Ligand-assisted degradation of carbon tetrachloride by microscale zero-valent iron

Degradation of carbon tetrachloride (CT) by microscale zero-valent iron (ZVI) was investigated in batch systems with or without organic ligands (ethylenediaminetetraacetic acid (EDTA), citric acid, tartaric acid, malic acid and oxalic acid) at pHs from 3.5 to 7.5. The results demonstrated that at 25°C, the dechlorination of CT by microscale ZVI is slow in the absence of organic ligands, with a pseudo-first-order rate constant of 0.0217 h(-1) at pH 3.5 and being further dropped to 0.0052 h(-1) at pH 7.5. However, addition of organic ligands significantly enhanced the rates and the extents of CT removal, as indicated by the rate constant increases of 39, 31, 32, 28 and 18 times in the presence of EDTA, citric acid, tartaric acid, malic acid and oxalic acid, respectively, at pH 3.5 and 25°C. The effect of EDTA was most significant; the dechlorination of CT at an initial concentration of 20 mg l(-1) increased from 16.3% (no ligands) to 89.1% (with EDTA) at the end of 8h reaction. The enhanced CT degradation in the presence of organic ligands was primarily attributed to the elimination of a surface passivation layer of Fe(III) (hydr)oxides on the microscale ZVI through chelating of organic ligands with Fe(III), which maintained the exposure of active sites on ZVI surface to CT.     

Modelling spills of water-reactive chemicals

This paper describes part of a programme of work undertaken at the Health and Safety Laboratory (HSL) to investigate the behaviour of selected water-reactive chemicals. Following an accidental release, such substances react exothermically with any water present, generating acidic vapours. The STAWaRS (Source Term Assessment of Water Reactive Substances) software was developed for the Health and Safety Executive (HSE) by ESR Technology to model this complex process. The aims of the study described here were to provide experimental validation of the heats of hydrolysis used within STAWaRS, and to perform sensitivity studies on selected STAWaRS input parameters.The heat of hydrolysis of acetyl chloride was measured and showed good correlation with the value used within STAWaRS. Some of the variables that influence the severity of acetyl chloride spills are examined, with reference to predictions made by the STAWaRS model. The heats of hydrolysis of titanium tetrachloride previously measured at HSL are also discussed, and the effect of adopting these experimentally derived values for modelling spills is shown for a hypothetical land use planning case. This study demonstrates the importance of using experimentally validated values for STAWaRS input parameters.     

Soil- and surfactant-enhanced reductive dechlorination of carbon tetrachloride in the presence of Shewanella putrefaciens 200

Sorption of organic contaminants to soils has been shown to limit bioavailability and biodegradation in some systems. Use of surfactants has been proposed to reverse this effect. In this study, the effects of a high organic carbon content soil and a nonionic surfactant (Triton X-100) on the reductive dechlorination of carbon tetrachloride (CCl₄) were examined in anaerobic systems containing Shewanella putrefaciens. Although more than 70% of the added CCl₄ was sorbed to the soil phase in these systems, the reductive dechlorination of CCl₄ was not diminished. Rather, rates of CCl₄ dechlorination in systems containing soil were enhanced relative to systems containing non-sorptive sand slurries. This enhancement was also observed in sterile soil slurries to which a chemical reductant, dithiothreitol was added. It appears that the organic soil used in these experiments contains some catalytic factor capable of transforming CCl₄ in the presence of an appropriate chemical or microbial reductant. The addition of Triton X-100 to sand and soil slurries containing S. putrefaciens resulted in increased CCl₄ degradation in both systems. The effect of Triton could not be explained by: (i) surfactant induced changes in the distribution of CCl₄, (i.e. decreased sorption) or the rate of CCl₄ desorption; (ii) a direct reaction between Triton and CCl₄; or (iii) increased cell numbers resulting from use of the surfactant as a substrate. Rather, it appears that Triton X-100 addition resulted in lysis of bacterial cells, a release of biochemical reductant, and enhanced reductive transformation of CCl₄. These results provide insights to guide the development of more effective direct or indirect bioremediation strategies.     

Heterogeneity of chlorinated hydrocarbon sorption properties in a sandy aquifer

Hydraulic conductivity and sorption coefficients for chlorinated hydrocarbons (chloroform, carbon tetrachloride and tetrachloroethylene) were evaluated for 216 sediment samples collected across a 15 m transect and a 21 m depth interval in a contaminated aquifer near Schoolcraft, Michigan. Relationships between hydraulic conductivity, linear sorption partition coefficients, grain size classes, and spatial location were investigated using linear regression analysis and geostatistical techniques. Clear evidence of layering was found in sorption properties, hydraulic conductivity and grain sizes. Conductivity correlated well with grain size, as expected, but sorption varied inversely with grain size, contrary to some previous reports. No significant correlation was found between sorption properties and hydraulic conductivity. This is likely due to the unexpected presence of small amounts of highly sorptive coal-like solids, which dominate the sorption behavior but have little effect on conductivity. The results demonstrate that recent findings regarding the high sorption capacity of coal materials found in soils can exert a controlling influence on contaminant transport. Designers of in situ remediation systems should be cautioned that 1) it is not reasonable to assume that sorption capacity and hydraulic conductivity are related, 2) sorption capacity and hydraulic conductivity are critical measurements for contaminant site characterization and subsequent transport modeling, 3) estimating sorption capacity from organic carbon measurement may lead to greater errors than performing sorption isotherms, and 4) it is more important to characterize vertical heterogeneity rather than horizontal heterogeneity because both sorption and hydraulic conductivity are correlated across longer distances in the horizontal plane.     

四氯化碳的生产与应用及其淘汰策略

四氯化碳是一种消耗臭氧层物质，其生产和消费都面临着严峻的淘汰形势。简要叙述了四氯化碳的生产技术，以四氯化碳为原料生产大宗化学品和精细化学品的转化技术，四氯化碳作为化工助剂在我国的应用情况以及相应的淘汰方法和技术进展。     

两种国标方法测定大气中二氧化硫的比较研究

国标方法中环境空气中二氧化硫的测定方法主要有甲醛吸收-副玫瑰苯胺分光光度法和四氯汞盐吸收-副玫瑰苯胺分光光度法.对国标方法中两种副玫瑰苯胺分光光度法测定环境空气中二氧化硫所用的两种吸收液(四氯汞钾、甲醛)的吸收效果及方法的准确性、精密度等条件作了比较试验.结果表明,采用甲醛溶液作吸收液与四氯汞钾溶液作吸收液相比,吸收效果、精密度和准确度更好,测定的检出限低.用甲醛溶液做吸收液,除了上述优点外,还可避免使用大量的汞盐,有利于环境保护.     

液上空间－气相色谱法测定工业废水中1，1，1－三氯乙烷等卤代烃的研究

本方法研究了液上空间气相色谱法测定工业废水１，１，１－三氯乙烷、四氯化碳、三氯甲烷三种挥发性卤代烃，采用填充气相色谱法以角鲨烷为固定液，用ＣｈｒｏｍｏｓｏｒｂＧＡＷ－ＤＭＣＳ作为担体，在选定的条件下，１，１，１－三氯乙烷、四氯化碳、三氯甲烷能完全分离．同时也能与经常共存的二氯甲烷、三氯乙烯、四氯乙烯、一氯二溴甲烷、三溴甲烷完全分离而互不干扰。本方法的定性检出限是按全程序空白值标准偏差的３倍值计算。１，１，１－三氯乙烷、四氯化碳、三氯甲烷的定性检出限分别为２．４×１０－２ｎｇ、２．１０×１０－４ｎｇ、０．１３ｎｇ，当进样量为２０ｕｌ时，１，１，１－三氯乙烷、四氯化碳、三氯甲烷的最低检出浓度分别为１．２×１０－３ｍｇ／１、１．０８×１０－５ｍｇ／１、６．４８×１０－３ｍｇ／ｌ。     

Dechlorination of carbon tetrachloride by the catalyzed Fe-Cu process

The electrochemical reduction characteristics of carbon tetrachloride (CT) were investigated using cyclic voltammetry in this study. In addition, the difference in reduction mechanisms of CT between Master Builders' iron and the catalyzed Fe-Cu process was discussed. The results showed that CT was reduced directly on the surface of copper rather than by atomic hydrogen produced at the cathode in the catalyzed Fe-Cu process. The reduction was realized largely by atomic hydrogen in Master Builders' iron. The entire CT in 350 ml aqueous solution with 320 mgL was reduced to trichloromethane and dichloromethane in 2.25 h when 100 g of scrap iron with FeCu ratio of 10:1 (ww) were used. Moreover, the reduction rate slowed with time. CT could be reduced at acidic, neutral and alkaline pH from solution by Fe-Cu bimetallic media, but the mechanisms were di?erent. The degradation rate was not significantly in?uenced by pH in the catalyzed Fe-Cu process; in Master Builders' iron it clearly increased with decreasing pH. The kinetics of the reductions followed pseudo-first order in both cases. Furthermore, the reductions under acidic conditions proceeded faster than that under the neutral and alkaline conditions. The catalyzed Fe-Cu process was superior to Master Builders' iron in treating CT-containing water and this advantage was particularly noticeable under alkaline conditions. The reduction was investigated in the cathode (Cu) and anode (Fe) compartments respectively, the results showed that the direct reduction pathway played an important role in the reduction by the catalyzed Fe-Cu process. The catalyzed Fe-Cu process is of practical value.     

某市南郊水源地土壤四氯化碳污染特征

含四氯化碳废水在排放的过程中沿排污渠侧壁和底部的渗漏对土壤造成污染.在对某市南郊受四氯化碳污染的水源地进行钻孔检测的过程中发现,土壤四氯化碳污染的特征:靠近排污沟的钻孔均检测出四氯化碳,而远离排污沟的钻孔则未检出;四氯化碳的垂向分布存在不连续性,且受降雨影响较大;大部分钻孔浅层土壤中基本未检测到四氯化碳,而在3 m以下的土层和基岩中检测到四氯化碳;抽水井的抽水行为导致抽水井附近土壤中四氯化碳明显高于其他钻孔点位检测结果.     

四氯乙烯代替四氯化碳测定水中油类物质初探

通过使用四氯乙烯代替四氯化碳测定水中油类物质的对比实验,得到如下结论：四氯乙烯作萃取剂时,标准曲线线性相关系数为0．9999,检出限为0．336mg／L,精密度和准确度符合质控要求。但标准曲线方程的斜率较差,在分析浓度较低的样品时,准确度相对误差较大,萃取回收率不高。由此可以看出,使用四氯乙烯分析油类物质的局限性较大,分析方法还需进一步研究。