农用化学物质、有毒化学物质污染及其防治

X592200602813新农药硫肟醚在土壤中的降解/欧晓明(湖南化工研究院国家南方农药创制中心湖南基地)…∥中国环境科学/中国环境科学学会.-2005,25(6).-705~709环图X-58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…     

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.     

中国火力发电燃料消耗的生命周期排放清单

介绍了火力发电因化石燃料消耗而引起主要气态污染物排放量的估算方法,计算得到中国火力发电燃料消耗所引起的生命周期总排放量及单位售电的生命周期排放清单.与2002年中国火力发电燃料消耗相关的CO₂、SO₂、NO_x、CO、CH₄、NMVOC、烟尘、As、Cd、Cr、Hg、Ni、Pb、V和Zn的单位售电生命周期排放量分别为1.07、9.93×10^-3、6.46×10^-3、1.55×10^-3、2.60×10^-3、4.87×10^-42.02×10^-22.00×10^-61.27×10^-81.69×10^-78.78×10^-82.50×10^-71.76×10^-62.88×10^-62.40×10^-6g/(kW     

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.     

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.     

小球藻对新杀虫剂HNPC-A9908的富集与降解

HNPC-A9908[O-(3-苯氧苄基)-2-甲硫基-1-(4-氯苯基)丙基酮肟醚]是国家南方农药创制中心湖南基地研制成功的具有自主知识产权的一种新型杀虫剂.作者研究了蛋白核小球藻对HNPC-A9908的富集与降解.结果表明,蛋白核小球藻具有降解HNPC-A9908的能力,在20,100,400mg/L的浓度下,5d内HNPC-A9908的降解率分别为90.50%、66.02%和43.19%,日平均降解速率分别为3.60,13.20,34.55mg/L,其降解动力学方程可用二级反应动力学方程很好地拟合,拟合度达到83%以上.此外,蛋白核小球藻对HNPC-A9908也具有一定的富集能力,当浓度为20,100,400mg/L时达到最大富集的时间分别为24,48,48h,富集量分别为11.58,15.15,16.42mg/gFW,此后随时间的延长而逐步降低.     

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).     

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     

吡草醚水解动力学的研究

研究了吡草醚在不同pH和温度条件下的降解动力学情况,以及在三种生态水样和土悬液中的水解情况。结果表明,吡草醚在酸性水环境中比较稳定,在中性和碱性环境中易降解;水解反应速率随反应温度的升高而增大;吡草醚在三种生态水中的降解速率较快,降解半衰期分别为：水库水4．56d,河水3．96d,池塘水1．35d;吡草醚在土悬液中降解较快,这与其碱性条件和含量较高的可溶性碳有关。     

吡草醚水解动力学的研究

研究了吡草醚在不同pH和温度条件下的降解动力学情况,以及在三种生态水样和土悬液中的水解情况。结果表明,吡草醚在酸性水环境中比较稳定,在中性和碱性环境中易降解;水解反应速率随反应温度的升高而增大;吡草醚在三种生态水中的降解速率较快,降解半衰期分别为：水库水4．56d,河水3．96d,池塘水1．35d;吡草醚在土悬液中降解较快,这与其碱性条件和含量较高的可溶性碳有关。     

环己酮肟槽风险控制技术

运用危险与可操作研究(HAZOP)和故障失效模式分析方法(FMEA),对己内酰胺装置的环己酮肟贮槽及其物料输送过程存在的危险有害因素进行了系统分析,并针对存在火灾爆炸等风险性,从工艺、设备及安全管理等方面提出了对策措施.     

环己酮肟液相重排工艺危险性分析

国内己内酰胺生产中环己酮肟液相重排反应主要分为溶剂法和非溶剂法。通过对两种工艺装置中的物料和工艺危险性进行分析,表明两种重排反应工艺危险区别主要在于:溶剂法中正己烷溶剂可能导致燃爆危险,非溶剂法中水泄漏将导致失控反应。为己内酰胺的重排装置的安全稳定运行提出建议。     

Dynamics of novel insecticide HNPC-A9908 residue in vegetable-field ecosystem

HNPC-A9908 （o-（3-phenoxybenzyl）-2-methylthio-1-（4-chlorophenyl） propyl ketone oxime）, a novel oxime insecticide, is a highly effective and broad-spectrum insecticide which can be widely used to control many species of foliar insects on various crops. A study was conducted to evaluate the fate of HNPC-A9908 and study the degradation dynamics of HNPC-A9908 residue in vegetable field ecosystem. The results showed that degradation of HNPC-A9908 was much faster in vegetable pakchoi than in soil, and its half-life in pakchoi and soil was 1.32 and 3.75 d, respectively. The final residue of HNPC-A9908 in pakchoi was at the undetectable level to 0.122 mg/kg. As a conclusion, a dosage of 90 g/hm^2 was suggested and considered to be safe to human beings and animals.     

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.