高锰酸钾光氧化六氟苯脱氟的研究

尝试利用KMnO₄ 光氧化C₆F₆ 脱氟,获得较好的脱氟效果.研究表明,溶液的pH 值、激光脉冲次数、KMnO₄ 的初始浓度、C₆F₆ 的初始浓度等因素均会影响F-的生成率.酸性条件更有利于KMnO₄ 光氧化C₆F₆ 脱氟.F-生成率随激光脉冲数的增加而单调上升.受到消光系数的影响, KMnO4 的浓度达到3.0×10^-4mol/L 时,脱氟效率达到最佳. pH 值为0.5 的2.0×10^-4 mol/L C₆F₆ 与6.0×10^-4mol/L KMnO4 的混合溶液在接受脉冲激光照射9000 次后,F-生成率可达1.61mol/mol C6F6.C6F6 的降解与MnO4-受激后产生的Mn(V)过氧复合物有关.     

pH值对有机垃圾厌氧水解和酸化速率的影响

通过易腐性有机垃圾的批式厌氧发酵实验,比较不同的发酵液pH值对水解和酸化速率的影响.结果表明,发酵液的pH值为5～7时有利于颗粒态有机物的水解;在pH值不控制及pH值为5,6,7,8条件下,微生物处于静止生长期时,水解速率常数K分别为6.81×10^-5,6.57×10^-4,3.51×10^-4,7.55×10^-4,2.47×10^-4h-1.发酵液pH=7时最有利于微生物的合成代谢,从而促进碳水化合物和蛋白质的水解过程和酸化过程,表现为代谢产物如乙醇、乙酸、丁酸和氨氮的大量生成,以及其他代谢产物种类的增加;pH=5和pH=6时,反应后期能促进酸化过程;pH=8时,会抑制酸化过程;对pH值不控制时,严重抑制水解和酸化过程.     

大气中痕量烯烃的观测与分析

采用两步深冷冻浓缩自动进样系统,配以气相色谱/质谱联机对北京大气中的烯烃进行了连续观测.结果表明,北京市大气中浓度最高的烯烃为C4烯烃,2000年日平均浓度为3.5×10^-9±3.0×10^-9(V/V).2h平均浓度的日变化在春、夏、秋、冬4季各有特点,但基本上呈双峰型模态,峰值分别出现在上午和傍晚;在季节变化中,1、10月份大气中C4烯烃的浓度最高,为6.0×10-9±1.2×10^-9(V/V),3、9月份最低,为0.31×10^-9±0.13×10^-9(V/V).     

广州市大气中过氧化物的研究

采用高效液相色谱(HPLC)荧光法于1998年7月和10月测定了广州市大气中的5种过氧化 物:过氧化氢(H₂O₂)、羟甲基过氧化氢(HMHP)、甲基过氧化氢(MHP)、1-羟乙基过氧化氢(1-H EHP)及乙基过氧化氢(EHP).其中主要过氧化物是H₂O₂、HMHP和MHP,其最高浓度分别为1.6(10 ^-9、0.67(10^-9和0.54(10^-9(V/V).在光照强,相对湿度低的情况下,H₂O₂和MHP呈现明显的日 变化规律,早晚浓度低,最大值多出现在14:00～16:00.同时测定了大气温度,湿度和紫外辐射U VB及大气中O₃, NO_X和SO₂,发现H₂O₂和MHP与O₃、温度和UVB具有一定的正相关关系,而与NO_X, SO₂ 和相对湿度具有一定的负相关关系.     

新农药硫肟醚在土壤中的降解

在实验室条件下对新农药硫肟醚[o-(3-苯氧苄基)-2-甲硫基-1-(4-氯苯基)丙基酮肟醚]在不同地区土壤中的降解动态进行了研究.结果表明,硫肟醚在土壤中的降解遵循一级动力学方程.硫肟醚在非灭菌与灭菌长沙粉砂质黏土中的降解速率常数(k)分别为8.106×10^-3和1.630×10^-3,半衰期分别为85.5d和425.2d,微生物对硫肟醚在土壤中的降解具有显著的影响.硫肟醚在3种土壤中的降解速率大小依次为湖南永州重黏土>甘肃天水黏土>辽宁沈阳粉砂质黏土,其降解半衰期分别为46.1,63.8,70.0d,降解速率常数分别为1.503×10^-2,1.087×10^-2,9.904×10^-3.根据国内农药在土壤中的残留期划分标准,硫肟醚属于较易降解类农药.     

水体系中正癸烷和正癸烯的光催化降解

以300W中压汞灯为光源,分别研究了水体系中正癸烷(n-C₁₀H₂₂)和正癸烯(n-C₁₀H₂₂)在TiO₂光催化氧化作用下的降解.结果表明,它们的降解反应均符合一级动力学方程,在17.2nm TiO₂下,n-C₁₀H₂₂反应速率常数(k)值为5.8010^-3min^-1,半衰期(t1/2)为120min;n-C₁₀H₂₂的k值为9.9010^-3min^-1,t1/2为70min.400℃热处理的TiO₂对n-C₁₀H₂₂、n-C₁₀H₂₂光解的降解率分别为31%﹑50%,高于其他热处理温度.利用自旋俘获-电子顺磁共振(ST-EPR)方法,在光照的TiO₂磷酸盐缓冲水溶液(pH=7.4)中检测到羟自由基加合物(DMPO-OH).产物分析表明,水体中n-C₁₀H₂₂光催化降解生成的中间产物为1-癸醇、2-戊酮、2-庚酮和2-癸酮;n-C₁₀H₂₂的中间产物为辛醛、壬醛、癸醛和2-癸酮.     

模拟酸雨对砂浆影响的研究

建立了周期浸泡法和喷淋试验法等两种加速腐蚀试验方法,并分别研究Ph为5.6、3.5和Ph为1.0、S²₄-为0、0.06、0.1、0.2mol/L六种模拟酸雨对砂浆的影响。研究结果表明：砂浆受蚀后强度降低,其下降的程度与材料中CaO和SO₃/CaO的比值成二元线性关系;酸雨中＋的侵蚀将使材料中CaO、MgO、Al₂O₃和Fe₂O₃组分流失,H⁺.和SO的协同作用,使材料中的SO₃/CaO的比值增大;受蚀后的砂浆其物相发生较大的变化,变化趋势是原［CaNa］［SiAI］₄0₈、KAISi₃0₈、0.62NaAISi_{208·0.38CaAl2等矿物晶体逐渐消失,而转化成CaSO4·2H2O、CaAl2i2O8、Ca－Fe－Al－S－Si－O,甚至体积更大的Ca3Al6O12·CaSO4。因此,酸雨对砂浆的影响,主要是H⁺侵蚀引起的溶解腐蚀和SO²4-侵蚀引起的膨胀腐蚀。}     

厌氧－缺氧－好氧工艺去除废水中COD、氮和磷的研究

为了减少废水中营养盐的排放量,采用实验室规模的厌氧─缺氧─好氧工艺处理豆制品废水。结果表明,TCOD、SCOD、NH⁺₄-N、NO^-₃－N、TN、TP、SP（可溶性磷）、SS、细菌总数和大肠菌群数的去除率分别为96%、94％、93％、89％、82％、88％、78％、98.0％、99.9％以上。厌氧相产气率平均0.4L/L·d,上所产气体中平均甲烷含量69.8％,CO₂3.8％,N226.4%。缺氧相产气率平均为0.2L/L·d,平均甲烷含量59.5％,CO₂12％,N₂39.2％。好氧相中亚硝酸细菌含量为1.1×10⁵/mL,硝酸细菌含量为1.4×10³/mL。     

尿液、头发、指(趾)甲高铊汞砷是铊矿区污染标志

铊矿区村民尿液、头发和指（趾）甲中铊汞砷的含量高是矿区和村民受铊汞砷污染的标志,也是判别汞铊病的标志根据村民尿液中铊含量高低初步得出区别不同程度汞铊病患者的标准TL＞1000×10^-9、100×10^-9－1000×10^-9和＜100×10^-9分别为重汞铊病患者、轻汞铊病患者和非汞铊病者。人体和生物体中TL、Hg、As含量高低与矿区岩矿石、土壤和水体中TI、Hg、As的背景含量密切相关     

中国大陆生物质燃烧排放的污染物清单

根据2000年各省市生物质的消耗资料,结合排放因子,计算了中国大陆生物质燃烧所排放的SO₂、NO_x、NH₃、CH₄、EC、OC、VOC、CO、CO₂的总量及各省市的排放清单,并进一步细化到县、区级行政区.研究表明,生物质燃烧排放的污染物在地区间的分布极不均衡,排放量较大的包括华东、中南地区的各省市;各种生物质燃烧对各污染物的排放量的贡献差异很大,其中秸秆和薪柴是最主要来源;单位面积生物质燃烧排放污染物的量较高的地区由东北至中南围绕中国的主要农业产地呈带状分布.     

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.     

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.     

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.