腐殖酸影响酸性水体中As(Ⅲ)光氧化的研究

为了考察紫外光(λ_(max)=365 nm)照射下三价砷(As(Ⅲ))在含有腐殖酸的水体中光氧化过程,该文研究了初始pH、HA浓度、外加铁离子以及不同分子量范围的HA组分等环境因子对As(Ⅲ)光氧化的影响。利用ESR检测和自由基猝灭实验以及不同气氛实验,量化不同活性物种对As(Ⅲ)光氧化的贡献率。结果表明,pH值对As(Ⅲ)在HA体系中的光氧化影响极大,低pH有利于As(Ⅲ)的光氧化。当pH为2.6,As(Ⅲ)浓度为100.0μg/L时,HA的最佳投加量为10.0 mg/L。Fe(Ⅲ)-HA络合物表现出低光活性,外加低浓度铁离子抑制As(Ⅲ)的光氧化,高浓度则促进As(Ⅲ)的光氧化。不同分子量范围的HA组分对As(Ⅲ)的光氧化贡献不同。As(Ⅲ)的形态转化是由于三重态腐殖酸(~3HA~*)的直接作用以及羟基自由基(HO·)直接氧化共同作用的结果。其中85%的As(Ⅲ)氧化是HO·直接氧化导致,HO·主要来自HO_2·/O_2·~-;剩余15%依赖于~3HA~*对As(Ⅲ)的直接氧化。研究结果有助于了解As(Ⅲ)在含有溶解性有机质的酸性水体中光化学转化行为。     

δ-MnO2/水界面17β-雌二醇的氧化转化

采用化学合成的新生态水合δ-MnO2为氧化剂,研究其对17β-雌二醇(E2)氧化转化的反应动力学,考察相关因素(如pH、δ-MnO2投加量等)对氧化转化的影响,并通过气相色谱质谱联用仪(GC/MS)分析δ-MnO2氧化转化E2的产物,探讨氧化转化的反应机制.结果表明,E2对新生态水合δ-MnO2的氧化作用具有较强的反应感受性,且在pH值一定和δ-MnO2充分过量的条件下,E2氧化转化的反应动力学并不是简单的准一级反应动力学,而是遵循复合的反应动力学.E2的氧化转化速率与δ-MnO2的投加量呈正相关,在δ-MnO2投加量为c(E2)∶c(MnO2)=1∶100时,反应体系中的δ-MnO2已足够,E2浓度在8h内降低了90%以上.E2的氧化转化速率与pH值的增加呈负相关,pH为4.0时,E2在0.25h内去除率达到95%,而在pH为6.8和9.0时,E2在1h内只去除了80%和75%.另外,在反应过程中检测到了2个主要产物,分别为雌酮(E1)和2-羟雌二醇,并在此基础上结合相关文献提出了氧化转化流程.     

纳米零价铁基生物炭活化过硫酸盐降解土霉素

采用纳米零价铁基生物炭(nZVI-BC)耦合过二硫酸钠(PDS)或过硫酸氢钾(PMS)构建吸附-高级氧化复合体系开展水中土霉素(OTC)的高效降解。考察了在不同PDS/PMS浓度、nZVI-BC投量、OTC浓度及初始pH条件下OTC的去除规律,并对体系中活性物种进行探究。结果表明:在0.20 mmol/L PDS/PMS,0.01 g nZVI-BC,50 mg/L OTC,原始pH为5.0±0.1条件下,OTC去除率可达到80%以上;SO₄-·在nZVI-BC/PDS体系中对OTC降解占有绝对主导地位(贡献度为57.00%),nZVI-BC/PMS体系则主要依靠SO₄-·、O₂-·和1O₂。     

不同波段下黄海中二甲基硫光氧化动力学研究

采集黄海表层海水样品,在模拟太阳光照射条件下研究二甲基硫(DMS)在UVB(280、295和305nm)、UVA(320、345和395nm)和可见光(435和495nm)8个不同波段下的光化学氧化动力学行为,并探讨其对二甲亚砜(DMSO)生成的贡献率.研究结果表明,DMS光氧化过程均符合一级反应动力学方程,在UVB、UVA和可见光波段的光氧化速率常数分别为2.71~5.52、2.23~4.09和1.5~2.65d-1.同一样品UVB波段下DMS的氧化速率明显大于UVA和可见光波段下的速率,且在280nm下最大.随着光照时间的增长,海水样品中DMS浓度与有色溶解有机物(CDOM)的光谱吸收系数(α(355))表现出明显的负相关性,表明CDOM吸光特性对DMS的光氧化过程有明显影响.此外,8个不同波段下DMS光氧化向DMSO的转化率在20.0%-31.9%范围之间,其中在280nm下达到最大值.     

亚磷酸盐在硝酸根溶液中的光氧化过程及影响因素

亚磷酸盐(HPO_3~(2-),H_2PO_3~-,+3价)是磷生物地球化学循环中的还原态形式,其在水环境中的光氧化过程可能是亚磷酸盐转化的重要途径之一.以300W汞灯为光源,研究了环境浓度(1μmol/L)的亚磷酸盐在NO_3~-溶液中的光氧化过程,探讨了NO_3~-浓度、溶液pH值、环境中普遍存在的离子(Cl~-、SO_4~(2-)、HCO_3~-、Fe~(3+)、Mn~(2+))及腐殖酸对亚磷酸盐光氧化过程的影响.结果表明,亚磷酸盐在NO_3~-溶液中的光氧化反应符合准一级动力学规律,当NO_3~-浓度由0增至120μmol/L时,其速率常数由0.020h~(-1)增至0.271h~(-1);酸性溶液(pH=4)有利于亚磷酸盐在硝酸根溶液中的光氧化,水环境中SO_4~(2-)及Cl~-对光氧化过程存在弱抑制,而HCO_3~-对光氧化过程产生较强的抑制作用.Fe~(3+)促进了亚磷酸盐在NO_3~-溶液中光氧化过程,而Mn~(2+)则是抑制作用.腐殖酸的加入对亚磷酸盐光氧化过程存在抑制作用.活性氧猝灭剂(异丙醇,叠氮化钠)的加入大大抑制了亚磷酸盐的光氧化过程,表明亚磷酸盐光氧化过程中,活性氧的产生对其光氧化起到关键作用.模拟太湖水样中亚磷酸盐的减少量与正磷酸盐的增加量一致,证明亚磷酸盐光氧化产物是正磷酸盐.     

水体系中十二烷基苯磺酸钠的光化学氧化动力学研究

系统研究了在天然日光和高压汞灯照射下十二烷基苯磺酸钠(SDBS)在蒸馏水、人工海水和天然海水中的光降解情况。结果发现,SDBS的光化学氧化的速率会受到溶液介质、光源、重金属离子、光敏剂以及pH的影响。SDBS的光化学氧化反应符合一级动力学规律,其一级反应速率常数为0.0184 min-1~0.0281 min-1。SDBS在蒸馏水中的光降解速率大于在人工海水和天然海水中的光降解速率,其主要原因是蒸馏水中溶解更多的氧。天然海水中重金属离子Zn2+和Cd2+能加快SDBS的光氧化速率,光敏剂的加入也会加快SDBS的光氧化速率。此外,酸性条件下有利于SDBS的光降解。     

UV体系中3种微量类固醇雌激素的竞争降解及同趋转化

采用UV体系(UV、UV/H2O2和UV/H2O2/TiO2)降解水中同时存在的3种微量类固醇雌激素雌酮(E1)、17-β雌二醇(E2)和17-α乙炔基雌二醇(EE2),结果表明,降解过程均符合一级反应动力学,通过不同UV系统对比发现,关键因素对混合污染降解的影响顺序为H2O2>光强>TiO2.E1光解特性良好,在混合基质中可优势降解;E2和EE2直接光解效果较差,优劣顺序受到光强的影响,光强升高EE2略占优势.H2O2和催化剂TiO2的投加可提高3种物质的降解效果及降解速率常数,但竞争条件下E2和EE2的去除率提高有限.E1,E2和EE2的光化学降解过程具有相似的转化趋势,均可生成与E1结构类似的副产物.     

苯酚液相臭氧氧化和复合氧化反应动力学

推导了苯酚液相臭氧氧化和复合氧化（O3/H2O2）反应动力学模型,研究了苯酚液相臭氧氧化和复合氧化过程的降解,得出了苯酚液相臭氧氧化和复合氧化在温度288～313K和pH3.2～9.8条件下的反应动力学,探讨了反应机理,认为：在酸性(pH3.2）及弱酸性（pH6.2～6.5）时,苯酚的臭氧化和复合氧化降解反应均为O3分子的直接氧化过程;在碱性（pH9.8）条件下,苯酚复合氧化降解机理以自由基反应为主。     

水体中N、Fe的存在形态对萘普生光解行为的影响

研究了水环境中不同形态的无机氮(NO_3~-、NO_2~-、NH_4~+)和铁(Fe~(3+)、Fe~(2+))对萘普生(NPX)紫外光降解的影响.结果表明,NO_3~-、NO_2~-、Fe~(3+)和Fe~(2+)均抑制NPX的紫外光降解,抑制率随添加浓度的增加而增大;NH_4~+对NPX的紫外光降解基本没有影响.同时,模拟在水体中不同p E值下,不同形态无机氮和铁体系分别对NPX紫外光降解的复合影响.研究发现,在无机氮体系,复合状态下对NPX的紫外光降解存在拮抗作用;在铁体系,复合状态下对NPX的紫外光降解存在协同作用.     

环境科学一般问题

X-1200703527光化学降解有机磷农药研究进展/喻龙(中国热带农科院环境与植物保护研究所)…∥安全与环境学报/北京理工大学.-2007,7(2).-36~40环图X-142光化学降解有机磷农药是一种高效、无二次污染的非生物转化过程,也是有机磷农药在环境中的主要降解途径.通过介绍光化学方法降解有机磷农药的基本原理、有机磷农药的主要光化学反应类型、光化学降解过程中光敏(猝灭)剂的作用及影响光化学反应的因素,分析了今后光化学降解有机磷农药研究中需关注的问题,提出将有机磷农药的光催化氧化技术与其他方法相结合,研发高效、经济的新技术是今后农药…     

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.     

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.     

Evaluation of phytoextracting cadmium and lead by sunflower, ricinus, alfalfa and mustard in hydroponic culture

Soil contaminated with heavy metals cadmium(Cd)and lead(Pb)is hard to be remediated.Phytoremediation may be a feasible method to remove toxic metals from soil,but there are few suitable plants which can hyperaccumulate metals.In this study,Cd and Pb accumulation by four plants including sunflower(Helianthus annuus L.),mustard(Brassica juncea L.),alfalfa(Medicago sativa L.), ricinus(Ricinus communis L.)in hydroponic cultures was compared.Results showed that these plants could phytocxtract heavy metals, the ability of accumulation differed with species,concentrations and categories of heavy metals.Values of BCF(bioconcentration factor)and TF(translocation factor)indicated that four species had dissimilar abilities of phytoextraction and transportation of heavy metals.Changes on the biomass of plants,pH and Eh at different treatments revealed that these four plants had distinct responses to Cd and Pb in cultures.Measurements should be taken to improve the phytoremediation of sites contaminated with heavy metals,such as pH and Eh regulations,and so forth.     

Effects of chitosan on growth of an aquatic plant (Hydrilla verticillata) in polluted waters with different chemical oxygen demands

Effects of chitosan on a submersed plant, Hydrilla verticillata, were investigated. Results indicated that H. venicillata could prevent ultrastructure phytotoxicities and oxidativereaction from polluted water with high chemical oxygen demand (COD). Superoxide dismutase (SOD) activity and malondialdehyde (MDA) contents in H. verticillata treated with 0.1% chitosan in wastewater increased with high COD (980 mg/L) and decreased with low COD (63 mg/L), respectively. Ultrastructural analysis showed that the stroma and grana of chloroplast basically remained normal. However, plant cells from the control experiment (untreated with chitosan) were vacuolated and the cell interval increased. The relict of protoplast moved to the center, with cells tending to disjoint. Our findings indicate that wastewater with high COD concentration can cause a substantial damage to submersed plant, nevertheless, chitosan probably could alleviate the membrane lipid peroxidization and ultrastructure phytotoxicities, and protect plant cells from stress of high COD concentration polluted water.     

Oxidation of As(Ⅲ) by potassium permanganate

The oxidation of As(Ⅲ) with potassium permanganate was studied under conditions including pH, initial As(Ⅲ) concentration and dosage of Mn(Ⅶ). The results have shown that potassium permanganate was an effective agent for oxidizing of As(Ⅲ) in a wide pH range. The pH value of tested water was not a significant factor affecting the oxidation of As(Ⅲ) by Mn(Ⅶ). Although theoretical redox analyses suggest that Mn(Ⅶ) should have better performance in oxidization of As(Ⅲ) within lower pH ranges, the experimental results show that the oxidation efficiencies of As(Ⅲ) under basic and acidic conditions were similar, which may be due to the adsorption of As(Ⅲ) on the Mn(OH)2 and MnO2 resulting from the oxidation of As(Ⅲ).     

Removal of cadmium using MnO2 loaded D301 resin

MnO2 loaded weak basic anion exchange resin D301 （Anion exchange resin, macroreticular weak basic styrene） as adsorbent has been prepared and applied to the removal of cadmium. The adsorption characteristics have been investigated with respect to effect of pH, equilibrium isotherms, removal kinetic data, and interference of the coexisting ions. The results indicated that the Cd^2＋ could be efficiently removed using MnO2 loaded D301 resin in the pH range of 3-8 from aqueous solutions with the co-existence of high concentration of alkali and alkaline-earth metals ions. The saturate adsorption capacity of the Cd^2＋ was 77.88 mg/g. The adsorption process followed the pseudo first-order kinetics. The equilibrium data obtained in this study accorded excellently with the Langmuir adsorption isotherm.     

Effect of coagulation pretreatment on the fouling of ultrafiltration membrane

The purpose of this study is to understand the effect and mechanism of preventing membrane fouling, by coagulation pretreatment, in terms of fractional component and molecular weight of natural organic matter （NOM）. A relatively higher molecular weight （MW） of hydrophobic compounds was responsible for a rapid decline in the ultrafiltration flux. Coagulation could effectively remove the hydrophobic organics, resulting in the increase of flux. It was found that a lower MW of neutral hydrophilic compounds, which could remove inadequately by coagulation, was responsible for the slow declining flux. The fluxes in the filtration of coagulated water and supernatant water were compared and the results showed that a lower MW of neutral hydrophilic compounds remained in the supernatant water after coagulation could be rejected by a membrane, resulting in fouling. It was also found that the coagulated flocs could absorb neutral hydrophilic compounds effectively. Therefore, with the coagulated flocs formed on the membrane surface, the flux decline could be improved.