光激发下硝酸纤维素膜降解对乙酰氨基酚的光解影响

硝酸纤维素膜(NCM)作为一种新型环保材料,在光激发下可产生强氧化性的羟基自由基,促进污染物降解. 为研究NCM对对乙酰氨基酚(APAP)的光解效果及影响因素,采用模拟太阳光源,考察了3种反应体系、光谱区间、APAP浓度、光照强度、温度、溶液pH以及水体成分等因素对光解效果的影响. 结果表明:APAP在纯水中几乎不发生光解,而在NCM体系中其光解速率常数为2.85×10?3 min?1;模拟太阳光源的UVA、UVB和可见光(Vis)波段均能促进APAP的光解,其中UVA波段对APAP光解的贡献最大. APAP的光解速率与其浓度呈负相关,低浓度APAP的光解效果更好. 在一定范围内,APAP光解速率与光照强度呈正相关,且随反应温度的增加而增大. 弱碱性环境更有利于APAP的光解,当pH=8.0时,APAP降解率为73.72%,降解效果最佳. 水体中NO₃?、Cl?、SO₄2?、CO₃2?、Mg2+、Ca2+和可溶性有机质(DOM)浓度的增加可以促进NCM对APAP的光解. 研究显示,光激发下利用NCM降解APAP反应迅速且效果显著,可为APAP的去除提供一种新方法.      

不同波段紫外光对微囊藻毒素光降解的影响

为优化光降解法去除饮用水中的微囊藻毒素,分别用UVA(l=300～400nm)和UVC(l=253.7nm)2种紫外光源研究了紫外光波长对MC-RR降解效率的影响.结果表明,不同波段的紫外光具有不同的催化效率和降解中间产物.在UVA下照射12h后,MC-RR仍有30%～50%残余,同时产生2种几何异构体4(Z)-Adda-MC-RR和6(Z)-Adda-MC-RR,且二者在整个反应过程中保持恒定的比例.而在UVC下,MC-RR除生成2种异构体外,还生成中间产物[三环-Adda]MC-RR,在0.850mW/cm2光强下照射60min后,这些中间产物随MC-RR一起基本消失.两种情况下,MC-RR浓度随时间的变化均可用二级反应速率方程描述,表观反应速率常数(k)均随着光强度的增加而增大.尽管UVC强度仅为UVA的10%,但MC-RR在UVC下的反应速率常数却比UVA下高了近2个数量级.这表明,利用光降解技术去除饮水中的微囊藻毒素宜选用UVC光源.     

不同波段紫外光在TiO2悬浊液中的消光特点

为确定TiO₂催化剂悬浊液对不同波段紫外光的消光规律,本试验以4-CBA-Na为模型污染物,针对催化剂/污染物悬浊液体系在不同催化剂投加量下,对UVA、UVB和UVC波段光子的消光效果进行了测定.结果表明,各悬浮体系对各波段紫外光的消光基本上符合比耳定律,即随着入射光程的增加,光强呈现负指数衰减;紫外光在催化剂悬浊液中的消光系数随催化剂投加量的增大而增加,其增加规律可以用二次多项式表示;污染物溶液本身对UVB和UVC紫外光有吸收,UVB和UVC紫外光在催化剂-污染物悬浮体系中的消光系数可视为污染物与催化剂颗粒的消光系数之叠加.催化剂悬浊液对紫外光的消光系数随紫外光波长的减小而增大,这意味着使用短波长的UVC作为光催化降解光源可以提高能量利用效率.     

电芬顿法处理重金属络合物Ni-EDTA的研究

本文首先研究了电絮凝与电芬顿对Ni-EDTA去除效率对比,结果发现电絮凝对Ni-EDTA去除效率较低.通过电化学阳极溶解产生Fe2+,外加H2O2反应的阳极电芬顿过程可有效去除Ni-EDTA.详细考察Ni-EDTA初始浓度、电流密度、p H值及H2O2投加量对Ni-EDTA去除率的影响.结果表明,电芬顿方法处理Ni-EDTA络合物其初始浓度越低,去除效果越好.反应最佳p H值为3.5,H2O2投加量在一定条件下存在最优值,而络合物的去除率随着电流密度的增加而提高.对Ni-EDTA去除过程进行了分析.     

响应面法优化硫酸根自由基高级氧化深度处理渗滤液生化尾水

针对垃圾渗滤液生化尾水中仍含有较高浓度的难生物降解COD、NH4+-N和NO2--N,无法满足现行排放标准的问题,采用基于硫酸根自由基的高级氧化技术(SR-AOP)对生化尾水进行深度处理.考察了pH值、温度、FeSO4和过硫酸钠浓度对TOC和TN去除效果的单独作用及交互作用.结果表明,影响因子对于处理效果的贡献排序为:pH值>温度>过硫酸钠浓度,各因素对TOC的去除有显著性影响,而对TN的去除没有显著性影响.各因素的复合效应为:TN去除效果影响:温度+过硫酸钠浓度>pH+过硫酸钠浓度>温度+pH, TOC去除效果影响:温度+pH>pH+过硫酸钠浓度>温度+过硫酸钠浓度.实验最终确定SR-AOP的最佳条件为:pH=5,温度为30℃,过硫酸钠浓度为0.5g/L,催化剂FeSO4剂量为3.8g/L,该条件下TOC去除率为35.5%,TN去除率为16.9%,同时可以显著提高出水BOD5/COD.因此,通过SR-AOP深度处理可以去除生化处理尾水大部分COD和TN,并大幅提高B/C比,为后续与适当的生化处理工艺组合进行达标处理奠定了良好的基础.     

光助芬顿反应催化降解气体中甲苯

以甲苯作为挥发性有机污染物(VOCs)的代表,利用连续进气动态实验装置,研究光助芬顿反应降解气体中甲苯的作用.考察了芬顿试剂溶液初始p H、H2O2浓度、Fe2+浓度以及甲苯初始浓度对降解甲苯的影响,并利用在线质谱和色谱对产物进行了定性、定量分析.结果表明,紫外光照加快了羟基自由基的生成,显著提高了气体中甲苯的去除率;p H=3.0、H2O2浓度为20 mmol·L-1、Fe2+浓度为0.3 mmol·L-1的条件下,甲苯去除率最高;当甲苯初始浓度为260 mg·m-3时,去除率能够达到98%;光助芬顿反应催化降解气体中甲苯实验未检测到CO2之外的中间产物,CO2产率分析表明去除的甲苯全部转化为CO2.     

新型无极准分子光源深度处理水相中含N-杂环化合物

采用微波激发Kr/I2混合气体产生的206 nm准分子紫外光降解水相含N-杂环化合物,考察了206 nm准分子光直接光解模拟喹啉和吲哚废水的效果.结果表明,初始浓度为20 mg.L-1的吲哚溶液,光照80 min时去除率达62.0%,150 min时TOC去除达50.7%.光照时间、初始浓度和溶液的pH值对喹啉的降解有一定的影响.相同条件下,喹啉的去除率和TOC损失率都明显低于吲哚.光解后的溶液经旋转蒸发提取,顶空注射进入气相色谱/质谱联用仪(GC/MS)定性分析,结果表明,光照下喹啉发生开环降解,生成了甲苯、二甲苯、酸、醛和酯类化合物,而吲哚降解过程中发生了聚合反应.最后,根据中间产物,推断了206 nm准分子光源光解喹啉和吲哚的机制.     

UV协同ClO2去除三氯生及其降解产物的研究

采用UV/Cl O2工艺对三氯生(TCS)的去除进行了研究,考察了初始p H、Cl O2投加量、TCS初始浓度、腐殖酸(HA)在UV/Cl O2联用工艺中对TCS降解的影响.研究表明,UV/Cl O2工艺可以有效去除TCS且具有协同作用,光强为6.5μW·cm-2、Cl O2投加量为0.5 mg·L-1和TCS浓度为300μg·L-1时,单独UV和Cl O2在1 min内对TCS的去除分别为5.23%和84.93%,UV/Cl O2联用工艺TCS在1 min内去除可达到99.13%.实验范围内(p H 6~9)随着p H的增大TCS去除率从99.4%升到99.63%;增大Cl O2投加量可以提高TCS的去除,Cl O2投加量从0.5~1.5 mg·L-1时TCS去除率由98.1%提高到99.89%;TCS初始浓度与去除率呈负相关,初始浓度从100~500μg·L-1时TCS去除率由99.98%下降到94.39%;低浓度的腐殖酸有利于TCS的去除,高浓度的腐殖酸则相反.GC/MS对TCS的UV、Cl O2和UV/Cl O2的降解产物分析表明,TCS的主要降解产物包括2,4-二氯苯酚(2,4-DCP)、2,7-二氯代二苯并-对-二英(2,7-DCDD)等.     

海绵状零价铁修复硝酸盐污染地下水试验研究

研究以50~100目的海绵状铁粉为还原剂,采用静态试验方法,研究了铁对硝酸盐氮的还原作用及其影响因素,分析了铁粉用量、铁炭比、pH值、硝酸盐氮初始浓度、温度以及铁粉表面预处理对硝酸盐去除率的影响。试验结果表明,最佳铁氮质量比为400∶1,铁粉投入过多对硝酸盐的去除率没有进一步促进;活性炭的加入有助于零价铁(Fe0)还原硝酸盐,降低反应后溶液中的NH+4-N浓度,试验最佳的铁炭比为1∶2;溶液的初始pH值降低有利于硝酸盐氮的去除;硝酸盐氮初始浓度越大,反应的平均速率越高;升高温度和酸洗预处理,有利于提高硝酸盐的去除率;产物分析表明,试验过程中,去除的NO-3-N含量中约60%以上转化为NH+4-N,NO-2-N浓度很低。     

UV/H_2O_2对氯消毒副产物TCM、DCBM的去除影响因素研究

针对UV/H_2O_2对氯化消毒副产物三氯甲烷(TCM)和一溴二氯甲烷(DCBM)的去除效果及影响因素进行研究,结果表明UV/H_2O_2方法对TCM和DCBM去除效果的影响因素有过氧化氢(H_2O_2)投加量、紫外光照强度、反应p H值和反应物初始浓度。通过不同的反应条件得出:H_2O_2在一定投加量变化范围(10~35 mmol/L)内,随投加量的增加,TCM和DCBM的去除率均呈先上升后下降趋势,H_2O_2最佳投加量分别为25,20 mmol/L;增大紫外光照(UV)强度,TCM和DCBM的去除率均显著提高;随初始p H值的增大,去除率均呈先上升后下降趋势,p H值为7.0时,去除率达到最佳;TCM和DCBM反应初始浓度分别为150,160μg/L时,其去除率最高,在有效时间内去除率分别为95.88%、92.56%。     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

基于综合水质标识指数和对应分析法的校园河道水质评价

以三峡大学的校园河道求索溪为研究对象,利用综合水质标识指数法确定求索溪水质类别,分析其水质时空变化规律,并利用对应分析法得出求索溪中不同监测点的主要污染因子.研究结果表明:求索溪整体的综合水质标识指数为7.423,整体水质为劣V类(地表水环境质量标准GB 3838-2002)且黑臭.从时间变化来看,求索溪4月份的水质最差,5月份次之,4、5月份所有监测点的水质都劣于V类且黑臭;8月份水质最好,水质为Ⅳ类;从空间分布来看,8个监测点综合水质标识指数均超过6.0,水质为劣V类,其中6号监测点的水质相对最好,监测点3号的水质相对最差;对应分析法得出求索溪的整体水体污染程度受总氮因子的影响最大,其次为总磷.该研究拟为求索溪及类似校园河道的水环境治理研究提供基础依据和参考.     

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.