巯基化合物存在下无机汞的光化学甲基化

本文研究了在巯基化合物L-半胱氨酸、硫代乙醇酸存在下醋酸水溶液中无机汞的光化学甲基化过程.结果表明巯基化合物对汞的甲基化具有明显的增强作用并在此过程中起光敏剂的作用.     

采用巯基捕收剂稳定化处理垃圾焚烧飞灰中的重金属

研究了3种巯基捕收剂,二乙基二硫代氨基甲酸钠（乙硫氮）、乙基黄原酸钾（乙基黄药）和二丁基二硫代磷酰铵（丁铵黑药）,对垃圾焚烧飞灰中重金属的稳定化效果.3种巯基捕收剂的用量均为62.5　μmol·g^-1飞灰.扫描电镜观察发现,飞灰经稳定化处理后,巯基捕收剂均匀地覆盖于飞灰晶体表面,使矿物晶体棱角变得模糊.利用酸浸提程序（TCLP法）和水浸提程序（水平振荡法）评价飞灰中重金属Cu、Pb、Cd、Cr和Zn的浸出毒性.在0.1 mol·L^-1醋酸浸提条件下,与Na₂S相比,巯基捕收剂对Cu和Pb的稳定化效果较好,其中乙硫氮对Cu的稳定化比率接近100%,丁铵黑药对Pb的稳定化比率达到69.2%;在水浸提条件下,乙硫氮、乙基黄药和丁铵黑药对5种重金属的稳定化比率分别为72.6%、73.5%和76.8%,显著高于Na₂S处理（52.4%）. 3种巯基捕收剂对5种重金属亲和力的强弱顺序大致为Cu＞Pb＞Cr＞Cd＞Zn,并且超过60%的巯基捕收剂与酸可浸提重金属离子发生了螯合沉淀反应.重金属-巯基捕收剂絮凝物在中性和碱性条件下（pH>6）比较稳定,在酸性条件下（pH<6）可发生部分溶解.为获得较好的重金属稳定化效果,维持稳定化飞灰的高酸缓冲容量十分重要.     

巯基功能化沸石吸附Hg2+特征及固化/稳定化含汞废物研究

采用3-巯基丙基三甲氧基硅烷在天然斜发沸石表面进行自组装巯基改性,制得巯基功能化沸石.研究了吸附剂用量、pH值、温度、Hg2+浓度和吸附时间对巯基功能化沸石吸附Hg2+的影响,测定了巯基含量,并进一步研究了吸附机理.同时,探讨了巯基功能化沸石吸附剂作为稳定化剂固化/稳定化含汞危险废物的可行性.结果表明,巯基功能化沸石具有较高的巯基含量（1.91%±0.01%）,对Hg2+的吸附容量为87.72 mg·g-1,比天然沸石对Hg2+的吸附容量（8.06 mg·g-1）提高了近10倍.巯基功能化沸石吸附Hg2+的机制主要是表面的巯基与Hg2+的反应,其受pH值、温度的影响小于天然沸石.动力学实验结果表明,巯基功能化沸石吸附Hg2+以较快的速率进行,3h时基本达到吸附平衡.巯基功能化沸石做稳定化剂能够促进汞的稳定,与单独使用水泥相比固化体浸出汞浓度显著降低,含汞1000 mg·kg-1的模拟废物固化体浸出汞浓度低于国家标准.     

巯基功能化重金属处理剂研究

巯基功能化重金属处理剂是人们目前关注的重金属废水新型处理药剂,已在重金属废水处理中得到广泛应用.文章就近年来巯基功能化有机高分子处理剂、巯基功能化无机介孔处理剂、巯基功能化磁性纳米处理剂的研究进展进行了综述,并分析了在种类开发、制备工艺和重金属捕集等方面存在的主要问题,指出了今后研究的发展趋势.     

巯基树脂的合成及对Hg2+的吸附特征

使用聚苯乙烯交联微球为前驱体,经一系列反应合成了一种苯环上含巯基的离子交换树脂(巯基树脂),研究了其对水中Hg2+的吸附特征. 巯基树脂的红外与元素分析结果表明,巯基官能团成功地嫁接到树脂表面,树脂中b(巯基)为2.89 mmol/g. pH对吸附的影响较大,当pH为1时,巯基树脂对Hg2+的吸附量很低,因此,可以用酸洗树脂使其再生. 当pH为2～7时,巯基树脂对Hg2+的吸附量相差不大. 巯基树脂对水中Hg2+的吸附等温线结果表明,温度的升高有利于吸附,吸附量高达14.500 mg/g,且符合Langmuir模型. Hg2+在巯基树脂上的吸附符合准二级动力学方程,对于初始ρ(Hg2+)为1 mg/L的溶液,吸附后最终ρ(Hg2+)可降到0.003 mg/L.      

采用巯基捕收剂稳定化处理垃圾焚烧飞灰中的重金属

研究了3种巯基捕收剂,二乙基二硫代氨基甲酸钠（乙硫氮）、乙基黄原酸钾（乙基黄药）和二丁基二硫代磷酰铵（丁铵黑药）,对垃圾焚烧飞灰中重金属的稳定化效果。3种巯基捕收剂的用量均为62.5μmol?g-1飞灰。扫描电镜观察发现,飞灰经稳定化处理后,巯基捕收剂均匀地覆盖于飞灰晶体表面,使矿物晶体棱角变得模糊。利用酸浸提程序（TCLP法）和水浸提程序（水平振荡法）评价飞灰中重金属Cu、Pb、Cd、Cr和Zn的浸出毒性。在0.1mol?L-1醋酸浸提条件下,与Na2S相比,巯基捕收剂对Cu和Pb的稳定化效果较好,其中乙硫氮对Cu的稳定化比率接近100%,丁铵黑药对Pb的稳定化比率达到69.2%;在水浸提条件下,乙硫氮、乙基黄药和丁铵黑药对5种重金属的稳定化比率分别为72.6%、73.5%和76.8%,显著高于Na2S处理（52.4%）。三种巯基捕收剂对5种重金属亲和力的强弱顺序大致为Cu＞Pb＞Cr＞Cd＞Zn,并且超过60%的巯基捕收剂与酸可浸提重金属离子发生了螯合沉淀反应。重金属-巯基捕收剂絮凝物在中性和碱性条件下（pH>6）比较稳定,在酸性条件下（pH<6）可发生部分溶解。为获得较好的重金属稳定化效果,维持稳定化飞灰的高酸缓冲容量十分重要。     

改性蒙脱土对稻田土壤甲基汞的阻控修复

采用3-巯丙基三甲氧基硅烷和壳聚糖对蒙脱土进行改性,利用XRD技术对改性蒙脱土进行表征,并通过室内模拟试验,探讨在不同的水分条件下,巯基蒙脱土和壳聚糖蒙脱土对甲基汞污染土壤的阻控修复效果.XRD分析结果显示,巯基和壳聚糖都成功负载于蒙脱土上.模拟试验结果表明,在甲基汞污染土壤中添加修复材料后,对土壤甲基汞均产生了较好的阻控修复效果.对比空白对照,在淹水条件下,土壤中甲基汞含量分别降低了82. 10%(巯基蒙脱土)和45. 20%(壳聚糖蒙脱土);在干湿交替条件下,土壤中甲基汞含量分别降低了66. 70%(巯基蒙脱土)和49. 79%(壳聚糖蒙脱土);在干旱条件下,土壤中甲基汞含量降低了44. 66%(巯基蒙脱土),添加壳聚糖蒙脱土4周后,土壤甲基汞含量降低了54. 37%.相比单加改性蒙脱土,联合添加改性蒙脱土和石灰处理后其修复效果没有明显提升.     

巯基改性玉米秸秆吸附Hg(Ⅱ)的热力学特征研究

采用化学反应的合成方法向玉米秸秆中引入巯基官能团,并进行电镜扫描、红外光谱和X射线电子能谱分析.在此基础上,以巯基改性玉米秸秆为吸附剂,通过批处理试验讨论了吸附时间、体系pH和温度等因素对水体中Hg(Ⅱ)吸附的影响.结果表明,采用该合成方法可以成功地向玉米秸秆中引入0.98%的巯基官能团,巯基改性玉米秸秆对水体Hg(Ⅱ)的吸附最佳pH为6,吸附能在120min内达到平衡,在285K时对Hg(Ⅱ)的最大吸附量可达80.04mg·g-1.吸附过程是自发的放热过程,可用Langmuir模型描述,其吸附机理可能为络合反应控制的化学吸附.研究表明,巯基改性玉米秸秆是一种对水体Hg(Ⅱ)具有良好吸附能力的生物吸附剂.     

Cr6+对人血红细胞膜的损伤及茶多酚对其保护作用的分子机理研究

采用TBA(thiobatbrturic acid)法和ESR自旅标记技术,测定了无机致癌物重铬酸钾(Cr~(6+))对红细胞膜的蛋白巯基和磷脂的作用,结果表明,Cr~(6+)引发红细胞膜产生脂质过氧化的同时,膜上蛋白巯基构象和磷脂的流动性发生改变.而茶多酚对Cr~(6+)引起红细胞膜上的这些变化均有明显抑制作用.     

巯基膨润土影响土壤镉形态及水稻酶活性研究

使用自主研发的巯基化膨润土作为钝化剂治理镉污染水稻土。在镉污染水稻土中添加不同量巯基化膨润土,种植水稻,实验结果表明,添加了巯基化膨润土,土壤有效镉含量下降,添加量越大,下降越明显,有效态镉下降量与巯基化膨润土添加量具有显著相关性;分蘖期水稻叶片中过氧化氢酶(CAT)、超氧化物歧化酶(SOD)、过氧化物酶(POD)活性最大分别下降了70.83%、29.42%和43.82%,酶活性下降量与巯基化膨润土添加量具有显著相关性。该研究为巯基化膨润土修复镉污染土壤提供了基础数据。     

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.     

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.     

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.