测定微量汞的问题

一、样品保存稀汞的蒸馏水溶液及天然水中之汞,储存时可迅速损失。储于密闭的容器中,溪水开始浓度为50ppb,15分钟损失达80％。汞损失的速度与量,随汞浓度、溶液组成及储存容器的类型而定。如其它金属离子一样,Hg~(2+)可被容器壁吸附而损失。水样中的汞可为悬浮粒子与聚乙烯容器吸附。有用10种不同材料的容器贮存20ppm及20ppb汞的2MHNO_3溶液,51天后对汞有不同程度的吸附,认为派立克司、聚碳酸酯及聚四氟塑料是合适的容器。汞溶液如不加硝酸调pH为0.5,可明显地被聚乙烯吸附。如不加硝酸保存,则80％聚集于颗粒物质,部分被容器吸附,仅10％留于溶液中。有用羊毛吸附汞,再以含有氯化钠的盐酸解吸,藉以保存水样。     

固定污染源非甲烷总烃测定中气袋影响研究

使用挥发性有机物标准气体对气相色谱法测定固定污染源中非甲烷总烃采样使用的气袋和阀体材质、进样前加热温度、样品保存时间等方面进行了研究,同时选择石化储运、涂料生产、工业涂装、包装印刷等4类典型行业进行了实际样品的验证。结果表明:FEP-进口和PVDF-进口气袋空白值最低;各类气袋样品加热至80℃的偏差均大于60℃,建议加热温度控制在60℃;对于成分复杂的样品,建议保存时间应在8 h以内。     

阳极溶出法研究容器壁表面对铅和镉的吸附特性

研究水的污染化学和野外采样或实验室分析工作中配制溶液和存放样品都涉及到在容器中贮存的问题,在贮存过程器壁对溶液中重金属离子有吸附作用.但环境中不少金属的测定值为ppb或亚ppb级,因此器壁对金属的吸附作用就不可忽视,否则会引起实     

铝箔复合膜气袋对二氧化硫吸附试验

通过铝箔复合膜气袋对二氧化硫在不同浓度、不同时间只附情况的实验，得出了不能用该气袋采集气体样品做二氧化硫测定的结论。     

不同植物废物对垃圾堆肥过程VSCs释放的影响

选取黄豆杆、红薯藤、菠萝蜜果核和紫檀树叶4种植物废物,分别与生活垃圾混合进行堆肥处理,考察堆肥过程中甲硫醇、甲硫醚、二甲基二硫醚3种含硫类可挥发性有机物(VSCs)释放量与植物废物性质之间的关系.结果表明,各工况下,3种VSCs释放均集中在堆肥初期(前6d),甲硫醇均为主要的恶臭贡献者.不同工况的3种VSCs释放浓度差异显著.其中,以红薯藤为堆肥配料的工况下3种VSCs累积释放浓度均最高,以黄豆杆和紫檀树叶分别为堆肥配料的工况相对较低,累积释放浓度仅为前者的16.0%~74.3%,并低于生活垃圾单独堆肥. VSCs释放水平与混合原料的易降解有机物含量呈正比,与其植物多酚的含量呈反比.     

淡水亚硝酸盐样品最佳保存条件的探讨

亚硝酸盐(NO_2~-)是自然界中生物地球化学氮循环重要关键物质,但不易保存。文章讨论了不同pH条件下对NO_2~-浓度测定的影响和不同储存条件下NO_2~-浓度的变化,并确定最佳保存条件。结果表明,当水样品调节pH>10,NO_2~-测定浓度偏低;而pH为自然或酸性时,对NO_2~-浓度测定几乎没有影响;HgCl_2的加入对测定结果不产生影响。但在长期保存时,pH为酸性时(pH=2),随保存时间增加,NO_2~-浓度快速下降。因此碱性条件下不适合测定,而酸性条件下不适合保存,并且建议野外采完样品后立即加入HgCl_2保存NO_2~-,并于60d内测定NO_2~-浓度。     

土壤样品保存过程中无机砷的形态变化及其样品保存方法

为选择合理的土壤样品保存方法,研究了不同保存条件下土壤样品及其水提取液中无机砷形态的动态变化．研究结果表明,采用常温方法保存土壤样品,其水溶态无机砷的总浓度变化不大,但水溶态As(Ⅲ)容易转化为As(Ⅴ);在风干条件下,随着保存时间的延长,样品中水溶态无机砷的总浓度和As(Ⅲ)浓度均会降低,As(Ⅲ)／As(Ⅴ)的比值呈增加趋势;在避光冷藏条件下,土壤样品中水溶态无机砷的总浓度、As(Ⅲ)和As(Ⅴ)浓度均基本保持不变．在避光冷藏、常温和冷冻条件下保存土壤水提取溶液,样品中无机砷的总浓度变化均不明显,但As(Ⅲ)浓度均呈下降趋势;避光冷藏条件下,As(Ⅲ)浓度在保存12d后缓慢下降,到第28天降低了9．0％;常温和冷冻条件下,As(Ⅲ)容易转化为As(Ⅴ)．因此,对于土壤中无机砷的形态测定而言,应采集新鲜土壤样品并在避光冷藏条件下保存．     

污染源非甲烷总烃CEMS参比方法温度问题讨论

从气袋的选择、气袋与温度、峰形与温度、样品气与柱箱温度几个方面探讨污染源非甲烷总烃CEMS参比方法温度问题。阐述了目前市场上流通的气袋材质不适宜加热;峰形与样品气成分及温度的联系;以及样品气分析时最佳柱箱温度条件。     

海底多金属硫化物矿床中的金

东太平洋海底扩张中心7个多金属硫化物矿床中的48个热液沉淀物样品的化学全分析表明,金的富集具有明显不同的模式。发现两个硫化物矿床样品中含金量高,即轴向海山和勘探者海岭南部。采自轴向海山矿床顶部的一个重达160kg的样品由二氧化硅、重晶石和闪锌矿组成。该样含金达6700ppb,平均为4900ppb。勘探者海岭南部的样品含金达1500ppb,平均660ppb。对这两个地区所采多种样品进行的详细矿物学研究及化学全分析表明,金的沉淀受元素伴生和共生次序的控制。浓度约为200ppb的金与高含量的铜(>1wt％)和钼(达470ppm)伴生;浓度高于800ppb的金与高含量锌(>10wt％)、钡(>3wt％)和二氧化硅(>20wt％)伴生;浓度高于1200ppb的金则与高含量的铅(>0.1wt％)、银(>100ppm)、砷(>300ppm)和锑(50—100ppm)伴生。两地所采的含金量最高的样品,均在非晶质二氧化硅基质中含有晚期泉华状低温铅、砷、锑、银和硫的硫盐。这些硫盐可能是金的贮集场所。 采于其他玄武岩型海底矿床(北纬21度地区、加拉帕戈斯裂谷、胡安德富卡海岭南部因代沃海岭)的贫金样品(<200ppbAu),与轴向海山和勘探者海岭南部样品相比,从发表的数据看,其金属和硫的含量高,但SiO_2含量低。瓜伊马斯盆地热液矿床下伏的沉积物,较洋中脊玄武岩富Au,但这些矿床中所采的样     

飞灰螯合剂中挥发性污染物的释放

采集了4个市售飞灰螯合剂样品，分析其在20，40℃下挥发性污染物的释放规律.结果表明，释放的挥发性污染物主要有甲醛、乙醛、苯、异戊醛/异丙醇、甲硫醇、乙硫醇等；其中3个螯合剂样品甲醛的释放浓度在20℃为748~1325 μg/L-螯合剂，占释放的易挥发污染物的68%~96%（质量比），在40℃为4282~6822 μg/L-螯合剂，占释放的易挥发污染物的87%~95%（质量比）.随着温度升高，释放的挥发性污染物种类变多，部分污染物浓度增加，40℃时，4个螯合剂样品释放的易挥发污染物浓度比20℃时增加了142%~444%.元素分析、拉曼光谱和热重分析结果表明，4个螯合剂的主要有效成分相似，为二硫代氨基甲酸盐类物质.因此，推测这种飞灰螯合剂在稀释和飞灰稳定化过程中，对工作人员的健康可能有潜在的危害风险，应收集释放的气体并进行处理；且在飞灰填埋过程中，可能会导致渗滤液中NH₄⁺-N等物质的浓度升高，增加渗滤液的处理难度.     

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.     

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.     

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.     

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.