平顶山矿区一矿煤矸石中微量元素赋存状态研究

采用逐级化学提取法研究平顶山矿区一矿煤矸石中Be、V、Cr、Co、Ni、Cu、Sr、Mo、Cd、Sb、Ba、Pb、Th、U、Hg、As、Se等17种有害微量元素的赋存状态,采用电感耦合等离子体质谱法(ICP-MS)和原子荧光光谱法(AFS)分析了煤矸石和各提取状态样品的微量元素含量。结果表明:煤矸石的有害微量元素均以残渣态为主,碳酸盐结合态、Fe-Mn氧化物结合态、有机物和硫化物结合态次之,可交换态的含量相对较少。各种微量元素在某一赋存状态下所占的质量比例相差较大,对环境的潜在危害性不同。V、Sr、Cd、Ba、Pb、Hg、Se的潜在可淋失率超过了10%,在表生地质条件下对环境具有较大的危害性。     

连环湖阿木塔泡沉积物中重金属形态及其对环境影响分析

采用了BCR三步提取法,对连环湖阿木塔泡AMT岩芯沉积物中的Mn、Cr、Cu、Fe、Ni、Pb和Zn等7种重金属元素的化学形态进行了分析。结果表明：Cr、Cu、Fe、Ni、Pb、zn元素以残渣态为主,Mn元素以可交换态及碳酸盐结合态为主。Cr、Cu、Ni、Pb的有机物及硫化物结合态、Fe—Mn氧化物结合态含量较高,Zn的有机物及硫化物含量较高。其中,Mn、Cr、Ni和Pb对环境产生危害的可能性最大,对这几元素应该予以足够的关注。     

厦门筼筜湖表层沉积物金属元素赋存形态及污染评价

用ICP-MS测定了厦门筼筜湖表层沉积物中15种金属元素的含量,分析了金属元素的分布特征,并用改进的BCR提取法分析其赋存形态.结果表明,Cd、Cu、Sr、Pb、Zn和U在不同湖区的含量表现为:外湖干渠内湖;Cr、Co、Ni、V、Fe、Li、Rb和Mn的含量表现为:内湖外湖干渠.Cu、Zn和Pb主要存在于可还原态;Cd元素主要存在于弱酸溶态和可还原态;Co、Ni、U、Fe和Mn元素主要存在于可还原态和残渣态;Li、V、Cr、Rb和Ba主要存在于残渣态.潜在生态风险评价结果表明,元素V、Cr、Co、Ni、Zn、Cu、Cd和Pb等处于轻微潜在生态风险水平.次生相与原生相分布比值法评价结果显示,Cu、Cd和Zn表现出重度污染;Pb表现出中度污染;Co、Mn、Sr和U表现出轻度污染;Ni、Fe、Cr、V、Li、Ba和Rb表现出无污染.筼筜湖表层沉积物已受轻微的金属元素污染,处于轻微生态风险水平.     

安溪铁观音茶园土壤重金属赋存形态及生态风险评价

用改进的BCR连续提取法提取安溪铁观音茶园土壤中重金属元素(Li、Fe、Zn、Ba、Sr、Ti、Co、Cr、Cd、Mn、Ni、Pb、V、Mg、Cu)的赋存形态,分析其生物有效性并作出生态风险评价。重金属赋存形态研究结果表明,Cd的形态总体分布为弱酸溶态残渣态可还原态可氧化态,Pb的形态总体分布为可还原态可氧化态弱酸溶态残渣态,Cu的形态总体分布为可还原态可氧化态残渣态弱酸溶态,其余重金属皆以残渣态为主。生物有效性分析结果表明,Pb、Cd、Cu、Mn、Ni、Sr等重金属的潜在生物可利用性较高,其所占百分比分别为90.4%、73.0%、36.6%、32.8%、23.8%、22.9%。对茶园土壤中的重金属作生态风险评价,地累积指数法和潜在生态危害指数法结果均表明,大部分土壤样品是清洁安全的,部分土壤受到Cd元素污染,污染程度达到中度污染级别。     

典型有色金属矿山城市小河流沉积物重金属形态分布及风险评估

采用改进的Tessier连续提取法分析了铜陵市惠溪河表层沉积物中7种重金属(Cd、Cr、Cu、Zn、Ni、Pb、As)的形态分布,并以风险评价编码法(RAC)和平均沉积物质量基准系数法(SQG-Q)对沉积物重金属污染程度和生态风险进行评价.结果表明:①Cr和As主要以残渣态存在,Zn、Ni和Pb主要以残渣态和Fe-Mn氧化物结合态存在,Cu主要以有机结合态存在,Cd有机结合态的质量分数较低,其它几种形态大体接近.②Cd、Cr、Cu、Zn、Ni、Pb和As有效态的质量分数分别为46.48%、4.62%、4.05%、4.12%、9.17%、0.97%和0.03%;按照RAC判定,Cd对环境构成高风险,Cr、Cu、Zn和Ni的环境危害处于低风险水平,Pb和As则无风险.③惠溪河沉积物SQG-Q均值为10.42,远大于1.0,表明该河流具有非常高的潜在生物毒性效应;Cd、Cr、Cu、Zn、Ni、Pb和As的PEL-Q系数分别为4.23、1.14、20.75、6.04、2.33、4.58和41.71,表明7种重金属的潜在生物毒性很大,不利生物效应将频繁发生.     

密云水库入库河流沉积物中重金属形态分析及风险评价

研究了北京市密云水库入库河流潮白河水系沉积物中重金属的总量及形态分布特征,采用风险评价准则法（RAC）和Tucker3 模型探讨沉积物中重金属的潜在危害性.结果表明,Hg、Cd、Cr、Cu、V、Zn的平均含量均超过北京市土壤背景值,呈现一定的富集.形态分析表明,Cu的残渣态含量占总量的72%,其次为有机结合态,占22%;Mn的残渣态含量占总量的62%,铁锰氧化物结合态占23%,碳酸盐结合态占10%;Ni的残渣态含量占总量的73%,铁锰氧化物结合态占13%,有机结合态占11%;Pb、Cd、V、Zn均以铁锰氧化物结合态和残渣态为主,含量占总量的90%以上.Ti、Cr则以残渣态为主要形态.RAC评价结果显示,Cr、V、Ti对环境无风险,Ni处于无风险到低风险级,Cu处于低风险级,Cd、Pb、Mn处于低风险到中等风险级.研究结果将为北京市水源保护、人体健康安全保护措施的制定提供科学依据.     

重金属元素BCR提取法及在太湖沉积物研究中的应用

采用BCR提取法,HCl-HNO3-HF消化法和ICP-AES仪器测定了西太湖沉积岩芯中Cu,Fe,Mn,Ni,Pb和Zn 6种重金属元素不同形态的质量分数.结果表明:采用BCR方法对太湖沉积物重金属元素形态进行提取,提取结果具有较高的精度和稳定性;受元素地球化学性质及沉积物理化性质的影响,Cu,Fe,Ni和Zn以残渣态为主;Mn以可交换态及碳酸盐结合态为主;Pb的有机物及硫化物结合态,Fe/Mn氧化物结合态以及残渣态的质量分数基本一致;重金属元素Fe/Mn氧化物结合态的质量分数与可还原态Mn质量分数有较好的正相关性,有机物及硫化物结合态的质量分数与有机质质量分数相关性较好.      

厦门西港潮间带柱状沉积物重金属赋存形态与污染评价

采用改进的BCR四步提取法研究厦门西港潮间带柱状沉积物中12种重金属元素(Ba、Co、Cr、Cu、Fe、Mn、Zn、Ni、Pb、Sr、V和Ti)不同形态的分布特征,并利用次生相和原生相比值法进行重金属污染评价。结果表明:在1975~2013年所对应的沉积柱中,Fe、Zn、Ba、Ti、Co、Cr、Ni、V和Cu主要以残渣态为主,Sr和Mn主要以弱酸溶态赋存,Pb以可还原态和残渣态为主。次生相和原生相比值法评价结果表明,Pb在1981~1983年、1991~2003年处于轻度到中度污染水平,作为生物成因元素的Sr和Mn不适于用本法评价,其他金属均未受到污染。     

工矿型绿洲城郊排污渠沉积物重金属的形态分布规律及风险评价

采用Tessier连续提取法、相关分析、富集因子法(EF)和风险评价编码法(RAC),研究了干旱区工矿型绿洲(以白银为例)城郊排污渠沉积物重金属Cu、Zn、Cd、Pb、Ni、Cr的形态分布规律及潜在环境风险.结果表明,东、西大沟沉积物中各重金属元素平均含量除Cr外,均明显高于甘肃省土壤背景值.富集因子法评价表明,东、西大沟沉积物中Cd富集较为严重,达极强污染水平.形态分析表明,东大沟沉积物中Zn、Ni、Cr以残渣态为主,Cu、Cd以有机结合态为主,Pb以铁锰氧化物结合态为主;西大沟沉积物中Pb以铁锰氧化物结合态为主,其余元素均以残渣态为主.风险评价编码法(RAC)结果显示,东大沟沉积物各重金属的风险等级为:NiCdPbCuZnCr,其中Ni的风险等级最高,处于高风险水平;西大沟沉积物各重金属的风险等级为:PbCdNiCuZnCr.其中Cd、Pb、Ni风险等级最高,处于高风险水平.     

铜陵市惠溪河滨岸带土壤重金属形态分布及风险评估

为揭示惠溪河滨岸带土壤重金属(Pb、Cu、Zn、Ni、Cr、Cd和As)形态分布和生态风险状况,沿河采集12个采样点的土壤样品,采用改进的Tessier五步连续提取法开展形态分析,并以Hkanson潜在生态危害指数法进行生态风险评估. 结果表明:①As和Cr以残渣态占绝对优势,Zn、Pb和Ni以残渣态和Fe-Mn氧化物结合态为主,Cu则以残渣态和有机结合态为主,Cd具有形态多样的分布特征;②7种重金属污染程度排序为As＞Cd＞Zn＞Cu＞Pb＞Ni＞Cr,潜在生态风险大小排序为Cd＞As＞Cu＞Pb＞Ni＞Zn＞Cr,其中Cd和As属极高风险等级,Cu为中等风险等级,其他4种元素则为轻微风险等级;③根据潜在生态风险指数,小倪村、狼尾湖右岸和大倪村采样点属于高风险等级,其他9个采样点均属于很高风险等级;④由综合污染及潜在生态风险贡献率水平,初步判定As和Cd为惠溪河滨岸土壤重金属污染治理和修复的优先控制对象.      

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.