UV-vis光照下唑类抗菌药氟康唑的光化学反应类型

以唑类抗菌药氟康唑为模型化合物,考察了其在纯水中的光降解动力学和光化学反应类型,发现模拟日光(λ>290nm)照射下氟康唑未发生光解,在UV-vis(λ>200 nm)光照下,氟康唑发生了光降解并服从准一级反应动力学.采用活性氧物种猝灭实验和竞争动力学方法,研究发现氟康唑发生了直接光解和·OH参与的自敏化光解,氟康唑与.OH的反应速率常数为(5.95±0.58)×109L·(mol·s)-1,表层水体中相应的半减期为(32.41±3.16)h·通过鉴定光解产物,得知氟康唑发生了脱氟、光致水解、光氧化等光化学反应.     

哒嗪硫磷在液相中的光化学降解

以高压汞灯为光源,研究了哒嗪硫磷在液相中的光化学降解及影响因素.结果表明,哒嗪硫磷浓度为5mg·L-1时,在纯水中光解半衰期为9.82h,哒嗪硫磷在不同有机溶剂中的光解速率大小依次为正己烷>乙酸乙酯>甲醇>乙腈,在碱性溶液中比中性和酸性溶液中光解快.在2～20mg·L-1浓度范围内,哒嗪硫磷在水与甲醇中光解速率均随初始浓度的增加而降低.硝酸盐对哒嗪硫磷水中光解有一定的光敏化作用,而表面活性剂(SDS)则表现出显著的光猝灭作用,且猝灭作用与剂量比正相关.Fe3+和Fe2+对哒嗪硫磷水中光解有极强的光敏作用,并且光敏效应随着离子浓度的提高表现出先增加后减小的现象.光解产物的HPLC-MS检测表明,哒嗪硫磷在水中光解主要的途径是发生光氧化和光异构化作用.     

新农药硫肟醚在有机溶剂中的光解

以紫外灯为光源,对硫肟醚在甲醇、丙酮、正己烷和二甲苯等有机溶剂中的光解反应动力学及降解机理进行了初步研究.结果表明,硫肟醚在4种有机溶剂中的紫外光解反应符合一级动力学规律,在4种溶剂中反应速率常数分别为1·14×10-1(正己烷)、8·90×10-2(甲醇)、2·46×10-2(二甲苯)和4·51×10-3min-1(丙酮),硫肟醚的降解半衰期分别为6·08,7·79,28·18和153·86min.通过对硫肟醚光解产物进行分离和LC-MS鉴定,初步推出在紫外光辐射下硫肟醚在有机溶剂中的降解主要涉及到硫肟醚分子的肟醚键(CNOC)断裂、甲硫键(C—S—CH3)光氧化、脱氯反应和光异构化作用等途径.     

2-烯丙基苯酚在液相中的光化学降解研究

以太阳光和紫外灯为光源研究了 2 烯丙基苯酚在溶液相中的光化学降解 .太阳光下 ,2 烯丙基苯酚在甲醇、正己烷、重蒸水以及不同pH的缓冲溶液中的光稳定性很强 ,但在丙酮中可以光解 ,10 4mg·L-1 的 2 烯丙基苯酚在丙酮中的光解半衰期为 36 4h .核黄素、过氧化氢、三氯化铁能加快 2 烯丙基苯酚在水溶液中的光解速率 ,其中核黄素的敏化效果最显著 .在紫外光照下 ,2 烯丙基苯酚在各种溶剂中光解迅速 ,速率遵循一级动力学方程 ;水中溶解物质对其光解有一定的抑制作用 ;在pH=9的缓冲溶液中的光解速率 >pH =7的缓冲溶液中的光解速率 >pH =4的缓冲溶液中的光解速度 ;紫外光照 2h ,2 烯丙基苯酚在甲醇中的主要光降解产物经GC MS和LC MS鉴定为 :2 ,4 ,5 三羟基苯甲醛、邻羟基苯乙酸甲酯、对烯丙基苯酚、2 甲基苯并二氢呋喃     

有机气溶胶组分对六氯苯光解的影响

以高压汞灯为光源,分别研究了六氯苯在正己烷和邻苯二甲酸二异辛酯(DIOP)为有机气溶胶表层模拟介质时的光解,发现六氯苯在正己烷和DIOP中的光解半衰期分别约为<5 min和5 h,相差70倍以上.研究发现蒽醌和甲氧酚类气溶胶组分对六氯苯的光解具有光敏化作用,其反应机制可能分别为能量转移和抽氢反应.六氯苯光解的主要产物是五氯酚.     

水体系中氧氟沙星的光化学降解研究

研究了高压汞灯和氙灯照射下氧氟沙星(OFLX)在蒸馏水、人工海水和天然海水中的光降解过程,探讨了光源、起始浓度、丙酮、表面活性剂等因素对OFLX光化学降解速率的影响.结果表明,OFLX在高压汞灯下的光反应速率比在氙灯下快得多,均符合一级反应动力学过程;在相同光源下,OFLX在海水中降解最快,其次是人工海水;当OFLX初始浓度为2、4、6mg.L-1时,其光解速率常数分别为0.163、0.140和0.132 min-1,随着OFLX初始浓度增大,其光解率降低;不同浓度的丙酮均能促进OFLX光降解的反应,其反应速率常数为0.084 2～0.102 min-1,且光敏效率与丙酮浓度呈正相关关系;然而当十六烷基三甲基溴化铵(CTAB)、十二烷基苯磺酸钠(SDBS)、吐温-20(TW-20)等表面活性剂的浓度为5 mg.L-1,它们均抑制了水体中OFLX光降解反应的进程.另外,利用金藻8701单种培养进行了OFLX光化学降解前后的毒性试验,表明OFLX光解过程产生风险较高的中间产物,随着光解进行,产物毒性降低.     

天然水体腐殖质对双酚A光降解影响的研究

以中压汞灯模拟太阳光光源,研究了双酚A(BPA)在水体腐殖质中的光降解过程,探讨了不同来源的腐殖质、腐殖质浓度、BPA初始浓度、溶解氧等因素对BPA光解速率的影响,实验结果表明,BPA在纯水体系中直接光解很慢,但在腐殖质溶液中光解迅速,符合拟一级动力学反应,改变BPA初始浓度对BPA光解速率的影响不明显,增大溶解氧浓度会抑制BPA光解,通过活性氧分子探针鉴定了腐殖质吸收光辐射产生的羟基与单线态氧,利用GC-MS鉴定了双酚A在Nordic湖富里酸(NOFA)中的光敏化降解产物,推测出BPA敏化降解的可能历程为能量转移导致的直接光解、羟基加成和羟基氧化。     

UV_(254)降解水中双氯芬酸的动力学及机理研究

研究了254 nm紫外光照(UV_(254))对水中双氯芬酸(DCF)的降解,考察了pH、天然有机物质(NOM)和硝酸盐(NO_3~-)对DCF光解的影响;探讨了DCF的光解产物和转化机理;最后,研究了DCF在实际水体中的去除.结果表明,DCF在UV_(254)辐射下发生快速降解,其光解遵循准一级反应动力学模型.在研究的pH范围内,DCF降解效率基本相同,其表观速率常数在5.9×10~(-3)cm~2·mJ~(-1)左右.NOM的存在会抑制DCF的光解,且NOM浓度越高,抑制作用越明显,这主要是由于NOM和DCF竞争入射的紫外光子.NO_3~-在UV_(254)光照下可被激发产生羟基自由基,故NO_3~-的存在可以明显促进DCF的降解.DCF在实际水体中的去除效率与纯水中的基本类似,在紫外光用量为320 mJ·cm~(-2)时,大约83%1μmol·L~(-1)DCF被去除.在UV_(254)光解DCF反应中,共检测到12种降解产物,基于这些检出的反应产物提出DCF可能的光解机理主要包括6种不同的转化路径,分别为脱氯环化、脱羧基反应、甲酰化反应、脱氯羟基化、脱氯氢化和醌化反应.     

甲黄隆在有机溶剂中的光解

以中压汞灯为光源,研究了甲黄隆在甲醇和丙酮等有机溶剂中的光解动力学,结果表明均为一级反应。甲黄隆在甲醇中的光解速率与在水中相差不大,而丙酮可明显促进其光解。甲黄隆在甲醇中光解先断裂脲桥,生成磺酰胺和取代三嗪,磺酰胺继续光解生成苯甲酸甲酯和微量的硫酚。     

含碳酸盐水溶液中扑热息痛的光解研究

采用动力学方法研究了环境浓度范围内的扑热息痛在含碳酸盐溶液中的光解,比较了碳酸盐自由基和羟基自由基对扑热息痛的光解效果,探讨了pH值、硝酸根离子、腐殖质、氯化钠、钙镁离子等因素对扑热息痛光解的影响.利用GC/MS技术鉴定了扑热息痛的光解产物,并探讨了扑热息痛在碳酸根体系中可能的光解途径.结果表明,扑热息痛与碳酸盐自由基反应的二级反应速率常数为 k.=5.0×107L·(mol·s)-1,低于与羟基自由基反应的二级反应速率常数kb=8.1×109L·(tool·s)-1,但是由于天然水体中碳酸盐自由基的稳态浓度较高,所以碳酸盐自由基对扑热息痛光解的影响和羟基自由基大致相当.提高体系pH值,加入硝酸根离子、氯化钠或者钙镁离子都会加快扑热息痛的光解速率;而加入Suwannee河富里酸则会降低光解速率.     

Effects of two sludge application on fractionation and phytotoxicity of zinc and copper in the soil

The potential harm of heavy metals is a primary concern in application of sludge to the agricultural land. A pot experiment was conducted to evaluate the effect of two sludges on fractionation of Zn and Cu in soil and their phytotoxicity to pakchoi. The loamy soil was mixed with 0%, 20%, 40%, 60% and 80% (by weight) of digested sewage sludge (SS) and composted sludge (SC). The additions of both sludges caused a significant raise in all fractions, resulting in that exchangeable (EXCH) and organic bound (OM) became predominance of Zn and organic bound Cu occupied the largest portion. There was more available amount of Zn and Cu in SS treatments than SC treatments. During the pot experiment, the concentration of Zn in EXCH, carbonate (CAR) and OM and Cu in EXCH and OM fractions decreased in all treatments, so their bioavailability reduced. Germination rate and plant biomass decreased when the addition rate was high and the best yield appeared in 20% mixtures at the harvest of pakchoi. The two sludges increased tissue contents of Zn and Cu especially in the SS treatments. Zn in pakchoi was not only in relationship to ΔEXCH and ΔCAR forms but also in ΔOM forms in the sludge-soil mixtures. Tissue content of Cu in pakchoi grown on SC-soils could not be predicted by ΔEXCH. These correlation rates between Zn and Cu accumulation in pakchoi and variation of different fractions increased with time, which might indicate that sludges represented stronger impacts on the plant in long-term land application.     

Intraspecific differences in effects of co-contamination of cadmium and

A hydroponic experiment was carried out to study intraspecific differences in the effects of different concentrations of cadmium (Cd)(0-10 mg/L) and arsenate (As(V)) (0-8 mg/L) on the growth parameters and accumulation of Cd and As in six wheat varieties Jing-9428, Duokang-1, Jingdong-11, Jing-411, Jingdong-8 and Zhongmai-8. The endpoints of wheat seedlings, including seed germination,biomass, root length and shoot height, decreased with increasing the Cd and As concentrations. Significant differences in seed germination, biomass, root length, shoot height and the accumulation of Cd and As were observed between the treatments and among the varieties (p ＜ 0.05). The lethal dosage 50% were about 20, 80, 60, 60, 80 and 20 mg As/L for Jing-9428, Duokang-1, Jingdong-11,Jing-411, Jingdong-8 and Zhongmai-8, respectively, and the corresponding values for Cd were about 30, 80, 20, 40, 60 and 10 mg Cd/L, respectively. Among the six varieties, Duokang-1 was found to be the most resistant to Cd and As toxicity, and Zhongmai-8 was the most sensitive to Cd and As co-contamination. The resistance of the six varieties was found dependant on the seedling uptake of Cd and As. Duokang-1 was the most suitable for cultivation in Cd and As co-contaminated soils.     

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.     

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.     

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.     

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.     

Effect of sorbed and desorbed Zn(Ⅱ) on the growth of a green alga (Chlorella pyrenoidosa)

Toxic effect of Zn(Ⅱ) on a green alga (Chlorella pyrenoidasa) in the presence of sepiolite and kaolinite was investigated.The Zn-free clays were found to have a negative impact on the growth of C.pyrenoidosa in comparison with control samples (without adding any clay or Zn(Ⅱ)).When Zn(Ⅱ) was added,the algae in the presence of clays could be better survived than the control samples,which was actually caused by a decrease in Zn(Ⅱ) concentration in the solution owing to the adsorption of Zn(Ⅱ) on the clays.When the solution system was diluted,the growth of algae could be further inhibited as compared to that in a system which had the same initial Zn(Ⅱ) concentration as in the diluted system.This in fact resulted from desorption of Zn(Ⅱ) from the zinc-contaminated clays,although the effect varied according to the different desorption capabilities of sepiolite and kaolinite.Therefore the adsorption and desorption processes of Zn(Ⅱ) played an important part in its toxicity,and adsorption and desorption of pollutants on soils/sediments should be well considered in natural eco-environmental systems before their risk of toxicity to aquatic organisms was assessed objectively.