulfur analogues of polychlorodibenzofurans (PCDFs) and have been detected in environmental samples. We used density functional theory calculations (Gaussian 98W) to predict the photodechlorination pathways of octachlorodibenzothiophene (OCDT) and octachlorodibenzofuran (OCDF) in hexane, and we compared the predicted pathways with those observed during UV irradiation experiments. OCDT and OCDF were observed to degrade through first-order dechlorination processes, and the rate constant for OCDT was less than one-third that for OCDF. The main experimental photodechlorination pathways of OCDT and OCDF led to hexachlorinated and tetrachlorinated congeners, respectively; that is, the photodechlorination pathway of OCDT differed from that of OCDF. On the assumption that the dechlorination mechanisms involved radical reactions, we used DFT calculations to estimate bond-dissociation energies and single-point energies of OCDT and OCDF and their dechlorinated congeners, and we used the resulting information, along with hypotheses regarding the rate-controlling step of the degradations, to predict theoretical degradation pathways. We propose that reaction of dechlorinated radicals with a hydrogen donor was the rate-controlling step for OCDT and that C-Cl bond dissociation by UV light was the rate-controlling step for OCDF.     

Photodegradation of pentachlorophenol catalyzed by semiconductor particles

The heterogeneous photocatalytic degradation of pentachlorophenol (PCP) in aqueous solutions containing a suspension of TiO₂ leads to the quantitative formation of CO₂ and HC1. The photodegradation has also been studied in other semiconductor dispersions such as ZnO, CdS, WO₃, and SnO₂. TiO₂ appears the most efficient. Oxygen and water are essential ingredients in the complete mineralization of this pollutant found near pulp and paper industries. Experiments with sunlight show a promising route for the water treatment processes; the half life of PCP (initial concentration 4.5 × 10^?5M) is about 8 minutes, in the presence of 2 g/l of TiO₂.     

Photodegradation of pentachlorophenol by sunlight in aquatic surface microlayers

Photodegradation of pentachlorophenol (PCP) in aquatic surface microlayer (SM) was examined under natural sunlight. SM samples were collected using a glass plate, along with corresponding subsurface waters. PCP was added to samples of the SM and subsurface water. When all samples were exposed to the same natural sunlight conditions, the first order photodegradation rates of PCP in the SM water samples were different from those of PCP in corresponding subsurface water samples. The difference was correlated with the enrichment of dissolved organic carbon (DOC) in SM compared to the corresponding subsurface waters. Enhanced photodegradation in SM may be due to increased abundance of photoreactants related to the UV-absorbing properties of dissolved organic materials in the SM as the result of photo-induced reactions. Effects of environmental factors, pH and salinity, on photodegradation process of PCP in SM were also evaluated.     

降解H2S功能菌的分离及降解特性

从污水处理厂曝气池污泥中分离纯化得到一株革兰氏阴性杆菌,命名为Y1.通过生理生化特性分析和16S rDNA序列测定,初步鉴定为纤维化纤维微细菌(Cellulosimicrobium cellulans).测定该菌株的生长曲线,知其延迟期约24 h,对数生长期约持续26 h,稳定期约持续18 h.通过单因素及正交实验考察了pH值、温度及摇床转速对该菌株生长情况的影响.结果表明,菌株的适宜生长条件为:pH值为6.5、温度为32℃,摇床转速为150 r/min.在适宜条件下培养菌株,其脱除高浓度H2S的效率可达98.29%.     

Microwave-induced nanoscale zero-valent iron degradation of perchloroethylene and pentachlorophenol

Microwave (MW) is applied to enhance perchloroethylene (PCE) or pentachlorophenol (PCP) removal using zero-valent iron (ZVI; Fe⁰) as the dielectric medium. ZVI has a much higher dielectric loss factor (39.5) than other media; it is capable of absorbing MW radiation rapidly to speed up the release of electrons, leading to rises of the ZVI particle surface temperature. If the MW power is continued, excessive electricity will accumulated inside ZVI particles, resulting in sparks. The results show that during the initial 5 sec (700 W), the linear aliphatic PCE has a faster decomposing rate than the ringed PCP (82.0% vs. 4.8%) because less energy is required for decomposing the linear-chlorine bond (90 kcal mol^?1) than ring-chlorine bonds (95 kcal mol^?1). Later, the removal rate for either PCE or PCP remains the same when the exposure time is between 5 and 60 sec. Without MW irradiation, linear PCE molecules have larger surface area to contact ZVI, and hence they have better removal efficiencies than PCP molecules. Using Fe⁰ as a microwave dielectric medium to treat PCE or PCP is a new and worthwhile treatment technology; it is environmentally friendly, and its use will eliminate the secondary pollution.

Implications Nanoscale iron particles are characterized by high surface-area-to-volume ratios, high specific surface area, and high surface reactivity. With a much higher dielectric loss factor, it is capable of absorbing MW radiation rapidly to speed up the release of electrons, leading to rise in temperature. The time needed to achieve a satisfactory treatment is also reduced, leading to significant saving of energy consumption to make this method cost-effective and also environmentally friendly for the industry to pursuit sustainable development.     

Photoelectrocatalytic degradation of pentachlorophenol in aqueous solution using a TiO2 nanotube film electrode

Titanium dioxide (TiO2) nanotube film electrodes are fabricated by the anodic oxidation method. Scanning electron microscopy (SEM) showed that these tubes were well aligned and organized into high-density uniform arrays. XRD analysis showed the TiO2 nanotubes to be in the anatase crystal form. The TiO2 nanotube film electrode exhibited increased photoelectrocatalytic (PEC) capability compared to a traditional TiO2 film electrode fabricated using the anodizing method for pentachlorophenol (PCP) degradation in aqueous solution. The bias potential, pH value, and electrolyte concentration were shown to be important factors influencing the degradation of PCP by the PEC method using the TiO2 nanotube film electrode as the working electrode.     

Photocatalytic degradation of pentachlorophenol on TiO2 sol-gel catalysts

The photocatalytic degradation of pentachlorophenol (PCP) in aqueous solution was investigated using TiO2 catalysts. The samples were prepared by the sol-gel method using different gelation pH and different calcination temperatures. The solids were characterized by specific surface area, X-ray diffraction, UV-Vis absorbance, FTIR and pentachlorophenol adsorption. The catalytic activity of the solids was evaluated in a conventional photoreactor at 298 K using 30 ppm of pentachlorophenol. It was found that the reaction follows a first-order reaction and the kinetic constant values change slightly with the pH of gelation and more significantly with the calcination temperature.     

A density functional theory/time-dependent density functional theory study of the structure-related photochemical properties of hydroxylated polybrominated diphenyl ethers and methoxylated polybrominated diphenyl ethers and metal ion effects

Environmental Science and Pollution Research - As the derivatives and structural analogs of polybrominated diphenyl ethers (PBDEs), hydroxylated polybrominated diphenyl ethers (OH-PBDEs)...     

降解SO_2功能菌的16S rRAN基因测序及降解特性

用低浓度SO2诱导驯化方法获得高效脱硫菌群,并用分离培养与16S rRNA基因测序技术相结合的方法鉴定菌群种属,分析驯化过程中种群结构的动态变化,同时研究分离纯菌种的脱硫性能。结果表明,从诱导驯化7 d和14 d菌液中分别分离出23株菌和22株菌,16S rRNA序列分析发现这些菌归属于13个种,其中有6个种（Rhodococcus erythropolis、Pseudomonas putida、Microbacterium oxydans、Sphingomonas koreensis、Acinetobacter junii、Acinetobacter johnsonii）对SO2-3有较强的降解能力,并在持续驯化过程中稳定的生长传代,降解产物以硫酸根为主,还有极少量的单质硫。与含混合菌的驯化菌液降解SO2-3的能力相比,单一脱硫菌的脱硫性能较弱。脱硫功能菌株及其基本特性的研究为微生物处理SO2烟气提供了丰富的菌源信息和理论基础。     

Crystal structure and density functional theory studies of toxic quinone metabolites of polychlorinated biphenyls

Lower chlorinated polychlorinated biphenyls (PCBs) are readily metabolized via hydroxylated metabolites to reactive PCB quinones. Although these PCB metabolites elicit biochemical changes by mechanisms involving cellular target molecules, such as the aryl hydrocarbon receptor, and toxicity by interacting with enzymes like topoisomerases, only few PCB quinones have been synthesized and their conformational properties investigated. Similar to the parent compounds, knowledge of the three-dimensional structure of PCB quinones may therefore be important to assess their fate and risk. To address this gap in our knowledge, the gas phase molecular structure of a series of PCB quinones was predicted using HF/3-21G, B3LYP/6-31G?? and UB3LYP/6-311G?? calculations and compared to the respective solid state structure. All three methods overestimated the Cl-C bond length, but otherwise provided a reasonable approximation of the solid state bond angles and bond lengths. Overall, the UB3LYP/6-311G?? level of theory yielded the best approximation of the molecular structure of PCB quinones in the solid state. Chlorine addition at the ortho position of both rings was found to increase the dihedral angle of the resulting quinone compound, which may have important implications for their interaction with cellular targets and, thus, their toxicity.     

土壤及其主要化学组分对五氯酚吸附特征研究

研究了土壤原样及其去锰氧化物、去铁氧化物、去有机质和去水溶性有机质(DOM)土壤样品对五氯酚(PCP)的吸附规律,分析了土壤及其主要化学组分对PCP的吸附机制.实验结果表明,Langmuir方程可较好地描述PCP在各土壤样品上的热力学吸附过程.PCP在土壤上的吸附行为与自身性质和土壤理化性质密切相关,有机质和铁氧化物对PCP的吸附起到促进作用,而锰氧化物和DOM则能在一定程度上抑制PCP的吸附.通过Langmuir方程得到的拟合结果,可判断PCP在各土壤样品上的最大吸附量为去锰氧化物土壤样品＞去铁氧化物土壤样品＞去DOM土壤样品＞土壤原样＞去有机质土壤样品.     

降解SO2功能菌的16S rRAN基因测序及降解特性

用低浓度SO2诱导驯化方法获得高效脱硫菌群,并用分离培养与16S rRNA基因测序技术相结合的方法鉴定菌群种属,分析驯化过程中种群结构的动态变化,同时研究分离纯菌种的脱硫性能。结果表明,从诱导驯化7 d和14 d菌液中分别分离出23株菌和22株菌,16S rRNA序列分析发现这些菌归属于13个种,其中有6个种(Rhodococcus erythropolis、Pseudomonas putida、Microbacterium oxydans、Sphingomonas koreensis、Acinetobacter junii、Acinetobacter johnsonii)对SO2-3有较强的降解能力,并在持续驯化过程中稳定的生长传代,降解产物以硫酸根为主,还有极少量的单质硫。与含混合菌的驯化菌液降解SO2-3的能力相比,单一脱硫菌的脱硫性能较弱。脱硫功能菌株及其基本特性的研究为微生物处理SO2烟气提供了丰富的菌源信息和理论基础。     

Evolutions of microbial degradation pathways for parent xenobiotic and for its metabolites follow different schemes

Background and purposes

The pathways used by microorganisms for the metabolism of every xenobiotic substrate are specific. The catabolism of a xenobiotic goes through a series of intermediate steps and lower intermediates (metabolites) appear in sequence. The structure of the metabolites can be similar to the parents due to kinship. The purposes of this study were to examine if the degradation pathways that were developed for a parent xenobiotic are effective to degrade the parent??s lower metabolites, and if the reverse is true.

Materials and methods

The xenobiotic substrates, 2,4-dichlorophenoxyacetic acid (2,4-D, the parent xenobiotic) and its metabolite 2,4-dichlorophenol (2,4-DCP), were independently subjected to acclimation and degradation tests by the biomasses of mixed-culture activated sludge and a pure culture of Arthrobacter sp.

Results

Activated sludge and Arthrobacter sp. that were acclimated to 2,4-D effectively degraded 2,4-D and the lower metabolites of 2,4-D, typically 2,4-DCP. During the degradation of 2,4-D, accumulations of the lower metabolites of 2,4-D were not found. The degradation pathways acquired from acclimation to 2,4-D are effective for all the metabolites of 2,4-D. However, pathways acquired from acclimation to 2,4-DCP are not effective in the degradation of the parent 2,4-D.

Conclusions

Microorganisms acclimated to 2,4-D evolve their degradation pathways by a scheme that is different from the scheme the microorganisms employ when they are acclimated to the metabolites of 2,4-D.     

Characterisation of the abiotic degradation pathways of oxytetracyclines in soil interstitial water using LC-MS-MS

The fate of oxytetracyclines (OTCs) in soil interstitial water was investigated and the structure of a number of degradation products elucidated in a time-related experiment. A previously developed separation method for LC–MS–MS able to base separate and quantify OTC and three of its epimers and degradation products was applied. Compounds detected were 4-epi-oxytetracycline (EOTC) (t_R=3.0 min), OTC (t_R=4.4 min), -apo-oxytetracycline (-apo-OTC) (t_R=11.4 min) and β-apo-oxytetracycline (β-apo-OTC) (t_R=18.4 min). Furthermore, we tentatively identified 4-epi-N-desmethyl-oxytetracycline (E-N-DM-OTC) (t_R=3.0 min), N-desmethyl-oxytetracycline (N-DM-OTC) (t_R=3.5), N-didesmethyl-oxytetracycline (N-DDM-OTC), 4-epi-N-didesmethyl-oxytetracycline (E-N-DDM-OTC) (t_R=3.7 and 4.7 min) and 2-acetyl-2-decarboxamido-oxytetracycline (t_R=8.7) in all samples. Most compounds were only present in trace concentrations (less than 2%) relative to the parent OTC. EOTC was on the other hand formed up to a ratio of 0.6 relative to parent OTC concentration. Only EOTC, E-N-DM-OTC, N-DM-OTC, N-DDM-OTC and E-N-DDM-OTC were formed during the time-related experiment. All other compounds were probably only present as impurities in the spiked OTC formulation as they declined in concentration from the start of the experiment. Half-lives (T_1/2, days) of the OTCs in soil interstitial water were in the order of 2 days (EOTC) to 270 days (β-apo-OTC).     

Effect of aging on catalytic properties in mechanochemical degradation of pentachlorophenol by birnessite

Mechanochemistry, a technique concerning with milling contaminated samples for prolonged times, induces massive degradation of pollutants by grinding them in ball mills with different soil components or additives. In the present study, laboratory experiments were conducted to evaluate the effect of aging on the mechanochemical efficiency of the Mn-oxide birnessite in degrading pentachlorophenol (PCP). A comparative study on an aged birnessite (KBiA), used after 3 years from synthesis, and a fresh birnessite (KBiF), employed immediately after synthesis, was carried out. The differences between the two birnessites, evidenced by spectroscopic and diffractometric techniques, are mainly relative to reduction of the Mn(IV) centered at the MnO₆ octahedra layers from the birnessite structure, which represent the most reactive sites for PCP degradation. The long term air drying at room temperature, by favouring reduction of Mn(IV) to Mn(III), produces an inorganic substrate that offers paucity of the less reactive sites for PCP degradation, thus reducing the oxidative potential of the KBiA. Accordingly, the more reactive fresh birnessite was employed in the experiment with a polluted soil. Adding a small amount of KBiF to soil only induces a light increase in PCP removal, probably due to the mechanically induced PCP adsorption and transformation onto clay minerals present in the soil. Besides, adding a higher dose of birnessite causes a stronger degradation of PCP.     

Combustion experiments using pentachlorophenol on a pilot scale and full-scale

Chlorinated phenols are used at many saw mills for impregnation of saw timber. Waste products containing the used compound follow this process. Tests have been performed on pilot and full-scale in order to investigate the possibility of destroying these wastes by combustion.The pilot scale tests with 70 g of pentachlorophenol show that at a transit time of approximately 3 seconds and a combustion temperature of 600°C the unburnt residue was 50 mg/kg fed in pentachlorophenol. At 800°C the residue decreased to 15 mg/kg. No formation of octachlorodioxin could be proved.The full-scale test with a small amount of pentachlorophenol and a large amount of tetrachlorophenol show that at a transit time of approximately 0.9 seconds and a temperature varying during one test between 620–875° (average 760°C), the unburnt residue was 9 mg/kg for tetrachlorophenol and 650 mg/kg for pentachlorophenol. At an increased load the residue increased gradually, being 5.900 mg/kg for tetrachlorophenol and 7.100 mg/kg for pentachlorophenol at a test when the temperature was varied between 460 and 850° (average 620°C). Analyses of chlorinated dioxins show that octachlorodioxin was found in the flue gas at one of the tests. This may indicate a formation.     

维生素B12协同纳米Fe/Cu双金属对五氯酚的催化降解与机理

针对水中含氯有机物的脱氯降解,制备了Fe/Cu双金属纳米颗粒,并引入维生素B12,研究铜负载率和维生素B12的剂量对以五氯酚为典型污染物的脱氯效果。结果表明：维生素B12和纳米零价铜能够有效提升五氯酚的脱氯速率及脱氯程度,脱氯率从4.52%增加到78.55%,降解产物从四氯酚进一步降解为苯酚。实验发现增加铜负载率可使双金属比表面积增大,催化活性位增多;增加维生素B12浓度可促进体系电子传递,使体系还原反应活性提升。铜负载率和维生素B12浓度过大均会使体系反应速率减缓甚至抑制。实验优化铜负载率为10%（质量分数）,维生素B12浓度为20 mg·L-1。探讨纳米零价铜和维生素B12的催化机理,以期对降解含氯有机物提供可操作性的参考。     

Immobilization of pentachlorophenol in soil using carbonaceous material amendments

In this study, three pentachlorophenol (PCP) laboratory-spiked and one field-contaminated soil were amended with 2.0% char, humic acid (HA) and peat, respectively. The amended soils were aged for either 7 or 250 days. After amendment, CaCl₂ extractability of PCP was significantly decreased. Desorption kinetics indicated that the proposed amendment could lead to a strong binding and slow desorption of PCP in soils. Amendment with char reduced the bioaccumulation factor (BAF) of PCP most significantly for earthworms (Eisenia fetida) in all soils studied. The results of both physicochemical and biological tests suggested that amendment reduced PCP bioavailability quickly and enduringly, implying that carbonaceous material amendment, especially char amendment, was a potentially attractive in situ remediation method for sequestration of PCP in contaminated soil.     

2-甲基-4-氯苯氧乙酸及其脱氯产物的光化学降解

紫外消毒工艺作为废水/给水处理的重要步骤,不仅可以有效控制水中的病原体,而且可使废水或水源水中存在的一些污染物发生化学降解作用,但目前对这一作用过程的研究尚不完善。本文针对一种典型的除草剂——2-甲基-4-氯苯氧乙酸（MCPA）及其脱氯产物二甲基苯氧乙酸（MPA）,研究了两者在紫外灯照射下的光化学行为,并进一步考察了波长、初始pH值、H2O2及水中其他共存物质对MCPA和MPA光降解效率的影响。研究结果表明,不同光源对MCPA的光降解速率大小为：254 nm波长紫外灯 > 365 nm波长紫外灯 > 可见光灯;低pH值不利于MCPA的光降解,但对MPA光降解的影响不大;在溶液中加入H2O2,会增大MCPA和MPA的光降解速率;MCPA的光降解过程符合一级动力学方程;腐殖酸（HA）会降低MCPA的光降解速率;MPA与MCPA呈现相似的光降解效应,但反应速率比MCPA略快,且在两者共存状态下会降低MCPA的光降解速率。