微波消解石墨炉原子吸收法测定空气中的锑及其化合物研究

建立了用微孔滤膜采集空气样品,经硝酸-双氧水混合液微波消解,以硝酸镁溶液为基体改进剂,热解涂层石墨管,塞曼扣背景,石墨炉原子吸收法测定空气中锑的方法.方法线性范围为3.00～20.0μg/L,当采样体积为100 L,锑的最低检出质量浓度为0.000 5 mg/m3,加标回收率在93.0％ ～ 105.0％间,相对标准偏差均小于3％.该方法具有操作简便、快速、准确度高和用酸量少等优点,适用于空气中微量锑及其化合物的测定.     

微波消解-原子荧光光谱法测定土壤中砷的分析方法

为了建立一种快速测定土壤中砷方法,用微波消解仪对土壤样品进行消解,通过AFS-3100双道原子荧光光度计,选择最佳的仪器条件,及酸度,硼氢化钾浓度,测定土壤中的砷.本法线性关系砷为0～10 μg/L,相关系数0.9994,检出限砷为0.003μg/L.本方法操作简单,灵敏度高,快速,适于土壤中砷的测定.     

ICP-MS法同时测定饮用水源水特定项目中10种痕量重金属

以Li,In,Bi混合内标为校正系统,采用电感耦合等离子体质谱法同时测定饮用水源水特定项目中铍、硼、钛、钒、钴、镍、钼、锑、钡、铊等10种金属元素,优化了仪器测量、内标元素等实验条件.10种金属元素在0～ 200μg/L范围内线形良好,检出限为0.006～1.0 μg/L,标准样品均在保证值范围内,平行测定RSD为0.25％～3.42％,实际水样的加标回收率为94.0％～ 104％.     

离子色谱法测定地下水中碘离子

建立毛细管离子色谱-积分安培检测法测定地下水中碘离子的方法.样品经0.20 μm滤膜过滤后注入离子色谱仪,采用IonPac AS16阴离子交换分离柱分离,62.5 mmol/L NaOH溶液梯度洗脱,由安培检测器积分安培检测模式定量检测.方法检出限为0.20 μg/L,线性范围5～100μg/L,相关系数0.9999.重现性良好,相对标准偏差小于0.6％(n=9).加标回收率为91.2％～106.0％.     

甲萘威的淡水水生生物水质基准研究

为保护我国淡水水生生物,收集、筛选出5门23科44个物种的急性毒性数据和1门1科2个物种的慢性毒性数据,分别采用毒性百分数排序法和物种敏感度分布法,对我国甲萘威的淡水水生生物水质基准进行推导. 结果表明:我国淡水水生生物物种的急性毒性平均值范围为2.25～27 609 μg/L,甲壳纲急性毒性平均值范围为2.25～1 000 μg/L,鱼纲急性毒性平均值范围为700～27 609 μg/L,最敏感的物种为棘爪网纹溞,最不敏感的物种为胡鲶. 毒性百分数排序法推导出的基准最大浓度和基准连续浓度均为2.6 μg/L,物种敏感度分布法推导出的短期危险浓度和长期危险浓度分别为3.3和1.6 μg/L. 中美甲萘威的水质基准值差异归因于两国生物区系的不同. 甲壳纲对甲萘威的敏感度大于鱼纲. 初步统计表明,在22个天然水体样品中,有50%样品的甲萘威浓度高于淡水水质基准,存在环境风险.      

长江武汉段水体邻苯二甲酸酯分布特征研究

分别采集了丰水期和枯水期时长江武汉段30个点位上的河水和沉积物样品,用气相色谱法对样品中的邻苯二甲酸酯类(PAEs)含量进行测定,分析其在长江武汉段水体中的分布特征.结果表明,[1]丰水期时支流和湖泊水中PAEs浓度范围为0.114～1.259 μg/L,枯水期时为0.25～132.12 μg/L.丰、枯水期干流水相中PAEs的浓度范围分别为0.034～0.456 μg/L和35.73～91.22 μg/L,均有沿程升高的趋势.[2]枯水期支流和湖泊沉积相中PAEs浓度范围为6.3～478.9 μg/g,邻苯二甲酸二丁酯(DBP)、邻苯二甲酸双(2-乙基己基)酯(DEHP)有由水中向沉积物中迁移的较强趋.丰、枯水期干流沉积相中PAEs浓度范围分别为151.7～450.0 μg/g和76.3～275.9 μg/g;丰水期时DBP由沉积相向水相迁移,枯水期时DEHP在沉积物中未达到吸附最大.[3]5种被研究的邻苯二甲酸酯类化合物中, DBP和DEHP是主要污染物,国家地表水环境质量标准规定这2种物质的标准限值分别为0.001、0.004 mg/L,丰水期时所有的干支流均符合此标准,枯水期时干支流超标率为82.4%.[4]长江武汉段PAEs污染水平与意大利Velino河以及黄河中下游水体相近,但丰水期时水相PAEs含量远低于国内外一般水平.     

鱼体中多氯联苯的气相色谱/质谱分析研究

建立了鱼体中共平面多氯联苯(co-PCBs)和指示性多氯联苯(indicator PCBs)残留量的快速溶剂萃取气相色谱质谱分析方法.结果表明,18种多氯联苯在20 μg/L～500 μg/L范围内线性良好(r＞0.998),方法的检出限为0.2 ng/kg～0.5 ng/kg.当添加浓度为100 ng/kg时,多氯联苯的回收率为70.2％～113.5％.该方法前处理简便快速,准确性高,满足鱼体痕量多氯联苯残留的分析要求.     

球磨仪制样-微波消解-GFAAS法测定土壤中铅

建立了行星式球磨仪制样一微波消解一石墨炉原子吸收光谱法测定土壤中铅的方法。标准曲线在0—10．01μg／L范围内线性良好,以称样0．5g、定容体积50ml计,方法检出限为0．10mg／kg,土壤样品测定的RSD〈4％,加标回收率为91．4％～102％。     

石墨炉原子吸收法测定土壤中的锡

研究了硝酸－高氯酸体系消解、石墨炉原子吸收法测定土壤中锡的方法。采用酒石酸－锆复合溶液作基体改进剂,锆涂层热解石墨管为原子化器。方法的检出限为3μg/L(样品消解溶液)。实际样品测定的相对标准偏差小于7.5%,加标回收率为90%～97%。      

夏季渤海湾及邻近海域颗粒有机碳的分布与物源分析

根据2006年8月在渤海湾及其邻近海域41个站位取得的155个样品的颗粒有机碳（POC）和颗粒氮（PN）的分析数据,结合同步获得的水文环境要素资料,分析了该区夏季POC和PN的空间分布特征、影响因子与有机碳物源．结果表明,夏季水体中POC的浓度为155.9～1363.1 μg/L,平均浓度为429.5 μg/L; PN的浓度为26.2～225.5 μg/L,平均浓度111.5 μg/L. POC与PN的空间分布特征一致,呈现近岸高、远岸低、表层低、底层高的特点. 生物作用、水体温盐跃层和总悬浮颗粒物（TSM）是影响研究区POC空间分布的重要原因. POC与TSM的相关分析表明,POC与TSM之间具有正相关关系,不同来源的TSM是控制水体中POC浓度高低的重要因素. 本区POC/PN的比值范围为3.4～7.0,但这一物源指标的应用受到海水中颗粒无机氮（PIN）的影响. 通过建立POC和PN的一元线性回归模型,估算了样品中PIN的含量. 扣除样品中PIN的影响后,本研究区的POC/PON (颗粒有机氮) 比值范围介于5.5～19.8之间,显示POC除了海洋生物为主要来源外,周边河流的陆源输入也有重要贡献.这一研究方法对认识中国近海的POC物源具有一定的参考价值．     

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.     

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.     

Removal of heavy metals from sewage sludge by low costing chemical method and recycling in agriculture

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Isolation and preliminary characterization of a 3-chlorobenzoate degrading bacteria

A study was conducted to compare the diversity of 2-, 3-, and 4-chlorobenzoate degraders in two pristine soils and one contaminated sewage sludge. These samples contained strikingly different populations of mono-chlorobenzoate degraders. Although fewer cultures were isolated in the uncontaminated soils than contaminated one, the ability of microbial populations to mineralize chlorobenzoate was widespread. The 3- and 4-chlorobenzoate degraders were more diverse than the 2-chlorobenzoate degraders. One of the strains isolated from the sewage sludge was obtained. Based on its phenotype, chemotaxonomic properties and 16S rRNA gene, the organism S-7 was classified as Rhodococcus erythropolis. The strain can grow at temperature from 4 to 37℃. It can utilize several （halo）aromatic compounds. Moreover, strain S-7 can grow and use 3-chlorobenzoate as sole carbon source in a temperatures range of 10-30℃ with stoichiometric release of chloride ions. The psychrotolerant ability was significant for bioremediation in low temperature regions. Catechol and chlorocatechol 1,2-dioxygenase activities were present in cell free extracts of the strain, but no （chloro）catechol 2,3- dioxygenase activities was detected. Spectral conversion assays with extracts from R. erythropolis S-7 showed accumulation of a compound with a similar UV spectrum as chloro-cis,cis-muconate from 3-chlorobenzoate. On the basis of these results, we proposed that S-7 degraded 3-chlorobenzoate through the modified ortho-cleave pathway.     

Single and joint effects of pesticides and mercury on soil urease

The influence of two pesticides including chlorimuron-ethyl and furadan and mercury （Hg） on urease activity in 4 soils （meadow burozem and phaeozem） was investigated. The soils were exposed to various concentrations of the two pesticides and Hg individually and simultaneously. Results showed that there was a close relationship between urease activity and organic matter content in soil. Chlorimuron-ethyl and furadan could both activate urease in the 4 soils. The maximum increment of urease activity by chlorimuronethyl was up to 14%-18%. There was almost an equal increase （up to 13%-21%） in the urease activity by furadan. On the contrary, Hg markedly inhibited soil urease activity. A logarithmic equation was used to describe the relationship （P〈0.05） between the concentration of Hg and the activity of soil urease in the 4 tested soils. Semi-effect dose （ED50） values by the stress of Hg based on the inhibition of soil urease in the 4 soils were 88, 5.5, 24 and 20 mg/kg, respectively, according to the calculation of the corresponding equations. The interactive effect of chlorimuron-ethyl or furadan with metal Hg on soil urease was mainly synergic at the highest tested concentrations.     

Organochlorine pesticides in soils under different land usage in the Taihu Lake region, China

A field study was conducted in the Taihu Lake region, China in 2004 to reveal the organochlorine pesticide concentrations in soils after the ban of these substances in the year 1983. Thirteen organochlorine pesticides (OCPs) were analyzed in soils from paddy field, tree land and fallow land. Total organochlorine pesticide residues were higher in agricultural soils than in uncultivated fallow land soils. Among all the pesticides, ΣDDX (DDD, DDE and DDT) had the highest concentration for all the soil samples, ranging from 3.10 ng/g to 166.55 ng/g with a mean value of 57.04 ng/g and followed by ΣHCH, ranging from 0.73 ng/g to 60.97 ng/g with a mean value of 24.06 ng/g. Dieldrin, endrin, HCB and α-endosulfan were also found in soils with less than 15 ng/g. Ratios of p,p'-(DDD DDE)/DDT in soils under three land usages were: paddy field ＞ tree land ＞ fallow land, indicating that land usage inlfuenced the degradation of DDT in soils. Ratios of p,p'-(DDD DDE)/DDT ＞1, showing aged residues of DDTs in soils of the Taihu Lake region. The results were discussed with data from a former study that showed very low actual concentrations of HCH and DDT in soils in the Taihu Lake region, but according to the chemical half-lives and their concentrations in soils in 1980s, the concentration of DDT in soils seemed to be underestimated. In any case our data show that the ban on the use of HCH and DDT resulted in a tremendous reduction of these pesticide residues in soils, but there are still high amounts of pesticide residues in soils, which need more remediation processes.     

Alterations of organ histopathology and metallolhionein mRNA expression in silver barb, Puntius gonionotus during subchronic cadmium exposure

Common silver barb,Puntius gonionotus,exposed to the nominal concentration of 0.06 mg/L Cd for 60 d,were assessed for histopathological alterations(gills,liver and kidney),metal accumulation,and metallothionein(MT)mRNA expression.Fish exhibited pathological symptoms such as hypertrophy and hyperplasia of primary and secondary gill lamellae,vacuolization in hepatocytes,and prominent tubular and glomerular damage in the kidney.In addition,kidney accumulated the highest content of cadmium,more than gills and liver.Expression of MT mRNA was increased in both liver and kidney of treated fish.Hepatic MT levels remained high after fish were removed to Cd-free water.In contrast,MT expression in kidney was peaked after 28 d of treatment and drastically dropped when fish were removed to Cd-free water.The high concentrations of Cd in hepatic tissues indicated an accumulation site or permanent damage on this tissue.