水和废水中多氯联苯(PCBs)的测定方法及进展

本文引用了七十余篇近几年国内外的有关著文,对水和废水中的多氯联苯(PCBs)的测定方法进行了评述,全面系统地介绍了水样的采集、富集、净化和分析测定等操作程序,着重于样品的前处理和气相色谱分析,并提出了这一领域今后的发展趋势。     

Chlorination of dibenzofuran and dibenzo-p-dioxin vapor by copper (II) chloride

Dibenzofuran (DF) is formed from phenol and benzene in combustion gas exhaust streams prior to particle collection equipment. Subsequent chlorination at lower temperatures on particle surfaces is a potential source of chlorinated dibenzofuran (CDF). Gas streams containing 8% O₂ and approximately 0.1% DF vapor were passed through particle beds containing copper (II) chloride (0.5% Cu, mass) at temperatures ranging from 200 to 400 °C to investigate the potential for CDF formation during particle collection. Experiment duration was sufficient to provide an excess amount of DF (DF/Cu=3). The efficiency of DF chlorination by CuCl₂ and the distribution of CDF products were measured, with effects of temperature, gas velocity, and experiment duration assessed. Results of a more limited investigation of dibenzo-p-dioxin (DD) chlorination by CuCl₂ to form chlorinated DD (CDD) products are also presented.

The efficiency of DF/DD chlorination by CuCl₂ was high, both in terms of CuCl₂ utilization and DF/DD conversion. Total yields of Cl on CDF/CDD products of up to 0.5 mole Cl per mole CuCl₂ were observed between 200 and 300 °C; this suggests that nearly 100% CuCl₂ was utilized, assuming a conversion of two moles of CuCl₂ to CuCl per mole Cl added to DD/DF. In a short duration experiment (DF/Cu=0.3), nearly 100% DF adsorption and conversion to CDF was achieved. The degree of CDF chlorination was strongly dependent on gas velocity. At high gas velocity, corresponding to a gas–particle contact time of 0.3 s, mono-CDF (MCDF) yield was largest, with yields decreasing with increasing CDF chlorination. At low gas velocity, corresponding to a gas–particle contact time of 5 s, octa-CDF yield was largest. DF/DD chlorination was strongly favored at lateral sites, with the predominant CDF/CDD isomers within each homologue group those containing Cl substituents at only the 2,3,7,8 positions. At the higher temperatures and lower gas velocities studied, however, broader isomer distributions, particularly of the less CDD/CDF products, were observed, likely due to preferential destruction of the 2,3,7,8 congeners.     

Observations of 2,4,6-trichlorophenol degradation by ozone

The aqueous reactivity of 2,4,6-trichlorophenol (TCP) with ozone has been studied at laboratory-scale using a simple gas bubble/liquid contacting system. Degradation rate constants were measured directly and found to be 7.6 and 77.2 M(-1)s(-1) at pH 2 and 7.5, respectively. At pH 7.5, 10 min of ozonation ( identical with 15 mM ozone consumption) achieved a 90% degradation of TCP, which corresponded to the release of approximately 2 mol Cl(-) per mol TCP. The presence of hydrogen peroxide in solution did not significantly increase the TCP degradation but increased the overall dechlorination to 2.7 mol Cl(-) per mol TCP. The presence of humic acid (HA) in solution was found to enhance the degradation rate of TCP at low relative HA concentrations (<0.6 g/g HA:TCP), but to reduce the rate at higher HA concentrations.     

微氧膜生物反应器同时去除有机物和氮的研究

采用微氧颗粒污泥膜生物反应器处理生活污水,进行同时去除有机物和氮的研究。结果表明,膜出水COD不受水力停留时间变化的影响一直稳定在较低值,为15~35mg/L,去除率在94%以上。氮通过发生同时硝化反硝化反应而去除。在水力停留时间为16h以上时, 系统总氮去除率为65% ~92%,平均去除率为77%。     

The degradation of endocrine disruptor di-n-butyl phthalate by UV irradiation: a photolysis and product study

The direct photolysis of an important endocrine disruptor compound, di-n-butyl phthalate (DBP), has been investigated under monochromatic UV irradiation at 254 nm over a wide pH range (3-11). The investigation was carried out under idealized conditions and has considered both reaction kinetics and the degradation mechanism. It was found that more than 90% of DBP can be degraded within an hour of irradiation in water. A simple model has been developed and used to predict the initial DBP photolysis rate constant at different pH values and initial DBP concentrations. The major decomposition mechanism of DBP is believed to involve the hydrolytic photolysis of the carbon in the alpha and/or beta-position of the ester chain with the production of aromatic carboxylic derivatives. Additionally, multi-degradation pathways are proposed for acid-catalyzed hydrolytic photolysis (pH 3-5), which was found to be useful in explaining the photo-degradation of DBP under acidic conditions. The use of 254 nm UV to photo-degrade DBP was found to be a relatively fast and clean process, especially in neutral to basic conditions.     

Influence of glyphosate and its formulation (Roundup) on the toxicity and bioavailability of metals to Ceriodaphnia dubia

This study examined the toxicological interaction between glyphosate (or its formulation, Roundup) and several heavy metals to a freshwater cladoceran, Ceriodaphnia dubia. We demonstrated that all binary combinations of Roundup and metals (Cd, Cu, Cr, Ni, Pb, Se and Zn) exhibited "less than additive" mixture toxicity, with 48-h LC50 toxic unit > 1. Addition of glyphosate alone could significantly reduce the acute toxicity of Ag, Cd, Cr, Cu, Ni, Pb and Zn (but not Hg and Se). The ratio between glyphosate and metal ions was important in determining the mitigation of metal toxicity by glyphosate. A bioaccumulation study showed that in the presence of glyphosate the uptake of some metals (e.g. Ag) was halted but that of others (e.g. Hg) was increased significantly. Therefore, our study strongly suggests that glyphosate and its commercial formulations can control the toxicity as well as the bioavailability of heavy metals in aquatic ecosystems where both groups of chemicals can co-occur.     

污染土壤的微波辐照技术研究进展

简要介绍了土壤污染的状况,总结了国外学者对重金属和有机物两大类污染土壤所进行的微波修复工作,探讨了修复机理及影响因素,最后展望了微波修复污染土壤的研究重点.     

等离子体协同光催化去除模拟烟气中SO2的实验研究

近年来,低温等离子体技术以及纳米TiO₂光催化技术在烟气脱硫中的应用越来越引起人们的关注。利用填充床反应器将这2种技术有机地结合起来，进行了大量脱硫实验研究。研究结果表明，等离子体协同光催化去除烟气中的SO₂与单独采用等离子体技术相比，其SO₂的去除率可提高5%～20%。同时，探讨了等离子体协同TiO₂光催化剂的脱硫机理，分别研究了外加电压、气体流量和SO₂初始浓度等因素对脱硫效率的影响。实验结果表明，当SO₂初始浓度为800 mg/m³，输入电压为17.5 kV，气体流量为0.2 m³/h时，SO₂脱除率可以达到77.6%。     

一种新型国产高效除尘滤筒在船厂分段涂装车间的应用

国产除尘滤材是将聚酯纤维热轧成型 ,再涂敷高分子发泡制成。滤材硬挺、耐压、抗撕裂 ,内部结构稳定 ,粉尘过滤精度高 ,实现表面过滤 ,易清灰再生 ,使用寿命长 ,耐水、酸、碱 ,可广泛用于各工业领域的气体净化和粉尘处理。大连新船重工集团把国产除尘滤材制成的滤筒配置到厂内原有的除尘系统中 ,通过 1年多的使用 ,获得非常满意的除尘效果。从而证明国产滤料性能已达到国际先进水平。     

Modeling the quantum yields of herbicide 2,4-D decay in UV/H2O2 process

The photodecay of herbicide 2,4-D in a hydrogen peroxide-aided photolysis process was studied and modeled. The decay rate of 2,4-D was known to be low in the natural environment, but rate improvement was achieved in an H2O2/UV system. The 2,4-D decay quantum yields under ultraviolet (UV) light at 253.7 nm increased from 4.86 x 10(-6) to 1.30 x 10(-4) as the ratio of [H2O2]/[2,4-D] increased from 0.05 to 12.5. Apparently, in the presence of UV light, the decay rate of 2,4-D could be greatly improved as the concentration of hydrogen peroxide increased. However, the efficiency of 2,4-D photodecay was retarded if the concentration of H2O2 was overdosed, because the excess hydrogen peroxide consumes the hydroxyl radicals (HO*) in the solution, resulting in a much weaker oxidant HO2*. The decay of 2,4-D was also pH dependent. A ranking of acid (highest), base (middle) and neutral (lowest) was observed owing to the property change of reactants and the shifting of dominant mechanisms among photolysis, photohydrolysis and chemical oxidation. Two mathematical models were proposed to predict the quantum yield for various [H2O2]/[2,4-D] ratios and initial pH levels, in which very good correlation was found for the ranges of regular application.