Chlorination of chlortoluron: kinetics, pathways and chloroform formation

Chlortoluron chlorination is studied in the pH range of 3-10 at 25 ± 1 °C. The chlorination kinetics can be well described by a second-order kinetics model, first-order in chlorine and first-order in chlortoluron. The apparent rate constants were determined and found to be minimum at pH 6, maximum at pH 3 and medium at alkaline conditions. The rate constant of each predominant elementary reactions (i.e., the acid-catalyzed reaction of chlortoluron with HOCl, the reaction of chlortoluron with HOCl and the reaction of chlortoluron with OCl⁻) was calculated as 3.12 (± 0.10) × 10⁷ M⁻² h⁻¹, 3.11 (±0.39) × 10² M⁻¹ h⁻¹ and 3.06 (±0.47) × 10³ M⁻¹ h⁻¹, respectively. The main chlortoluron chlorination by-products were identified by gas chromatography-mass spectrometry (GC-MS) with purge-and-trap pretreatment, ultra-performance liquid chromatography-electrospray ionization-MS and GC-electron capture detector. Six volatile disinfection by-products were identified including chloroform (CF), dichloroacetonitrile, 1,1-dichloropropanone, 1,1,1-trichloropropanone, dichloronitromethane and trichloronitromethane. Degradation pathways of chlortoluron chlorination were then proposed. High concentrations of CF were generated during chlortoluron chlorination, with maximum CF yield at circumneutral pH range in solution.     

Dissipation of carbendazim and chloramphenicol alone and in combination and their effects on soil fungal:bacterial ratios and soil enzyme activities

The dissipation of carbendazim and chloramphenicol alone and in combination and their effects on soil fungal:bacterial ratios and soil enzyme activities were investigated. The results revealed that carbendazim dissipation was little affected by chloramphenicol, whereas chloramphenicol dissipation was found to be retarded significantly by the presence of carbendazim. The inhibitory effect of carbendazim on the fungal:bacterial ratios was increased by the presence of chloramphenicol, and the inhibitory effect of chloramphenicol on neutral phosphatase was increased by the presence of carbendazim. Carbendazim increased soil catalase and urease activities, but this increase was partially diminished by the presence of chloramphenicol. Little interaction was observed between carbendazim and chloramphenicol with regard to their influence on soil invertase. The results obtained in this study suggest that combinations of fungicides and antibiotics may alter the compounds’ individual behaviors in soil and their effects on soil enzymes.     

Levels of polybrominated diphenyl ethers and hexabromocyclododecane in the atmosphere and tree bark from Beijing, China

Air samples in four seasons at one site and tree bark samples from four districts were determined to investigate seasonal variation and regional distribution of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD) in Beijing, China. The total concentrations of PBDEs (∑PBDE) and HBCD (∑HBCD) were in the range of 57-470 and 20-1800 pg m⁻³ in the atmosphere, respectively. The ∑PBDE and ∑HBCD concentrations were significantly influenced by the total suspended particulate matter in atmosphere. The total concentrations of PBDEs and HBCD in tree bark samples were in the range of 99-3700 and 26-3400 ng g⁻¹ lipid weight. It was found that regional distribution of PBDEs and HBCD was related to the function of each district. In addition, the study found that weeping willow bark was an ideal atmospheric PBDEs and HBCD passive sampler. Finally, atmospheric levels of BDE-209 and HBCD at tree bark sampling districts were estimated via applying an established bark/air partitioning model, which had been verified by the measured concentrations in tree bark and atmosphere in Beijing.     

Removal of Rhodamine B under visible irradiation in the presence of Fe⁰, H₂O₂, citrate and aeration at circumneutral pH

A new Vis-Fe⁰-H₂O₂-citrate-O₂ system comprising zero-valent iron, hydrogen peroxide, citrate anion and aeration at circumneutral pH under visible irradiation was studied. 21 μmol L⁻¹ of Rhodamine B (RhB) was chosen as the substrate to be tested. Experiments were conducted under conditions of 2.9 mmol L⁻¹ of H₂O₂, 12.6 g of Fe⁰ and 1.0 mmol L⁻¹ of citrate at pH 7.5. Results showed that, in 1 h reaction, 54% of RhB was removed with corresponding 26% of COD reduced. Meanwhile, the amount of released dissolved irons from Fe⁰ surface was found to be at a very low level as <5.4 μmol L⁻¹. Extinguishing tests with isopropanol suggested that RhB oxidation by hydroxyl radicals was the main process taken place in Vis-Fe⁰-H₂O₂-citrate-O₂ system, which accounted for 75% of substrate removal in 3 h reaction. Control and factor influencing experiments showed that the prohibitive extents of individual factor importance on RhB removal followed a decreasing order of Fe⁰ > H₂O₂ > citrate > Vis > O₂. This study showed an excellent system that could remove refractory organic compounds from water in laboratory researches, and also provided a good idea to reduce secondary contamination by dissolved irons in future investigations.     

Reprint of: Concentrations, distribution, and bioaccumulation of synthetic musks in the Haihe River of China

Seven typical synthetic musks (SMs) in the samples from the surface water, sediment and fish of the Haihe River were measured. The SM concentrations in the sediment and surface water of the Haihe River were significantly lower than those in the Dagu Drainage River and Chentaizi Drainage River (p < 0.05). Along the flow direction, the SM concentrations in surface water and sediment tended to increase from the upstream to the downstream of Dagu Drainage River. The Bioaccumulation factors (BAFs) of galaxolide (HHCB) and tonalide (AHTN) were calculated at high levels in the muscles of crucian carp, common carp, and silver carp. Most of the biota-sediment accumulation factors (BSAFs) for HHCB and AHTN were higher than 1.7, suggesting magnification possibly exist in the musk bioaccumulations of the three fishes in the Haihe River. No significant differences in HHCB/AHTN ratios were observed among the water, fish, and sediment samples (p > 0.05). However, the HHCB/AHTN values in the Haihe River were much lower than those in the Dagu Drainage River and Chentaizi Drainage River (p < 0.05). Compared with several typical persistent organic pollutants (POPs), the musk concentrations were higher or comparable in the Haihe River.     

Atmospheric particle characterization, distribution, and deposition in Xi'an, Shaanxi Province, Central China

Physical characterization and chemical analysis of settled dusts collected in Xi’an from November 2007 to December 2008 show that (1) dust deposition rates ranged from 14.6 to 350.4 g m⁻² yr⁻¹. The average deposition rate (76.7 g m⁻² yr⁻¹) ranks the 11th out of 56 dust deposition rates observed throughout the world. The coal-burning power was the major particle source; (2) on average (except site 4), ∼10% of the settled dusts having size <2.6, ∼30% having size <10.5, and >70% having size <30 μm; (3) the concentrations for 20 out of 27 elements analyzed were upto 18 times higher than their soil background values in China. With such high deposition rates of dusts that contain elevated levels of toxic elements, actions should be taken to reduce emission and studies are needed to assess the potential impacts of settled particles on surface ecosystem, water resource, and human health in the area.     

Bioanalytical and instrumental analysis of thyroid hormone disrupting compounds in water sources along the Yangtze River

Thyroid hormone (TH) agonist and antagonist activities of water sources along the Yangtze River in China were surveyed by a green monkey kidney fibroblast (CV-1) cell-based TH reporter gene assay. Instrumental analysis was conducted to identify the responsible thyroid-active compounds. Instrumentally derived l-3,5,3′-triiodothyronine (T₃) equivalents (T₃-EQs) and thyroid receptor (TR) antagonist activity equivalents referring to dibutyl phthalate (DBP-EQs) were calculated from the concentrations of individual congeners. The reporter gene assay demonstrated that three out of eleven water sources contained TR agonist activity equivalents (TR-EQs), ranging from 286 to 293 ng T₃/L. Anti-thyroid hormone activities were found in all water sources with the TR antagonist activity equivalents referring to DBP (Ant-TR-EQs), ranging from 51.5 to 555.3 μg/L. Comparisons of the equivalents from instrumental and biological assays suggested that high concentrations of DBP and di-2-ethylhexyl phthalate (DEHP) were responsible for the observed TR antagonist activities at some locations along the Yangtze River.     

钛基IrO2-SnO2电极在烟气海水脱硫恢复系统中的应用

采用浸渍-热分解法制备了含IrOx-TiO2中间层的IrO2-SnO2电极,得到的电极具有较高的析氯电催化活性和较强的稳定性,并通过电化学氧化法对Na2SO3海水脱硫模拟液进行处理,考察了电流密度、温度、pH值和电解时间等电解工艺参数对Na2SO3去除率和化学需氧量COD的影响。结果表明,在电流密度为200 mA/cm^2,pH值为3.5,电解440 mg/L的Na2SO3海水脱硫模拟液,15 min时Na2SO3去除率可达96.5%,COD去除率可达82.6%。     

淀粉-g-丙烯酸/凹凸棒土复合物制备及其吸附废水中NH_4~＋-N性能

采用反相乳液聚合法以凹凸棒土为原料,合成了新型NH4＋-N吸附剂淀粉-g-丙烯酸/凹凸棒土,并进行了氨氮吸附对比实验。结果表明：凹凸棒土氨氮单位吸附量为4.243 mg/g;淀粉-g-丙烯酸/凹凸棒土氨氮单位吸附量为5.301 mg/g,吸附能力比未改性的凹凸棒土提高了25%。淀粉-g-丙烯酸/凹凸棒土的氨氮吸附过程比凹凸棒土更符合Freundlich等温吸附模型。随着pH、温度的升高,凹凸棒土和淀粉-g-丙烯酸/凹凸棒土对NH4＋-N吸附量逐渐增大。     

西安市城市主干道路面径流污染及沉淀特性研究

在西安市城市主干道南二环路建立路面径流采样站,利用自制流量等比例采样装置,采集2009年3-11月的34场降雨径流,测试研究径流SS、COD事件平均浓度(EMC)、有机污染物赋存状态,并就降雨特征对径流污染的影响进行相关分析,还采用累积曲线法对16场径流水样进行沉淀实验,研究沉淀对径流中污染物的去除效果.结果表明,城市...