天然水中Cr(Ⅵ)与硫化物的氧化还原反应环境动力学的研究

本文模拟研究了地表水及土壤水介质中Cr(Ⅵ)在硫系统作用下的氧化还原反应动力学.在通常的pH及夏、秋温度和厌氧还原条件下进行动力学实验,采用了流动注射技术分析测定.初步确定了在一定的温度及pH条件下,当Cr(Ⅵ)与硫化物浓度相近时,二者之间的氧化还原反应为二级反应,其反应速率与Cr(Ⅵ)及总硫化物浓度的一次方乘积成正比.其速率常数随温度升高而增大,随pH升高却产生较为复杂的变化,总的说来,在pH5.5—7.0范围内速率常数较大.而在pH>7时反应很慢,近于停止了.当硫化物浓度远大于Cr(Ⅵ)时,二者之间的反应为准一级反应,Cr(Ⅵ)的还原速率与Cr(Ⅵ)浓度的一次方成正比,其反应速率常数随温度升高而增大,在pH5.0—7.8范围内速率常数随pH升高而逐渐减小.     

加压水解法处理含氰废水的研究

文章研究了含氰废水加压水解的反应条件及动力学,结果表明:水解温度影响最显著,反应时间次之,pH值及初始浓度影响都较小;氰化钾的加压水解反应规律符合一级反应动力学;在不同水解温度下,溶液中CN-加压水解的反应速率常数不同,并计算出该实验条件下的平均反应活化能。同时建立了氰化钾水解去除率与水解温度、反应时间的数学模型。     

没食子酸还原六价铬反应动力学规律研究

实验研究了不同pH值,温度和六价铬初始浓度等条件对没食子酸还原六价铬的反应动力学的影响,分别建立六价铬还原反应速率常数关于氢离子浓度和温度的函数方程.结果表明:pH值 为2.0~5.0时,没食子酸与六价铬发生的氧化还原反应符合准一级动力学反应;而pH值为6时,因[H+]不足,二者的反应不符合准一级动力学反应.在pH值为2.0~5.0时,六价铬反应速率常数(103kobs)分别是是951.6、103.6、17.3和7.5h-1.pH值 为2.5时,温度升高,反应速率常数快速增加;温度为30℃时,没食子酸还原六价铬的反应速率常数分别是温度为20℃和10℃时反应速率常数的1.61倍和3.68倍.不同初始浓度六价铬的反应体系中,六价铬反应速率常数随着反应体系中六价铬与没食子酸初始浓度比值的增加而逐渐减小.利用最小二乘线性回归法和阿伦尼乌斯公式分别建立了六价铬还原反应速率常数关于氢离子浓度和温度的函数方程,为预测和分析没食子酸还原六价铬反应过程中六价铬的反应速率常数和浓度变化情况提供动力学模型参考.     

除草剂绿草定-2-丁氧基乙酯的降解特性及降解机制研究

按照《化学农药环境安全评价试验准则》的规定并参考美国EPA导则,采用室内模拟试验方法,研究了绿草定-2-丁氧基乙酯在环境中的降解特性.结果表明,25℃时绿草定-2-丁氧基乙酯在pH =4、7、9缓冲溶液中的水解半衰期分别为533 d、21.8 d、＜1 d;高温、碱性条件下绿草定-2-丁氧基乙酯极易水解,其水解反应速率随反应介质pH值的增大、反应温度的升高而增大;初步确定绿草定-2-丁氧基乙酯分子在水溶液中生成的水解产物主要是绿草定.绿草定-2-丁氧基乙酯在土壤中迅速降解,酸性土壤中其降解趋势遵循一级动力学模型,中性和碱性土壤中其降解动态不能用一级动力学模型进行简单的拟合;绿草定-2-丁氧基乙酯在土壤中的降解形式主要为化学水解作用,降解生成绿草定和丁氧基乙醇;土壤pH和有机质含量是影响其土壤降解速率的主要因素,pH和有机质含量越高,其土壤降解速率越快.在人工光源氙灯条件下,绿草定-2-丁氧基乙酯在水溶液和土壤表面的光化学降解均符合一级动力学反应,不同介质对绿草定-2-丁氧基乙酯光解的影响差异显著.     

常用缓冲溶液对解草唑水解的催化效应研究

研究了温度、pH值以及常用缓冲溶液对解草唑水解的影响.结果表明.解草唑在不同pH值和温度下的水解遵循一级动力学反应,其水解速率随着pH和温度的升高而增大.利用Bronsted酸碱催化理论推导了所用缓冲溶液对解草唑水解的影响,结果表明缓冲溶液对解草唑水解存在明显的催化作用,加快了解草唑的水解速率.而且不同缓冲盐体系的缓冲催化能力也不同,同一缓冲盐体系在不同pH值条件下的缓冲催化能力也不同.其中pH=7的磷酸盐缓冲溶液表现出最大的催化作用.通过建立基于缓冲因子校正的以温度和pH值为变量的方程,预测了模拟天然水体中解草唑的水解半减期,结果表明其水解半减期为7～790 d.液相色谱.质谱分析表明,在碱性条件下(pH 8-10),解草唑通过乙酸乙酯基团水解生成解草唑酸.     

α—和γ六氯环己烷的盐基水解

六氯环己烷(HCHs)是世界海洋和大湖中污染量较大的有机氯农药,因此在测定环境的最终状况时,了解其(HCHs)化学反应性是十分重要的。在本研究中,α—和γ—HCHs的水解是在含叠氮化物的缓冲蒸馏水里进行的,该蒸馏水被放在严格密封的暗色瓶子里,以避免生物降解、光解和挥发方面的损失。试验操作条件:(a)恒定温度(45℃),pH7～9;(b)恒定pH(9),温度5～45℃,时间为4～248天(取决于反应条件)。在pH值恒定的情况下,HCHs的破坏遵循准一级动力学。由准一级速率常数(K′,min~(-1))可计算出二级盐基速率常数(K_b,M~(-1)min~(-1))、被检测的pH,及随温度变化的水的高子产物。在20℃,K_b值为1.57(α—HCH)和1.10(γ—HCH)。从随温度而变化的K_b数值里,可以测定出α—HCH和γ—HCH的活化能为78.3和84.6KJ/mol。当pH为7时,与H_2O的反应可以促使HCHs的破坏,估计的中性速率常数(K_n,min~(-1))为1.1×10~(-6)(α—HCH)和2.0×10~(-6_(γ—HCH)。当pH8和5℃时,α—HCH和γ—HCH的水解半衰期为26年42年.从海洋和大湖深处寒冷的水域里去除HCHs的水解作用要求其它过程的速度,如:沉积和微生物的破坏等。     

Fenton法氧化甲基橙溶液的脱色动力学实验研究

实验对甲基橙的Fenton氧化脱色降解反应过程进行了研究,结果表明在pH值为3、反应温度为30℃的反应条件下,Fenton试剂氧化甲基橙溶液脱色反应可以用一级动力学过程来描述,而且其反应速率常数受到亚铁离子初始浓度和过氧化氢初始浓度的影响很大,经过数据拟合分别得到了反应速率常数与亚铁离子初始浓度和过氧化氢初始浓度之间的数学关系。实验还对30℃～60℃不同温度下的Fenton反应过程进行了考察,结果表明不同温度下Fenton氧化甲基橙的脱色反应仍可以用一级动力学过程来描述,而且其反应速率常数受温度变化的影响不大,基本保持恒定。     

温度对WAO/CWAO处理垃圾渗滤液的影响

催化湿法氧化 (CWAO)是用于处理有机废水十分有效的物理化学方法 ,本实验将该方法用于垃圾渗滤液的处理 .使用CWAO处理垃圾渗滤液 ,温度是一个重要的影响因素 ,因此本研究着重研究温度对污染物去除效率、降解速率的影响 ,建立了温度与速率常数之间的定量关系 ,并初步考察了催化剂 (Co/Bi)在降解垃圾渗滤液过程中的作用 .实验中利用高压反应釜并使用催化剂 ,在封闭条件下对垃圾渗滤液进行处理 ,研究温度对降解反应的影响 .结果表明 :有、无催化剂存在的条件下 ,随着温度的升高 ,总有机碳 (TOC)和COD的去除率均显著增大 ;用Elovich方程可以描述垃圾渗滤液降解反应的动力学过程 ,速率常数k值随着温度的升高而逐渐增大 ,并建立了速率常数k与温度的定量关系式 ;反应液 pH值在反应过程中先迅速降低 ,之后缓慢上升 ,主要由于反应初期生成了大量的有机酸 ,而随着有机酸逐渐被降解 ,反应液 pH值缓慢上升 .通过本研究可知 ,以Co/Bi作催化剂 ,利用CWAO降解稀释后的垃圾渗滤液 ,可以在较为温和的条件下达到较好的处理效果 ,但本研究仅探讨了温度对催化湿法氧化降解垃圾渗滤液有较大的影响 ,其它反应条件如氧化剂、催化剂用量以及垃圾渗滤液浓度等对CWAO法降解效率的影响还有待于进一步研究     

α—萘酚—6,8—二磺酸的水解

本文测定了100—130℃下α—萘酚—6,8—二磺酸(G 酸)的酸催化水解动力学,此反应唯一产物是α—萘酚—6—磺酸(S 酸).α—磺酸基比β—磺酸基水解更快.水解反应在动力学上,可描述为一级反应.还确定了反应速度常数和活化能.该研究结果可用于消除在 G 酸生产过程中造成的产品损失.     

铁屑置换沉淀海绵铜动力学研究

从动力学角度研究了铁屑置换沉淀海绵铜的化学反应机理,探讨了溶液pH,Cu2+初始浓度,振荡强度和温度等因素对铜置换率的影响及动力学模型。通过测定不同温度条件下的表观反应速率常数(k);求得置换反应活化能为16.21kJ/mol。试验结果表明,置换反应的所有动力学数据服从一级反应速率规律,置换过程符合扩散控制机理。     

Toxic effects of acetochlor, methamidophos and their combination on nifH gene in soil

Toxic effects of two agrochemicals on nifH gene in agricultural black soil were investigated using denaturing gradient gel electrophoresis （DGGE） and sequencing approaches in a microcosm experiment. Changes of soil nifH gene diversity and composition were examined following the application of acetochlor, methamidophos and their combination. Acetochlor reduced the nifH gene diversity （both in gene richness and diversity index values） and caused changes in the nifH gene composition. The effects of acetochlor on nifH gene were strengthened as the concentration of acetochlor increased. Cluster analysis of DGGE banding patterns showed that nifH gene composition which had been affected by low concentration of acetochlor （50 mg/kg） recovered firstly. Methamidophos reduced nifH gene richness that except at 4 weeks. The medium concentration of methamidophos （150 mg/kg） caused the most apparent changes in nifH gene diversity at the first week while the high concentration of methamidophos （250 mg/kg） produced prominent effects on nifH gene diversity in the following weeks. Cluster analysis showed that minimal changes of nifH gene composition were found at 1 week and maximal changes at 4 weeks. Toxic effects of acetochlor and methamidophos combination on nifH gene were also apparent. Different nifH genes （bands） responded differently to the impact of agrochemicals： four individual bands were eliminated by the application of the agrochemicals, five bands became predominant by the stimulation of the agrochemicals, and four bands showed strong resistance to the influence of the agrochemicals. Fifteen prominent bands were partially sequenced, yielding 15 different nifH sequences, which were used for phylogenetic reconstructions. All sequences were affiliated with the alpha- and beta-proteobacteria, showing higher similarity to eight different diazotrophic genera.     

Arsenic uptake by arbuscular mycorrhizal maize （Zea mays L.） grown in an arsenic-contaminated soil with added phosphorus

The effects of arbuscular mycorrhizal (AM) fungus (Glomus mosseae) and phosphorus (P) addition (100 mg/kg soil) on arsenic (As) uptake by maize plants (Zea mays L.) from an As-contaminated soil were examined in a glasshouse experiment.Non-mycorrhizal and zero-P addition controls were included.Plant biomass and concentrations and uptake of As,P,and other nutrients,AM colonization,root lengths,and hyphal length densities were determined.The results indicated that addition of P significantly inhibited root colonization and development of extraradical mycelium.Root length and dry weight both increased markedly with mycorrhizal colonization under the zero-P treatments,but shoot and root biomass of AM plants was depressed by P application.AM fungal inoculation decreased shoot As concentrations when no P was added,and shoot and root As concentrations of AM plants increased 2.6 and 1.4 times with P addition,respectively.Shoot and root uptake of P,Mn,Cu,and Zn increased,but shoot Fe uptake decreased by 44.6%,with inoculation, when P was added.P addition reduced shoot P,Fe,Mn,Cu,and Zn uptake of AM plants,but increased root Fe and Mn uptake of the nonmycorrhizal ones.AM colonization therefore appeared to enhance plant tolerance to As in low P soil,and have some potential for the phytostabilization of As-contaminated soil,however,P application may introduce additional environmental risk by increasing soil As mobility.     

Degradation of metabolites accumulated of benzo[a]pyrene by coupling Penicillium Chrysogenum with KMnO4

Several main metabolites of benzo[a]pyrene （BaP） formed by Penicillium chrysogenum, Benzo[a]pyrene-1,6-quinone （BP 1,6- quinone）, trans-7,8-dihydroxy-7,8-dihydrobenzo[a]pyrene （BP 7,8-diol）, 3-hydroxybenzo[a]pyrene （3-OHBP）, were identified by high-performance liquid chromatography （HPLC）. The three metabolites were liable to be accumulated and were hardly further metabolized because of their toxicity to microorganisms. However, their further degradation was essential for the complete degradation of BaP. To enhance their degradation, two methods, degradation by coupling Penicillium chrysogenum with KMnO4 and degradation only by Penicillium chrysogenum, were compared; Meanwhile, the parameters of degradation in the superior method were optimized. The results showed that （1） the method of coupling Penicillium chrysogenum with KMnO4 was better and was the first method to be used in the degradation of BaP and its metabolites; （2） the metabolite, BP 1,6-quinone was the most liable to be accumulated in pure cultures; （3） the effect of degradation was the best when the concentration of KMnO4 in the cultures was 0.01% （w/v）, concentration of the three compounds was 5 mg/L and pH was 6.2. Based on the experimental results, a novel concept with regard to the bioremediation of BaP-contaminated environment was discussed, considering the influence on environmental toxicity of the accumulated metabolites.     

Impact of atrazine and nitrogen fertilizers on the sorption of chlorotoluron in soil and model sorbents

Sorption of chlorotoluron in ammonium sulfate, urea and atrazine multi-solutes system was investigated by batch experiments. The results showed application of nitrogen fertilizers to the soil could affect the behavior of chlorotoluron. At the same concentration of N, sorption of chlorotoluron decreased as the concentration of atrazine increased on the day 0 and 6 in soil, respectively. The sorption of chlorotoluron increased from 0 to 6 d when soils were preincubated with deionized water, ammonium sulfate and urea solution for 6 d. That indicated incubation time was one of the most important factors for the sorption of chlorotoluron in nitrogen fertilizers treatments. The individual sorption isotherms of chlorotoluron in rubbery polymer and silica were strictly linear in single solute system, but there were competition sorption between pesticides or between pesticides and nitrogen fertilizers. That indicated the sorption taken place by concurrent solid-phase dissolution mechanism and sorption on the interface of water-organic matter or water-mineral matter.     

Distribution and ecological effect of mercury in Laogang landfill, Shanghai, China

Laogang landfill near Shanghai is the largest landfill in China, and receives about 10000 t of daily garbage per day, Samples of topsoil and plants were analyzed to evaluate mercury pollution from the landfill. For topsoil samples, there were significant correlations among total mercury （HgT）, combinative mercury （Hgc） and gaseous mercury （HgG）, and content of total organic carbon （TOC）, but, no significantly relationship was found between Hg content and filling time. Hg content changes in vertical profiles with time showed that the average Hgv of profiles 1992, 1996, and 2000 was similar, but their average HgG was quite different. HgT was significantly correlated with Hgc in profile 1992 and 2000, and Hgv was significantly correlated with Hg6 in profile 1996. HgG/Hgv ratio in profile samples decreased in the order of （HgG,/HgT）1992〉（HgG/HgT）1996〉〉（HgG/HgT）2000. A simple outline of Hg release in landfill could be drawn： with increasing of filling time, degradation undergoes different biodegradation, accordingly, gaseous mercury goes through small, more, and small proportion to total mercury. Distribution of Hg in plants was inhomogeneous, following the order of leaf〉root〉stem. The highest value of leaf may be associated with higher atmospheric Hg from landfill. Ligneous plants （e.g. Phyllostachys glanca, Prunus salicina and Ligustrum lucidum） are capable of enriching more Hg than herbaceous plants.     

EDTA-enhanced phytoremediation of lead contaminated soil by Bidens maximowicziana

Phytoremediation is a potential cleanup technology for the removal of heavy metals from contaminated soils.Bidens maximowicziana is a new Pb hyperaccumulator,which not only has remarkable tolerance to Pb but also extraordinary accumulation capacity for Pb.The maximum Pb concentration was 1509.3 mg/kg in roots and 2164.7 mg/kg in overground tissues.The Pb distribution order in the B. maximowicziana was:leaf>stem>root.The effect of amendments on phytoremediation was also studied.The mobility of soil Pb and the Pb concentrations in plants were both increased by EDTA application.Compared with CK(control check),EDTA application promoted translocation of Pb to overground parts of the plant.The Pb concentrations in overground parts of plants was increased from 24.23-680.56 mg/kg to 29.07-1905.57 mg/kg.This research demonstrated that B.maximowicziana appeared to be suitable for phytoremediation of Pb contaminated soil,especially,combination with EDTA.     

Decomposition of alachlor by ozonation and its mechanism

Decomposition and corresponding mechanism of alachlor, an endocrine disruptor in water by ozonation were investigated. Results showed that alachlor could not be completely mineralized by ozone alone. Many intermediates and final products were formed during the process, including aromatic compounds, aliphatic carboxylic acids, and inorganic ions. In evoluting these products, some of them with weak polarity were qualitatively identified by GC-MS. The information of inorganic ions suggested that the dechlorination was the first and the fastest step in the ozonation of alachlor.     

Enzymatic oxidation of aqueous pentachlorophenol

The influence of the nonionic surfactant Tween 80 on pentachlorophenol （PCP） oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration （CMC）. Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.     

Potential of plant polyphenol oxidases in the decolorization and removal of textile and non-textile dyes

In this study an effort has been made to use plant polyphenol oxidases; potato （Solanum tuberosum） and brinjal （Solanum melongena）, for the treatment of various important dyes used in textile and other industries. The ammonium sulphate fractionated enzyme preparations were used to treat a number of dyes under various experimental conditions. Majority of the treated dyes were maximally decolorized at pH 3.0. Some of the dyes were quickly decolorized whereas others were marginally decolorized. The initial first hour was sufficient for the maximum decolorization of dyes. The rate of decolorization was quite slow on long treatment of dyes. Enhancement in the dye decolorization was noticed on increasing the concentration of enzymes. The complex mixtures of dyes were treated with both preparations of polyphenol oxidases in the buffers of varying pH values. Potato polyphenol oxidase was significantly more effective in decolorizing the dyes to higher extent as compared to the enzyme obtained from brinjal polyphenol oxidase. Decolorization of dyes and their mixtures, followed by the formation of an insoluble precipitate, which could be easily removed simply by centrifugation.     

Removal of heavy metals from sewage sludge by low costing chemical method and recycling in agriculture

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