Effects of reductive inorganics and NOM on the formation of chlorite in the chlorine dioxide disinfection of drinking water

Chlorine dioxide (ClO₂) disinfection usually does not produce halogenated disinfection by-products, but the formation of the inorganic by-product chlorite (ClO₂^–) is a serious consideration. In this study, the ClO₂^– formation rule in the ClO₂ disinfection of drinking water was investigated in the presence of three representative reductive inorganics and four natural organic matters (NOMs), respectively. Fe²⁺ and S^2– mainly reduced ClO₂ to ClO₂^– at low concentrations. When ClO₂ was consumed, the ClO₂^– would be further reduced by Fe²⁺ and S^2–, leading to the decrease of ClO₂^–. The reaction efficiency of Mn²⁺ with ClO₂ was lower than that of Fe²⁺ and S^2–. It might be the case that MnO₂ generated by the reaction between Mn²⁺ and ClO₂ had adsorption and catalytic oxidation on Mn²⁺. However, Mn²⁺ would not reduce ClO₂^–. Among the four NOMs, humic acid and fulvic acid reacted with ClO₂ actively, followed by bovine serum albumin, while sodium alginate had almost no reaction with ClO₂. The maximum ClO₂^– yields of reductive inorganics (70%) was higher than that of NOM (around 60%). The lower the concentration of reductive substances, the more ClO₂^– could be produced by per unit concentration of reductive substances. The results of the actual water samples showed that both reductive inorganics and NOM played an important role in the formation of ClO₂^– in disinfection.     

A novel co-catalyzed system between persulfate and chlorite by sonolysis for removing triphenylmethane derivative

Triphenylmethane (tpm) derivatives (e.g. tpm_CV) have threatened the safety of the aquatic environment due to the potential toxicity and carcinogenicity. In this study, the novel ultrasonic/persulfate/chlorite (US/S₂O₈²⁻/ClO₂⁻) oxidation process was developed for the effective removal of tpm_CV in wastewater. The apparent non-integer kinetics (n around 1.20) of tpm_CV degradation under different factors (R²_Adj > 0.990) were investigated, respectively. Inhibiting effects of anions were greater than those of cations (except Fe(II/III)). The adding of micromolecule organic acids could regulate degradation towards positive direction. The double response surface methodology (RSM) was designed to optimize tpm_CV removal process, and the acoustic-piezoelectric interaction was simulated to determine the propagation process of acoustic wave in the reactor. The possible degradation pathway was explored to mainly include carbonylation, carboxylation, and demethylation. The estimated effective-mean temperature at the bubble-water interface was calculated from 721 to 566 K after introducing the ClO₂⁻, however, the adsorption or partitioning capacity of tpm_CV in the reactive zone was widened from 0.0218 to 0.0982. The proposed co-catalysis of US/S₂O₈²⁻/ClO₂⁻ was based on the determined active species mainly including ClO₂, SO₄⋅⁻, and ⋅OH. Compared with other US-based processes, the operating cost (3.97 $/m³) of US/S₂O₈²⁻/ClO₂⁻ with the EE/O value (16.8 kWh/m³) was relatively reduced.     

HPLC determination of chlorate metabolism in bovine ruminal fluid

Salmonella and Escherichia coli are two bacteria that are important causes of human and animal disease worldwide. Chlorate is converted in the cell to chlorite, which is lethal to these bacteria. An HPLC procedure was developed for the rapid analysis of chlorate (ClO₃ ^?), nitrate (NO₃ ^?), and nitrite (NO₂ ^?) ions in bovine ruminal fluid samples. Standard curves for chlorite, nitrite, nitrate, and chlorate were well defined linear curves with R² values of 0.99846, 0.99106, 0.99854, and 0.99138, respectively. Concentrations of chlorite could not be accurately determined in bovine ruminal fluid because chlorite reacts with or binds a component(s) or is reduced to chloride in bovine ruminal fluid resulting in low chlorite measurements. A standard curve ranging from 25 to 150 ppm ClO₃ ^? ion was used to measure chlorate fortified into ruminal fluid. The concentration of chlorate was more rapidly lowered (P < 0.01) under anaerobic compared to aerobic incubation conditions. Chlorate alone or chlorate supplemented with the reductants sodium lactate or glycerol were bactericidal in anaerobic incubations. In anaerobic culture, the addition of sodium formate to chlorate-fortified ruminal fluid appeared to decrease chlorate concentrations; however, formate also appeared to moderate the bactericidal effect of chlorate against E. coli. Addition of the reductants, glycerol or lactate, to chlorate-fortified ruminal fluid did not increase the killing of E. coli at 24 h, but may be useful when the reducing equivalents are limiting as in waste holding reservoirs or composting systems required for intense animal production.     

水中二氧化氯,氯,亚氯酸根和氯酸根区分测定法

为了保护人类健康制定卫生规范,同时为ＣｌＯ２的研究和应用提供基础手段,必须要建立一种能准确区分测定水中ＣｌＯ２,Ｃｌ２,ＣｌＯ＾－１２,ＣｌＯ＾－３浓度的方法。回顾了现有水中ＣｌＯ２,Ｃｌ２,ＣｌＯ＾－２和ＣｌＯ＾－３的区分测定方法,评述了各种测定方法的优缺点和适用性,指出了目前在区分测定这恨氧化物的方法中存在的问题,提出了解决问题的途径。     

苯磺酸法制备二氧化氯的研究

亚氯酸钠-苯磺酸制备二氧化氯的方法进行了系统研究,通过正交试验确定了最佳反应条件,并考察了反应时间和反应温度对二氧化氯浓度和纯度的影响。该法反应迅速,可以制备出高纯二氧化氯,反应易于控制,苯磺酸可作为快速释放型二氧化氯固体制剂的活化剂。     

Sorption behavior of U(VI) on phyllite: experiments and modeling

The sorption of U(VI) onto low-grade metamorphic rock phyllite was modeled with the diffuse double layer model (DDLM) using the primary mineralogical constituents of phyllite, i.e. quartz, chlorite, muscovite, and albite, as input components, and as additional component, the poorly ordered Fe oxide hydroxide mineral, ferrihydrite. Ferrihydrite forms during the batch sorption experiment as a weathering product of chlorite. In this process, Fe(II), leached from the chlorite, oxidizes to Fe(III), hydrolyses and precipitates as ferrihydrite. The formation of ferrihydrite during the batch sorption experiment was identified by M?ssbauer spectroscopy, showing a 2.8% increase of Fe(III) in the phyllite powder. The ferrihydrite was present as Fe nanoparticles or agglomerates with diameters ranging from 6 to 25 nm, with indications for even smaller particles. These Fe colloids were detected in centrifugation experiments of a ground phyllite suspension using various centrifugal forces. The basis for the successful interpretation of the experimental sorption data of uranyl(VI) on phyllite were: (1) the determination of surface complex formation constants of uranyl with quartz, chlorite, muscovite, albite, and ferrihydrite in individual batch sorption experiments, (2) the determination of surface acidity constants of quartz, chlorite, muscovite, and albite obtained from separate acid-base titration, (3) the determination of surface site densities of quartz, chlorite, muscovite, and albite evaluated independently of each other with adsorption isotherms, and (4) the quantification of the secondary phase ferrihydrite, which formed during the batch sorption experiments with phyllite. The surface complex formation constants and the protolysis constants were optimized by using the experimentally obtained data sets and the computer code FITEQL. Surface site densities were evaluated from adsorption isotherms at pH 6.5. The uranyl(VI) sorption onto phyllite was accurately modeled with these newly determined constants and parameters of the main mineralogical constituents of phyllite and the secondary mineralization phase ferrihydrite. The modeling indicated that uranyl sorption to ferrihydrite clearly dominates uranyl sorption, showing the great importance of secondary iron phases for sorption studies.     

离子色谱法测定地表水和饮用水中亚氯酸盐、溴酸盐和氯酸盐

采用KOH梯度淋洗离子色谱法测定地表水和饮用水中ClO2-、BrO3-和ClO3-,在试验确定的条件下,3种离子与F-、Cl-、NO2-、NO3-、SO2-4、Br-、I-等7种离子分离度良好。 ClO2-、BrO3-、ClO3-在50．0μg/L～1000μg/L范围内线性良好,检出限分别为5．2μg/L、8．9μg/L、7．6μg/L,环境水样加标平行测定的RSD分别为2．1％～5．4％、4．1％～5．4％、2．5％～4．8％,两个质量浓度水平加标的平均回收率分别为93．7％～96．5％、90．3％～94．8％、98．7％～111％。     

微污染水源水ClO2消毒中ClO-2的来源与控制技术

综述了ClO2消毒微污染水源水的主要无机副产物ClO2-的来源,ClO2-的产生前控制和生成后去除等方法,以减少ClO2-在饮用水中的含量。并提出了氯气氧化控制饮用水中ClO2-含量的新方法。