江汉平原高砷地下水原位微生物的铁还原及其对砷释放的影响

微生物参与铁氧化物矿物的还原性溶解是高砷地下水形成的关键过程,其中具有砷还原功能的微生物如何参与含水层砷释放的生物地球化学过程亟待研究.利用从江汉平原典型高砷含水层中厌氧条件下分离出的四株细菌(Citrobacter sp.JH-1、Clostridium sp.JH-6、Exiguobacterium sp.JH-13、Paenibacillus sp.JH-33),通过室内厌氧模拟培养实验,查明其砷、铁还原能力,并通过分别与铁氧化物矿物及原位沉积物共同培养,探究原位含水层微生物参与的砷释放机理.结果表明:四株细菌均具有厌氧条件下砷、铁还原功能,Citrobacter sp.JH-1砷还原能力最强,96 h内还原的As(Ⅴ)浓度为2.22 μmol/L.其中Citrobacter sp.JH-1不仅可在厌氧和有氧条件下还原溶液中的As(Ⅴ),还可在厌氧条件下还原溶液中的Fe(Ⅲ)和无定型的水铁矿,在与含水层沉积物共培养12 d后,沉积物中铁与砷的释放量分别为510 mg/kg及1 150 μg/kg.江汉平原含水层中的原位微生物兼具砷/铁还原功能,在厌氧条件下可还原沉积物中的铁氧化物矿物并促进砷的释放,为深入揭示高砷地下水成因机理与地下水砷污染的防控提供重要科学依据.      

氧化还原生物对石门雄黄矿区尾矿砷释放行为研究

对石门4处典型不同种类的含砷尾矿进行样品采集,并采用1种氧化菌(氧化亚铁硫杆菌,Thiobacillus ferrooxidans,简称T.f)和2种还原菌(硫酸盐还原菌,sulfate reducing bacteria,简称SR;嗜酸铁还原菌,Acidiphilium cryptum JF-5,简称JF-5)分别对其进行作用,据此研究生物还原和氧化条件下原生和次生含砷矿物的释砷情况,进而确定潜在的释砷风险。ICP-OES定量分析显示,3种细菌作用后,雄黄矿和雌黄矿的砷释出浓度都不断升高。168 h氧化菌T.f作用后的砷释出顺序为雌黄矿>淋滤液次生含砷矿物>雄黄矿>含砷夹矸尾矿。LC-AFS原子荧光分析释出液砷形态结果表明:①T.f作用后,雄黄矿和雌黄矿表现出非常明显的差异;1.5 h作用后4种含砷矿物释放As(Ⅴ)的顺序为含砷夹矸尾矿>雄黄矿>淋滤液次生含砷矿物>雌黄矿;②2种还原菌作用后,SR更能促进雌黄矿释放的As(Ⅲ),其释放量是JF-5的2倍;雌黄矿释出As(Ⅲ)在168 h达到20.64 mg/L(SR)和9.54 mg/L(JF-5)。96 h SR作用后4种含砷矿物释放As(Ⅲ)的顺序为雌黄矿>淋滤液次生含砷矿物>含砷夹矸尾矿>雄黄矿。96 h JF-5作用后4种含砷矿物释放As(Ⅲ)的顺序为雄黄矿>雌黄矿>含砷夹矸尾矿>淋滤液次生含砷矿物。     

安徽铜陵杨山冲浅层富硫化物尾矿中砷的赋存状态

含硫化物尾矿常常释放大量的酸性排水和重金属,污染地下水、地表水和土壤,破坏生态系统,因此日益成为人们关注的焦点。本文以安徽铜陵杨山冲尾矿库浅层富硫化物尾矿为研究对象,利用扫描电镜(SEM)、电子探针(EPMA)、粉末X射线衍射(XRD)、拉曼光谱(Raman)、光电子能谱(XPS)和同步辐射近边吸收精细结构谱(XANES)等方法,系统分析了尾矿中砷的赋存形式,发现尾矿中的砷有3种价态: As(-Ⅰ)、As(Ⅲ)、As(Ⅴ)。在风化较弱的下部尾矿中,砷以As(-Ⅰ)、As(Ⅲ)和As(Ⅴ)的形式赋存;而强烈风化的表层尾矿中只检测到As(Ⅴ)的存在。从下部到表层,从低价态的As(-Ⅰ)和As(Ⅲ)逐渐变为高价态的As(Ⅴ)。下部尾矿中的砷主要赋存于黄铁矿中,而表层尾矿中的砷主要赋存在铁的(氢)氧化物和硫酸盐中。     

向山垃圾填埋场-尾矿混合带硫酸盐还原菌分离

马鞍山向山垃圾填埋场建设在向山硫铁矿尾矿库之上、混入玢岩铁矿尾矿和酸性排水,是富含有机质的废物与富含硫酸盐、铁氧化物废物混杂的地带,这是一个微生物电子受体和电子供体长期共存的场所。对这样一个特殊的体系进行微生物矿物交互作用研究具有十分重要的意义。本文对向山垃圾填埋场-尾矿混合带的微生物进行富集培养,经过富集培养和平板划线分离得到一株纯菌。经光学显微和扫描电镜观察、16SrDNA测序、还原硫酸盐能力检测,鉴定该纯菌株为梭状硫酸盐还原菌(Clostridium Sulfate Reducing Bacteria,简称C.SRB)。其生理生化特性研究结果表明,该菌可以利用葡萄糖和乳糖为碳源生长,甲基红试验为阴性,吲哚试验、接触酶试验均为阳性。考查该菌株的生长代谢以及温度、pH、盐度等外界环境影响因素发现,培养该菌株36 h消耗硫酸盐比速率最高为0.73 mmol/g·h;最适生长条件为温度35℃、pH值7、盐度0.5 g/L。     

广东河台金矿尾矿库金属硫化物环境地球化学效应

对河台金矿尾矿库中尾矿、尾水及生长植物进行采样分析，研究了尾矿库剖面中金属硫化物的环境地球化学效应，结果显示金属硫化物的化学风化作用呈规律性变化，从而导致尾水的pH值降低，游离态重金属离子浓度增加。通过对水生植物凤眼莲和尾矿坝上的植物蜈蚣蕨的分析发现，它们对矿山污染环境中的砷和铜有显著富集作用。     

高效耐盐碱石油烃降解菌筛选及降解特性研究

为探究长庆油田污染土壤中微生物对石油的降解特性,在该油田多个油井附近采集了10处含油污染土壤进行石油烃降解菌的筛选、分离及降解实验。通过对筛选出的四株石油烃降解菌株5-5、5-X、9-2、10-3进行革兰氏染色、菌落形态观察、生化理化试验及16S rDNA测序,鉴定出这四株菌株分别为醋酸钙不动杆菌（Acinetobacter calcoaceticus）、不动杆菌（Acinetobacter sp.）、蒙氏假单胞菌（Pseudomonas monteilii）和乳酸不动杆菌（Acinetobacter lactucae）。14 d降解实验结果显示,这四种菌株对总石油烃的降解率分别为50.92%、51.27%、78.30%和44.39%;尤其菌株Pseudomonas sp.9-2表现出优异的降解性能,且对不同组分石油烃（正构烷烃、异构烷烃及芳烃）的降解率分别达到了94.65%、69.73%和59.07%,对长链正构烷烃也体现出了较好的降解性能。另外,抗逆性试验结果表明菌株Pseudomonas sp.9-2对pH和盐度的耐受范围分别为5.0~10.0、0.5%~6.0%,表明该菌株对盐碱环境具有较好的适应性,可用于盐碱石油污染土壤的微生物修复研究。     

离子类型对石油污染含水层中微生物去除苯的影响

近来利用微生物原位修复受石油污染的含水层已被广泛关注,然而地下水中含有许多离子成分,这些无机离子对微生物降解有机污染物的影响机制还不清楚。本文采用批量实验研究了淄博齐鲁石化污染地下水中常见的7种无机离子(NO3-、PO4 3-、SO4 2-、Cl-、Ca2+、Mg2+、Fe3+)对微生物生长及生物降解苯的影响规律,利用高通量测序技术进一步探究了苯降解菌的种群特征。结果表明：7种离子都存在一个最适宜微生物生长的离子浓度,低于或超过该浓度苯的去除率明显降低,其中NO3-、SO42-、Fe3+最适宜浓度为0. 4mmol/L,PO4 3-、Cl-、Ca2+、Mg2+最适宜浓度分别为0. 2mmol/L、0. 1mol/L、2. 5mmol/L、2mmol/L;从微生物含量及其变化幅度来看,地下水环境中的NO3-离子对微生物的生长及苯的去除影响最显著,其他离子的影响则较小,但微生物对Cl-的耐受浓度较高。高通量测序结果显示驯化出的苯降解菌主要属于脱硫弧菌属(Desulfovibrio sp)、脱硫芽胞弯曲菌属(Desulfosporosinus sp)、不动杆菌属(Acinetobacter sp)和假单胞菌属(Pseudomonas sp)中的菌株。研究结果可为石油污染地下水的原位生物修复提供一定的科学依据。     

土著微生物作用下含水层沉积物砷的释放与转化

在原位采集内蒙古河套平原高砷含水层中沉积物和土著微生物的基础上,进行了室内微生物淋滤实验研究。实验过程中,使用了3种水溶液(包括去离子水和2种人工配水)和2种营养条件(包括添加2%葡萄糖和未添加葡萄糖)。结果表明,葡萄糖可强化土著微生物的活性,使得悬浮液pH值明显降低,并增加悬浮液中As质量浓度。配水成分影响悬浮物中As质量浓度。在第9 d之后,添加葡萄糖的样品中存在一定强度的硫酸根还原作用,且这种脱硫酸作用受配水成分的影响较小。研究表明,土著微生物影响下砷的释放和转化过程包括沉积物中As(V)的释放、溶液中As(V)的还原以及沉积物中As(Ⅲ)的释放等。与溶液As(V)相比,As(Ⅲ)更有利于沉积物As的释放。在As释放的过程中,溶液中Fe/Mn含量同时增加,且呈很好的线性相关关系。这意味着土著微生物作用下Fe/Mn氧化物矿物的还原性溶解是导致沉积物As释放的主要原因之一。     

江汉平原浅层含水层中土著硫酸盐还原菌对砷迁移释放的影响

硫酸盐还原菌是厌氧环境中参与砷形态转化的重要微生物种群,其介导的生物地球化学循环过程对铁氧化物表面吸附态砷迁移转化的影响亟待深入研究.选取江汉平原典型高砷含水层原位沉积物分离纯化出一株严格厌氧硫酸盐还原菌Desulfovibrio JH-S1,对其进行砷和铁还原能力鉴定,并通过模拟培养实验探究硫酸盐还原菌参与下的铁矿物相转化对吸附态砷迁移的影响.Desulfovibrio JH-S1具有Fe(III)还原能力,无硫和有硫体系中Fe(III)均能被还原,但在硫酸盐充足条件下铁还原量显著增加;该菌株不具备As(V)还原能力,但添加硫酸盐的培养体系中As(V)去除率可达96%以上.Desulfovibrio JH-S1能够还原硫酸盐从而促进载砷的水铁矿还原转化为纤铁矿,并导致吸附的砷释放.江汉平原高砷含水层土著硫酸盐还原菌兼具硫酸盐/铁还原功能,参与了高砷含水层系统中砷-铁-硫耦合循环,对高砷地下水的形成具有重要作用.      

两株异化铁还原菌与蒙脱石交互作用实验研究

本文选用采自辽宁某矿的天然钠基蒙脱石与两株异化铁还原菌模式菌株Shewanella putrefaciensCN32和She-wanellaoneidensisMR-1,研究了蒙脱石与微生物之间的交互作用。结果表明这两株菌均能还原蒙脱石晶格中的三价铁,使微生物作用于蒙脱石之后的反应体系中二价铁离子浓度明显升高,反应悬浊液颜色由无色变为浅绿色。透射电子显微镜晶格条纹像显示微生物作用后的粘土矿物微结构发生明显变化,其层间距d001值从1.29 nm分别减小为1.06 nm(CN32)和1.02nm(MR-1)。上述结果综合指示这两株异化铁还原菌能够通过还原天然蒙脱石结构中的三价铁促进矿物发生物相转变。     

四川拉拉铜矿尾矿中重金属资源和环境意义

尾矿中高含量重金属具有潜在的资源和环境意义。通过分析拉拉铜矿尾矿中的重金属含量及其赋存形式,讨论了尾矿中有价元素的回收利用可能性,并评价了尾矿中重金属的生态风险。结果表明,拉拉铜矿各期尾矿中仅Ⅲ期尾矿的铁、铜、钴具有综合利用价值;各期尾矿中多种重金属元素潜在的生态危害程度轻微,但是各期尾矿中汞的生态危害程度中等,Ⅲ期尾矿中铜的生态危害程度中等。因此,矿区不仅要注意各期尾矿汞对环境的潜在污染,同时也应注意Ⅲ期尾矿铜对环境污染的生态风险。     

Environmental geochemistry of the Gulf Creek copper mine area, north-eastern New South Wales, Australia

 Past mining and smelting of sulphide ore (pyrite-chalcopyrite-sphalerite) at the abandoned Gulf Creek mine has resulted in a stream highly contaminated by acid mine drainage (pH: 2.2–3.4), as well as degradation of local soil and vegetation. Physical dispersion of secondary metal-bearing minerals from abandoned ore and waste dumps into Gulf Creek and adsorption and coprecipitation of dissolved metals and metalloids in the stream bed cause elevated Ag, As, Cd, Cu, Fe, Pb and Zn values in stream sediments. The bioavailability of individual heavy metals to freshwater organisms changes downstream, however, selective bioaccumulation processes in algae reject readily bioavailable Zn and concentrate less bioavailable Cu. Polluted soils in the vicinity of the mine and smelter sites are subject to continuing soil erosion and either support no vegetation, or a depauperate flora with certain species showing bioaccumulation of metals and resistance to high metal contents. Rehabilitation of disturbed areas should involve covering and sealing sulphidic mine waste or removal of ore and waste dumps, installation of a physical and chemical plant or construction of a wetland environment (plus anoxic lime drains), and import of topsoil and planting of local, metal-tolerant plant species. Received: 17 March 1998 / Accepted: 6 October 1998     

典型岩溶区地下水系统重金属元素分布特征浅析——以广西坡月地下河为例

地下河为岩溶地下水系统的重要组成部分,为查清典型岩溶区地下水系统中重金属指标的含量变化及空间分布特征,文章以广西坡月地下河系统为例,通过不同断面两次采样分析,重点剖析地下河系统在水文地球化学作用下,地下水中以“五毒”元素及Zn、Al和Mn为代表的重金属元素含量。分析结果表明:坡月地下河水体pH值在7.34～8.10 之间,水体中“五毒”元素、Zn、 Al和Mn的检出含量极低或未检出,质量浓度均远小于国家地下水环境质量标准中的Ⅲ类水质标准,适合各种用途。检出含量较高的点主要为地下河明流段或补给区地表水,含量最高分布在坡心地下河出口水体,其原因是坡心地下河系统区内工矿企业和其它经济活动干扰相对较强,特别是工矿企业的矿石和尾矿渣的露天堆放（如金矿）是引起地下水中重金属元素的检出或超标的重要因素。      

铅锌矿尾砂重金属污染物对不同土地利用类型土壤性质影响的典范对应分析

广西阳朔思的村铅锌矿尾矿砂坝坍塌造成了大面积农田污染,已往报道多集中在金属矿山开采过程中产生的废液及大量固体废弃物堆砌而造成的环境污染,较少关注因尾矿砂坝坍塌所造成的这种土壤重金属特殊污染模式。本文运用典范对应分析(CCA)研究铅锌矿尾砂坝坍塌对不同土地利用类型(玉米地、柑橘园、水稻田)造成的重金属(铅、锌、铜、镉)污染以及对土壤理化性质(有机碳、碱解氮、速效磷、速效钾、阳离子交换量、碳氮比、pH值)的影响。CCA分析结果表明,研究区污染以铅、锌、镉为主,铜次之,其中锌和镉的空间分布格局受土地利用类型的影响更明显,并且镉对水稻田产生的环境风险最高。此外,在土壤中尾矿砂分布不均的前提下,土地利用类型是造成土壤重金属污染空间分布不同的重要驱动力,受土壤质地和矿砂性质的影响,重金属污染引起的酸化效应在供试土壤中不明显,使得CCA图中pH值所代表的点远离重金属箭头连线;阳离子交换量距重金属连线较近,受重金属影响明显并随重金属污染的加剧而减小;碱解氮、速效磷、速效钾等速效养分受重金属污染的影响并不显著,但与施肥配比和农业管理密切相关;有机碳与重金属箭头连线分布象限相同且包裹于其中,与重金属质量分数呈正相关关系,相较于玉米地和柑橘园,水稻田中有机碳积累量更大,达到18.14 g/kg,可能因稻田中微生物的碳源代谢利用能力明显降低,土壤中有机碳的矿化分解受阻,导致水稻土中有机碳的积累。此外,尾矿砂作为土壤重金属的持续性释放源,尽管对土壤的基本理化性质尤其是速效养分的影响并不明显,但能够通过影响土壤微生物群落间接影响土壤碳循环。     

Geochemical study of different-aged mining dump materials in the Freiberg mining district, Germany

Historical mining dumps are useful archives for the investigation of weathering processes. The objective of this study was to investigate the weathering behavior of waste-rock material derived from the 800-year-old silver ore mining in Freiberg, Germany. For identifying time-dependent weathering indices, dumped material of four dumps of different ages and corresponding rock was examined regarding the geochemical composition. The dumped material is characterized by high contents of heavy metal containing sulfidic ores, such as pyrite, arsenopyrite, sphalerite and galena. Acid mine drainage is produced by the oxidative weathering of the sulfide minerals and causes the increased dissolving of soluble metals with increasing age of dumps. As a result of these weathering processes, a clear depletion of chalcophile elements in the older dump material (800 years) compared to the youngest dump (100 years) was observed. In the soil horizons downstream the dumps, high quantities of heavy metals (e.g., up to 12,000 ppm As, 3,300 ppm Pb, 640 ppm Zn), mainly adsorbed on organic matter, were determined and indicate a time-dependent element transfer from the dumps into their surrounding soils.     

Sequential extraction and leaching characteristics of heavy metals in abandoned tungsten mine tailings sediments

The chemical speciation of potentially toxic elements (As, Cd, Cu, Pb, and Zn) in the contaminated soils and sulfides-rich tailings sediments of an abandoned tungsten mine in Korea was evaluated by conducting modified BCR sequential extraction tests. Kinetic and static batch leaching tests were also conducted to evaluate the potential release of As and other heavy metals by acidic rain water and the leaching behaviors of these heavy metals. The major sources of the elements were As-, Zn- and Pb-bearing sulfides, Pb carbonates (i.e., cerussite), and Pb sulfates (i.e., anglesite). The biggest pollutant fraction in these soil and tailing samples consists of metals bound to the oxidizable host phase, which can be released into the environment if conditions become oxidative, and/or to residual fractions. No significant difference in total element concentrations was observed between the tailings sediments and contaminated soils. For both sample types, almost no changes occurred in the mobility of As and the other heavy metals at 7 days, but the mobility increased afterwards until the end of the tests at 30 days, regardless of the initial pH. However, the mobility was approximately 5–10 times higher at initial pH 1.0 than at initial pHs of 3.0 and 5.0. The leached amounts of all the heavy metal contents were higher from tailings sediments than from contaminated soils at pH > 3.0, but were lower at pH < 3.0 except for As. Results of this study suggest that further dissolution of heavy metals from soil and tailing samples may occur during extended rainfall, resulting in a serious threat to surface and groundwater in the mine area.     

内蒙古废弃钨钼矿区周围土壤重金属污染生态环境评价及成因分析

为研究内蒙古赤峰市废弃钨钼矿区周围土壤重金属污染特征、潜在生态风险及成因分析，共采集83份表层土壤样品和6个土壤钻孔。采用ArcGIS空间插值分析方法研究As、Cd、Cr、Cu、Ni、Pb、Mo和Zn的空间分布，构建重金属扰动指数函数研究重金属受人类活动的污染程度，利用地累积指数法验证矿区周围土壤重金属污染程度，通过相关性分析判断重金属来源并讨论污染成因。结果表明：矿区周围土壤As、Cd、Cu、Pb、Zn和Mo平均含量明显高于矿区周边背景值，高含量主要分布尾矿库周围，主要来源为矿山采选活动；Cr和Ni基本无污染，主要来源为母岩风化。通过重金属扰动指数函数计算发现：采用区域背景值对矿区周围进行重金属污染评价夸大了矿山采选活动对矿区周围土壤重金属的污染，矿区周围土壤重金属污染是由于天然重金属富集和采矿活动共同作用下的“双驱动模式”导致，尾矿库周围土壤重金属污染程度随着与尾矿库水平距离的增加和深度的加大而逐渐降低。降水量丰富程度是影响重金属迁移能力的关键因素，该矿处于降水量匮乏地区，尾矿库对周围土壤重金属污染范围有限，对生态环境影响轻微。     

A study on soil physico-chemical, microbial and metal content in Sukinda chromite mine of Odisha, India

Soil samples from chromite mining site and its adjacent overburden dumps and fallow land of Sukinda, Odisha, were analysed for their physico-chemical, microbial and metal contents. Chromite mine soils were heterogenous mixture of clay, mud, minerals and rocks. The pH of the soils ranges between 5.87 and 7.36. The nutrient contents of the mine soils (N, P, K and organic C) were found to be extremely low. Analysis of chromite mine soils revealed accumulation of a number of metals in high concentrations (Fe > Cr > Mn > Ni > Zn > Pb > Sr) which exceeded ecotoxicological limits in soil. Correlation and cluster analysis of metals revealed a strong relation between Cr, Ni, Fe, Mn among the different attributes studied. Assessment of different microbial groups such as fungi, actinomycetes and bacteria (heterotrophic, spore forming, free-living nitrogen fixing, phosphate solubilising and cellulose degrading) from mine soils were found to be either extremely low or absent in some soil samples. Further chromium tolerant bacteria (CTB) were isolated using 100 mg/L Cr(VI) enriched nutrient agar medium and were screened for their tolerance towards increasing concentrations of hexavalent chromium and other toxic metals. Out of 23 CTB isolates, three bacteria tolerated up to 900 mg/L, 6 up to 500 mg/L, 20 up to 200 mg/L of Cr(VI). These bacteria were also found to be sensitive towards Cu > Co > Cd and very few CTB strains could show multiple metal tolerance. These strains have great scope for their application in bioremediation of toxic chromium ions in presence of other metals ions, which needs to be explored for their biotechnological applications.     

Surface Mineralogy of Oxidized Pyrite by Acidithiobacillus Ferrooxidans

Sulfide oxidation by microbial activities play an important role in the release of heavy metals. An important source of contamination and formation of AMD is the heavy metals convey to soil, rivulet and groundwater. Pyrite is a commonly sulfide minerals in mine wastes, so it is vitally to prove up the microbial oxidation process.     

Geochemical behaviour of some heavy metals of the Grot flotation tailing, Southeast Serbia

Grot tailing dump has the highest altitude of all tailing dumps in the Republic of Serbia. About 5.5 million tons of hydrocycloned sand was deposited in the tailing dump. This material was formed by flotation processing of ore from the Blagodat ore field. Vegetation was not developed in any part of the tailing. Minerals determined by X-ray diffraction analyses of representative samples form the tailing are quartz, clay minerals, calcite, feldspars, hematite, siderite, pyrite, sphalerite, galena and chalcopyrite. No regularities were noticed in their quantitative distribution. Statistical analysis of chemical fluctuations of lead, zinc, copper, arsenic and manganese concentrations showed that those with the highest concentrations are usually found on the central plateau. Lead displays the largest concentration range in the whole tailing. Maximal concentrations are found on the central and minimal in the south-western plateau. Zinc concentrations are up to 5,000 mg/kg, except in the central plateau where they reach extreme several times higher values. Copper concentrations are increased in the central plateau. In other parts of the tailing, concentrations are uniform and several times lower. Arsenic concentrations are mostly uniform, with the exception of extreme values in the north-western parts of the central plateau. Manganese shows uniform concentrations, somewhat increased on the south-eastern plateau. Chemical heterogeneity of the tailing material was influenced by the chronological discontinuity of the deposition and resedimentation. Resedimentation was the main cause of the fluctuation in the concentrations of the most mentioned heavy metals.