沈阳市新城子铬渣堆存区土壤铬污染分布及形态分析

采用Tessier A连续提取法,研究分析了沈阳市新城子铬渣堆存区土壤中重金属铬的污染分布和迁移转化规律,土壤中重金属铬的5种形态分布,主要以残渣态和碳酸盐结合态为主,分别占总量的49.74%和21.4%,而有机结合态含量最低,占总铬含量的6.25%。不同的功能区域铬的形态分布有所不同。总体的分布特征是残渣态>碳酸盐结合态>交换态>铁猛氧化态>有机态。     

化学修饰电极预富集—石墨炉原子吸收法测定土壤中可溶性铅

研究了用Ｎａｆｉｏｎ化学修饰电极预富集－石墨炉原子吸收法测定土壤中可溶性铅的方法。土壤经０．１ｍｏｌ／Ｌ ＨＣｌ处理，以Ｎａｆｉｏｎ修饰的钨丝电极富集可溶性痕量铅后，放入石墨杯中进行原子吸收法测定。实验结果，在ｐＨ３．５的ＨＣｌ介质中，测定的线性范围为０～４．５μｇ／Ｌ，检测限为０．０４μｇ／Ｌ；对浓度为２μｇ／Ｌ的铅标准溶液平行测定１０次，相对标准偏差为２．６％；１０多种离子不干扰测定，样品回收     

添加稳定剂对尾矿土中砷形态及转换机制的影响

土壤中As的不同存在形态影响着其毒性、可移动性、生物有效性,且产生不同的环境影响.本研究以粉煤灰、干化污泥、硫酸亚铁、碎花生壳为稳定剂,探讨其对土壤As的稳定化效果以及p H、有机质和阳离子交换量与土壤As形态的关系.结果表明添加稳定剂后,土壤p H及有机质含量上升,残渣态砷含量升高.添加10%粉煤灰、10%干化污泥后,可交换态As、碳酸盐结合态As、铁锰氧化物结合态As、有机结合态As分别下降了34.2%、17.5%、19.9%、53.7%,并转化为残渣态As,其含量增长了1.14%.当同时添加10%粉煤灰、10%干化污泥和1%硫酸亚铁后,土壤中可交换态As、碳酸盐结合态As、铁锰氧化物结合态As、有机结合态As含量的降幅分别为62.3%、55.2%、29.6%、58.2%,残渣态As含量增加8.1%.添加10%粉煤灰、10%干化污泥、1%硫酸亚铁和1%粉碎花生壳后,可交换态As下降最显著,最大降幅为73.3%.施用适量的粉煤灰、干化污泥、硫酸亚铁能使土壤中的可交换态、碳酸盐结合态、铁锰氧化物结合态、有机结合态As的一部分转化为残渣态As,降低其毒性.提高p H,残渣态As含量上升,可交换态As、碳酸盐结合态As、铁锰结合态As、有机结合态As含量下降,As在接近中性的环境中稳定性最好;提高有机质含量,碳酸盐结合态As与残渣态As含量上升,可交换态As、铁锰结合态As、有机结合态As含量下降,有机结合态As含量下降明显;阳离子交换量上升,残渣态As含量上升,可交换态As、碳酸盐结合态As、铁锰结合态As、有机结合态As含量下降.     

Cr(VI)离子在TiO_2表面的吸附与光催化还原消除

随着体系ｐＨ值增大，Ｃｒ（ＶＩ）离子在ＴｉＯ２表面的吸附下降．当Ｃｒ（ＶＩ）离子初始浓度为３００μｍｏｌ／Ｌ时，其在ＴｉＯ２表面具有最大值吸附．Ｈ２ＰＯ４－阴离子及乙酸的存在对Ｃｒ（ＶＩ）离子的吸附有阻抑作用，甲酸存在会提高Ｃｒ（ＶＩ）离子的吸附．Ｃｒ（ＶＩ）离子在ＴｉＯ２半导体催化剂表面的光催化还原受体系的酸度影响较大．Ｈ２ＰＯ４－阴离子或Ｍｎ２＋离子存在会降低Ｃｒ（ＶＩ）离子的光催化还原效率．在太阳光照下，Ｃｒ（ＶＩ）离子在ＴｉＯ２上的光催化还原也可实现．通过调节反应结束后水溶液的酸碱度，Ｃｒ（ＶＩ）离子得以消除．反应后催化剂经酸处理，其活性恢复并可重复使用．     

土壤中铝的溶出及形态研究

用连续提取法研究１ｍｏｌ／ＬＫｃｌ,１ｍｏｌ／ＬＮＨ４Ａｃ,１ｍｏｌ／ＬＨｃｌ和０．５ｍｏｌ／ＬＮａＯＨ４种化学浸提液对土壤中铝的溶出,溶出名中用羊毛羊花菁Ｒ比色法测定。结果表明,铝的溶出量与与土壤类型、总铝、有机质含量等因素有关。１ｍｏｌ／ＬＫｃｌ浸提液对酸性土能溶出一定量的变换态铝,而对非酸性土则不能溶出或铝溶出量极微。０．５ｍｏｌ／ＬＮａＯＨ浸提出的铝量与总铝量之间有显著相关性。     

土壤铜、 铬(Ⅵ)复合污染重金属形态转化及其对生物有效性的影响

通过盆栽试验和室内化学分析相结合的方法,研究了外源铜、铬（Ⅵ）单一和复合污染中土壤金属形态转化及其对生物有效性的影响.结果表明,外源铜、铬（Ⅵ）单一污染土壤中,铬主要以残渣态和有机结合态形式存在,而铜则主要以铁锰氧化物结合态和残渣态形式存在.铜、铬（Ⅵ）复合污染时,低浓度铜（≤400 mg.kg-1）促进铬向交换态转化...     

2，4－二氯苯基荧光酮与铬显色反应的研究及其应用

研究了铬（Ⅵ）－２，４－二氯苯基荧光酮（ＤＣＩＰＦ）－溴化十六烷基三甲铵（ＣＴＭＡＢ）体系的显色条件。试验结果表明，在ｐＨ５．２～７．０范围内，铬与ＤＣＩＰＦ及ＣＴＭＡＢ形成红色三元胶束配合物，其最大吸收波长为５７８ｎｍ，表观摩尔吸光系数为１．４０×１０５ｌ·ｍｏｌ（－１）·ｃｍ（－１），铬（Ⅵ）含量在０～９．０μｇ／２５ｍｌ范围内符合比耳定律，配合物的组成为Ｃｒ（Ⅵ）：ＤＣＩＰＦ＝１：２。拟定方法用于水中铬的测定，结果满意。     

混凝沉淀法处理钮扣生产废水

进行了混凝沉淀法处理钮扣生产废水的研究，结果表明，当原水ＳＳ为１２００，ｇ／Ｌ，ＣＯＤＣｒ为１６５０ｍｇ／Ｌ，在水温１５℃，ｐＨ６．０－６．５，搅拌时间３－５ｍｉｎ，Ａｌ２（ＳＯ４）３投加量４００－５００ｍｇ／Ｌ，沉淀时间３０－４０ｍｉｎ的条件下，ＳＳ，ＣＯＤＣｒ去除率分别达到９０％，７５％以上。     

几种化学浸提剂对底泥重金属生物有效部分浸提效果的比较

采用微生态系统生物长期暴露试验,比较５种化学浸提剂对底泥重金属生物有部分的浸提效果。结果表明,０．００５ｍｏｌ／ＬＤＴＰＡ＋０．１ｍｏｌ／Ｌ ＴＥＡ＋０．０１ｍｏＬ ＣａＣｌ２,ｐＨ７．３０是一种适合于食腐屑底栖动物的底泥重金属生物有效部分浸提剂;而０．００５ｍｏｌ／ＬＤＴＰＡ＋１ｍｏｌ／Ｌ ＮＨ４ＨＣＯ３．ｐＨ７．６８则一种适合于滤食性动物和水生根系植物底泥重金属生物有效部分浸提剂。     

铁锈及Fe(OH)3处理硫酸盐废水厌氧方法试验

投加铁锈或Ｆｅ（ＯＨ）３可明显改善含高浓度硫酸盐有机废水的厌氧处理能力，使趋于失败的升流式厌氧污泥床ＵＡＳＢ恢复正常工作对ＳＯ４２－为５０００ｍｇ／Ｌ，ＣＯＤＣｒ为１５０００ｍｇ／Ｌ的合成脂肪酸废水，在水力停留时间为４ｄ，由４０％以下的ＣＯＤ去除率提高到投加铁锈或Ｆｅ（ＯＨ）３后的７３％和８２％，出口ｐＨ值由５３上升到７３，产甲烷气量由０.３Ｌ／ｄ上升为２２Ｌ／ｄ.并提出了Ｆｅ（ＯＨ）３比铁锈在去除Ｓ２－干扰更有效，去除Ｓ２-干扰可使厌氧处理恢复正常     

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

ＲｅｍｏｖａｌｏｆｈｅａｖｙｍｅｔａｌｓｆｒｏｍｓｅｗａｇｅｓｌｕｄｇｅｂｙｌｏｗｃｏｓｔｉｎｇｃｈｅｍｉｃａｌｍｅｔｈｏｄａｎｄｒｅｃｙｃｌｉｎｇｉｎａｇｒｉｃｕｌｔｕｒｅＷｕＱｉｔａｎｇ，ＮｙｉｒａｎｄｅｇｅＰａｓｃａｓｉｅ，ＭｏＣｅｈｕｉＦ...     

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.