Desorption process of copper chlorides from copper surface

Gaseous copper chlorides can be employed as precursors in a newly developed Cu-CVD method called metal chloride reduction-chemical vapor deposition (MCR-CVD). More than one species exists in the gas phase of copper chloride. We studied the gas phase composition of copper chlorides generated by etching of copper surface by electron impact-mass spectrometry. The composition of gaseous species can change because of gas phase reactions. After desorbing from the copper surface, copper chloride reached equilibrium composition immediately.     

Predictive Chlorine Dosing: A New Paradigm

Disinfection by chlorine is common practice in potable water treatment. The most frequently used dose control method is to inject an overdose of chlorine at the inlet to the contact tank and adjust to the desired residual chlorine level in the effluent stream. However, this method of control may not be optimal. The advent of reliable predictions of retention time distributions and the widespread use of programmable logic controllers, coupled with a greater understanding of chlorine disinfection kinetics, offers the potential for more efficient chlorine dosing algorithms. This paper describes one possible algorithm, based on theoretical models, for predictive chlorine dosing.     

利用Wiener过程探究镁水泥混凝土中涂层钢筋在盐类环境下的腐蚀寿命

采用氯盐溶液和硫酸盐溶液浸泡镁水泥钢筋混凝土构件,使构件中的涂层钢筋加速锈蚀,并利用电化学工作站进行电化学试验;以腐蚀电流密度作为钢筋耐久性退化指标,建立一元Wiener过程预测模型进行钢筋腐蚀寿命预测.结果 表明:在氯盐溶液环境下,镁水泥混凝土构件中的钢筋受腐蚀问题较之硫酸盐溶液环境更为突出,且涂层在2种盐溶液环境中均对钢筋起到了较好的防护效果;在氯盐溶液环境中,涂层钢筋在1500 d附近进入中等腐蚀阶段,在硫酸盐溶液环境中,涂层钢筋在22000 d进入中等腐蚀阶段.     

Disinfection by-products from halogenation of aqueous solutions of terpenoids

We report the formation of trihalomethanes and other disinfection by-products from four polyfunctional terpenoids during simulated chlorination of natural waters. Complex suites of products were identified by closed loop stripping analysis (CLSA)/gas chromatography-mass spectrometry (GC-MS) from halogenation of β-carotene and retinol. β-Ionone appeared to be a key intermediate in the halogenation of β-carotene and retinol, reacting further under the reaction conditions to produce trans-β-ionone-5,6-epoxide and β-cyclocitral. Halogenation of the four terpenoids also produced trihalomethanes (THMs), most likely through haloform reaction on methyl ketone groups within many of the intermediates. Since halogenation of retinol produced a significant quantity of THMs at a slow reaction rate, retinol-based structures may possibly contribute to the slow reacting phase of THM formation in natural waters. Two polyhydroxyphenol model compounds were halogenated for comparison. The only products identified by CLSA/GC-MS from halogenation of 4′,5,7-trihydroxyflavanone and ellagic acid were THMs. 4′,5,7-Trihydroxyflavanone rapidly produced THMs, with an extremely high molar yield (94%) at pH 7. Terpenoids of the β-ionone and retinol type should be considered to be significant THM precursors, while 4′,5,7-trihydroxyflavanone has been shown to be an extremely significant THM precursor, potentially present within natural organic matter in water treatment processes and distribution systems.     

Formation of carbonaceous and nitrogenous disinfection by-products from the chlorination of Microcystis aeruginosa

Formation of carbonaceous disinfection by-products (C-DBPs), including trihalomethanes (THMs), haloacetic acids (HAAs), haloketones (HKs), chloral hydrate (CH), and nitrogenous disinfection by-products (N-DBPs), including haloacetonitriles (HANs) and trichloronitromethane (TCNM) from chlorination of Microcystis aeruginosa, a blue-green algae, under different conditions was investigated. Factors evaluated include contact time, chlorine dosages, pH, temperature, ammonia concentrations and algae growth stages. Increased reaction time, chlorine dosage and temperature improved the formation of the relatively stable C-DBPs (e.g., THM, HAA, and CH) and TCNM. Formation of dichloroacetonitrile (DCAN) followed an increasing and then decreasing pattern with prolonged reaction time and increased chlorine dosages. pH affected DBP formation differently, with THM increasing, HKs decreasing, and other DBPs having maximum concentrations at certain pH values. The addition of ammonia significantly reduced the formation of most DBPs, but TCNM formation was not affected and 1,1-dichloropropanone (1,1-DCP) formation was higher with the addition of ammonia. Most DBPs increased as the growth period of algal cells increased. Chlorination of algal cells of higher organic nitrogen content generated higher concentrations of N-DBPs (e.g., HANs and TCNM) and CH, comparable DCAA concentration but much lower concentrations of other C-DBPs (e.g., THM, TCAA and HKs) than did natural organic matter (NOM).     

Kinetics of aqueous chlorination of some pharmaceuticals and their elimination from water matrices

Apparent rate constants for the reactions of four selected pharmaceutical compounds (metoprolol, naproxen, amoxicillin, and phenacetin) with chlorine in ultra-pure (UP) water were determined as a function of the pH. It was found that amoxicillin (in the whole pH range 3-12), and naproxen (in the low pH range 2-4) presented high reaction rates, while naproxen (in the pH range 5-9), and phenacetin and metoprolol (in the pH range 2.5-12 for phenacetin, and 3-10 for metoprolol) followed intermediate and slow reaction rates. A mechanism is proposed for the chlorination reaction, which allowed the evaluation of the intrinsic rate constants for the elementary reactions of the ionized and un-ionized species of each selected pharmaceutical with chlorine. An excellent agreement is obtained between experimental and calculated rate constants by this mechanism.The elimination of these substances in several waters (a groundwater, a surface water from a public reservoir, and two effluents from municipal wastewater treatment plants) was also investigated at neutral pH. The efficiency of the chlorination process with respect to the pharmaceuticals elimination and the formation THMs was also established. It is generally observed that the increasing presence of organic and inorganic matter in the water matrices demand more oxidant agent (chlorine), and therefore, less chlorine is available for the oxidation of these compounds. Finally, half-life times and oxidant exposures (CT) required for the removal of 99% of the four pharmaceuticals are also evaluated. These parameters are useful for the establishment of safety chlorine doses in oxidation or disinfection stages of pharmaceuticals in treatment plants.     

Flux enhancement of thin film composite RO membrane by controlled chlorine treatment

A major stumbling block in polyamide thin film composite RO membrane performance is its incompatibility with chlorine and oxidizing agents. The amide bond of the membrane is highly vulnerable to chlorine attack. Two reactions are possible with chlorine exposure i.e. N-H bond chlorination and/or aromatic ring chlorination. In this way, chlorine may cause degradation/modification in the membrane leading to deterioration in performance.However, low concentration of chlorine up to a certain time may give synergistic effect on membrane and improve its performance. Chlorine solution, if exposed to membrane for certain time gives enhancement in trans-membrane flux of the membrane.The same solution if exposed for more time deteriorates ultra-thin polyamide layer of TFC membrane. Conspicuously, the membrane with poor salt rejection and flux benefited more as compared to the membrane with better performance. In the present study, membranes with different salt rejection and flux were taken and exposed to the inorganic chlorine solution. The inorganic chlorine solutions were made by dissolving sodium hypochlorite in pH buffer. The different solutions were made by varying pH to investigate the pH dependence. The membrane samples were kept in solution for different time durations. The exposure time was monitored and the exposure level was taken in terms of ppm h (ppm chlorine solution exposed to membrane for a fixed time in h). With the same chlorine concentration, effect of varying pH was studied. Spiral wound TFC membrane modules were also subjected to chlorine solution to study its effect.     

Factors affecting bulk to total bacteria ratio in drinking water distribution systems

Bacteria in drinking water systems can grow in bulk water and as biofilms attached to pipe walls, both causing regrowth problems in the distribution system. While studies have focused on evaluating the factors influencing the bacteria in bulk water and in biofilms separately, there is a need for understanding biofilm characteristics relative to the bulk water phase. The current study evaluated the effects of chlorine and residence time on the presence of culturable bacteria in biofilms relative to that in bulk water. The results showed that when no chlorine residual was present in the system, the median ratio of bulk to total bacteria was 0.81, indicating that 81% of the bacteria were present in bulk water, whereas only 19% were present in the biofilm. As chlorine concentration increased to 0.2, 0.5, and 0.7 mg/L, the median percentage of bacteria present in bulk water decreased to 37, 28, and 31, respectively. On the other hand, as the residence times increased to 8.2, 12, 24, and 48h, the median percentage of bacteria present in bulk water increased to 7, 37, 58, and 88, respectively, in the presence of a 0.2mg/L chlorine residual. The common notion that biofilms dominate the distribution system is not true under all conditions. These findings suggest that bulk water bacteria may dominate in portions of a distribution system that have a low chlorine residual.     

二氧化氯的发生与应用研究

二氧化氯是目前使用的消毒剂中最理想的杀菌消毒剂，国外称之为第4代消毒剂。二氧化氯的应用领域涉及水处理、饮食、造纸、养殖、食品等行业，其研究应用正在相关领域展开。本文详细论述了二氧化氯的性质、制备和应用，并得出制约二氧化氯使用的两大因素。