多金属矿山环境中矿物的微生物分解及环境效应研究进展

多金属矿山矿物的分解不仅可以形成酸矿水,而且可释放大量有害元素,造成严重的环境污染.在矿物分解、元素释放、迁移、沉淀和富集过程中微生物起了非常重要的作用.在总结微生物分解矿物的机制、微生物-矿物界面作用及生物膜在矿物分解过程中所起的作用基础上,概述了酸矿水中微生物群落的特征和种系演化,对矿山环境金属硫化物生物氧化释放的有害元素的微生物地球化学循环过程以及重金属元素对微生物氧化作用的影响做了系统的论述并讨论了微生物在环境修复中的作用.     

含硫化物方解石脉地表风化产物

<正>金属硫化物矿山环境中大量暴露于地表的金属硫化物(如黄铁矿、方铅矿、闪锌矿、黄铜矿)会发生氧化而生成酸性矿山排水(AMD)。尾矿和废石中的碳酸盐矿物往往与AMD反应而溶解,同时使AMD的酸度下降,并形成多种具有固定重金属元素能力的次生矿物,因此,碳酸盐矿物常常被作为治理AMD污染的重要矿物材料。由于方解石和黄铁矿广泛存在于多种岩石类型中,岩石露头的地表风化作用常常存在硫化物氧化分解、酸性岩石排水(ARD)形成、碳酸盐矿物分解、次生矿物形成的连续过程,这一过程     

Acidithiobacillus ferrooxidans氧化分解毒砂的次生产物研究

毒砂是常见的含砷硫化物矿物。在金属硫化物矿山环境中,含毒砂矿石和尾矿的风化会导致严重的重金属污染,在其风化过程中,微生物能够显著促进毒砂的氧化分解。本文实验研究了Acidithiobacillus ferrooxidans氧化分解毒砂矿物的现象,利用X射线衍射和扫描电子显微镜,分析了毒砂微生物氧化作用形成的次生矿物类型,发现毒砂表面存在As含量明显不同的2类次生产物,观察到黄钾铁矾、臭葱石、自然硫和施威特曼石等矿物;借助光电子能谱仪重点分析了微生物作用前后毒砂晶面的表面化学组成,基本查明了Fe、As和S三种元素的价态变化,初步探讨了毒砂表面次生矿物成因和As的化学态转化。     

含方解石铜矿石微生物氧化作用的实验研究

矿山固体废物中硫化物经微生物作用形成的酸性矿山排水及其引起的重金属污染是备受关注的环境问题,而岩石和矿石中的方解石能够影响酸性矿山排水的生成和迁移。为了考察方解石对硫化物-微生物氧化作用的影响,开展了系统的模拟实验,利用ICP-AES、XRD、XRF等分析手段,测定了实验溶液的pH值、Eh值、离子浓度和次生沉淀成分。结果表明,在无方解石或方解石含量低时,黄铜矿的微生物氧化过程中,pH值下降、Eh值上升,有多种重金属离子进入溶液,并生成大量黄钾铁矾、自然硫等次生沉淀。添加过量方解石能有效中和氧化过程产生的酸并能显著抑制氧化菌的活动。因此通过添加碳酸盐矿物的方法可使溶液pH调节至微碱性,降低微生物的活性、阻滞铜矿石的氧化,能够有效降低重金属的释放。     

风化过程中矿物表面微生物附着现象及意义

微生物风化作用作为最为重要的表生过程之一,与多种元素的地球化学循环和局部环境污染的形成有着密切的联系.微生物在矿物表面的附着能够显著提高矿物的风化速率.本文在总结矿物表面微生物附着现象及特征的基础上,概述了微生物附着导致的矿物表观风化速率的上升和表面侵蚀现象,初步分析了微生物在矿物表面附着的驱动力和影响因素,强调了微生...     

含钾岩石微生物转化的分子机制及其碳汇效应

岩石矿物的微生物风化是地球表层系统最为活跃和普遍发生的地质营力之一。微生物对含钾岩石(以硅酸盐矿物为主)的风化能够释放其中的钾、硅和钙等元素,并在合适的环境条件下促进矿物元素的碳酸化沉淀,这是地表元素地球化学循环的重要环节之一。微生物对岩石的生物转化作用既涉及微生物的生长繁殖和代谢调控,也与元素的迁移转化和次生矿物的演化序列有关,具有重要研究价值。采用矿物学、微生物学和分子生物学等相结合的研究方法,有助于系统地研究微生物促进含钾硅酸盐矿物的风化并耦联碳酸化过程及其分子调控机制。研究证实,在纯培养条件下,微生物风化含钾矿物主要采用酸解、螯合、氧化还原等多种方式的协同作用,并可通过调控相关功能基因的表达来响应缺钾的环境以实现其对含钾矿物的有效风化,显然这有赖于微生物通过长期进化而形成的精细的分子调控机制。在土壤生态环境中,微生物对矿物风化的显著特征是该生态环境中微生物群落协同互作的群体作用效应。微生物碳酸酐酶参与的硅酸盐矿物风化伴随碳酸盐矿物的形成过程可能是个长期被忽视的地表碳增汇过程,对该问题的深入探索有助于进一步理解地质演化历史中微生物对碳素迁移转化的驱动机制。加入含钾硅酸盐矿粉的有机肥已经显示出其在土壤改良、作物生长和增加土壤碳汇等方面的正面应用效果,这为利用硅酸盐矿物的生物风化作用来延缓大气CO₂浓度的持续升高提供了新的思路。介绍了有关微生物对含钾岩石生物转化释放钾素的分子机理及其碳汇效应方面的研究进展,以期抛砖引玉,推动该领域研究的快速发展。     

微生物对碳酸盐岩的风化作用

微生物-矿物相互作用可以促进许多表生生物地球化学反应过程,是表生地球化学研究的重要内容。通过综合岩石表面的微生物类群及其地质作用,分析碳酸盐岩微生物风化的各种现象,特别是微观尺度上的各种形态,阐述碳酸盐岩的微生物风化机制与风化产物,笔者提出微生物对碳酸盐岩风化的4种途径:(1)通过微生物在岩石表面和缝隙中生长,导致岩石表层发生生物溶蚀、生物磨蚀和生物钻孔作用,加速岩石风化进程;(2)微生物群体形成的钻孔网络可以增强岩石化学溶蚀的有效表面积并导致其表面强度减弱而促进机械侵蚀作用,微生物对周围岩石颗粒胶结结构的破坏、疏松作用也会导致岩石矿物颗粒的分解;(3)微生物的持水作用,微生物分泌的有机酸以及微生物呼吸所释放的CO2对岩表水分的酸化过程亦加速岩石矿物的分解;(4)微生物生长过程中从岩石内摄取营养元素和产生复杂的有机配体,能促进矿物元素的释放。文中提出在开展微生物对碳酸盐岩风化过程和机理研究的基础上,有必要引入微生物生物技术来综合开发本地低品位含钾磷矿产资源,加速岩溶地区山地土壤的形成与演化。     

施氏矿物吸附Cu2+及氧化亚铁硫杆菌的实验研究

在金属硫化物的表生氧化过程中,施氏矿物是最常见的一种次生矿物.施氏矿物具有粒度小、比表面积大、表面吸附能高的特点,能够吸附环境流体中的重金属离子和微生物细胞,从而影响重金属元素及微生物的表生地球化学行为.利用化学合成的施氏矿物,开展了施氏矿物吸附Cu2+及氧化亚铁硫杆菌的实验.结果显示:施氏矿物对金属Cu2+及氧化亚铁硫杆菌均有较强的吸附性;施氏矿物对Cu2+的吸附基本符合Langmuir吸附模型,而对氧化亚铁硫的吸附行为不符合Langmuir模型,可用Freundlich模型描述;施氏矿物的存在对流体中微生物的活动性及其地球化学行为有重要影响,可能会降低氧化菌分解金属硫化物的效率.     

微生物对硅酸盐矿物风化作用研究进展

微生物对硅酸盐矿物风化的影响研究取得了一系列重要进展。在贫营养环境中,微生物风化硅酸盐矿物获取营养物质,加速了硅酸盐矿物的风化;由于微生物的作用,矿物的风化会不遵循正常的矿物化学风化序列,表现出稳定矿物比不稳定矿物更易风化的特征。微生物风化硅酸盐矿物时会在硅酸盐矿物表面留下痕迹,即富集或转移相应的元素和矿物,而且还能改变硅酸盐矿物的化学组成和结构。微生物的上述行为受营养基质含量、有机酸、生物膜、胞外聚合物以及氧化还原作用的影响。     

黑色岩层的风化特征研究

黑色岩层是一种分布广泛且较为特殊的一类岩石，它的风化往往会加速各类岩石以及工程建筑物材料的风化与化过程，本文从矿物岩石学特征、黑色岩层风化的环境特征、黑色岩层中硫化物矿物氧化的地球化学过程中以及硫化物矿物氧化形成的酸性条件下其它矿物的稳定性等方面对湘西地区黑色岩层的风化特征进行了分析，为进一步深入研究黑色岩层的风化过程及机理打下了基础。     

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.     

Influences of Microbial Oxidation/Reduction on Mineral Transformation in Sulfide Tailings and Environmental Consequence in Shizishan Cu-Au Mine,Tongling, Eastern China

Mining activities have created great wealth, but they have also discharged large quantities of tailings. As an important source of heavy metal contamination, sulfide tailings are usually disposed of in open-air impoundments and thus are exposed to microbial oxidation. Microbial activities greatly enhance sulfide oxidation and result in the release of heavy metals and the precipitation of iron (oxy) hydroxides and sulfates. These secondary minerals in turn influence the mobility of dissolved metals and play important roles in the natural attenuation of heavy metals. Elucidating the microbe–mineral interactions in tailings will improve our understanding of the environmental consequence of mining activities.     

尾矿中硫化物风化氧化模拟实验研究

为防治矿山尾矿造成环境污染，对方铅矿，闪锌矿，磁黄铁矿、黄铜矿，黄铁矿进行了风化氧化实验研究，结果显示，硫化物的氧化速率顺序为：方铅矿＞闪锌矿＞磁黄铁矿＞黄铜矿＞黄铁矿，侵蚀液pH值越低，硫化物氧化速率越大，有机物存在对硫化物氧化起缓冲和抑制作用。     

Mineralogical and geochemical constraints on environmental impacts from waste rock at Taojiang Mn-ore deposit,central Hunan,China

The mineralogy and geochemistry of the waste rocks distributed at Taojiang Mn-ore deposit, central Hunan province, China, were studied using X-ray powder diffraction (XRD), electron microprobe analysis (EMPA) fitted with energy dispersive spectrometer (EDS) and inductively coupled plasma mass spectrum (atomic emission spectra) ICP-MS (AES), with the aim of predicting the environmental impacts of weathering of the waste rocks. The mineralogical results from microscope observation and XRD and EMPA studies show that the waste rock is composed of black shale and minor Mn carbonates. The oxidation of sulfide minerals such as galena, pyrite and chalcopyrite is accompanied by decomposition of Mn carbonates and K-feldspar during exposure to atmospheric O₂. The geochemical characteristics of major, rare earth elements (REE) and trace elements of the waste rocks also show that the waste rock can be divided into black shale and Mn carbonate, and both of them are currently under chemical weathering. The major alkalies and alkaline elements (Ca, Mg, Na, K, Rb, Sr and Cs) and major elements (Fe, S and P) and heavy metals (Sc, V, Cr, Th, U, Sn, Co, Ni, Cu, Zn, Pb, Mo, Cd, Sb, an Tl) are being released during weathering. The mobility of alkalis and alkaline elements Ca, Mg, Na, K, Rb, Sr and Cs is controlled by decomposition of Mn carbonates. The dispersion of Cr, Sc and Th (U) might be related to weathering of K-feldspar, and the release of the heavy metals Co, Ni, Cu, Zn, Pb, Mo, Cd Sb and Tl is dominated by the breaking of sulfide minerals. The REE of the waste rocks and surrounding soils and the spidery distribution patterns of heavy metals in the waste rocks, the surrounding soils and the surface waters show that weathering of the waste rocks and bedrock might be the sources of heavy metal contamination for the surrounding soils and surface water system for the mining area. This is predicted by the mass-balance calculation by using Zr as an immobile element. Therefore, it is urgently necessary take measures to treat the waste rocks distributed throughout the area for the local environmental protection.     

Isotope geochemistry of waters affected by mining activities in Sierra Minera and Portman Bay (SE,Spain)

The objective of this work was to evaluate processes affecting waters from Portman Bay by way of stable isotopic analysis, particularly H and O stable isotopes from water and S and O from dissolved sulfates. In addition, surface waters from Sierra Minera were examined for the purpose of determining if these waters are affected by similar processes. The results obtained indicate that Portman Bay waters are meteoric, and marine infiltration only takes place in the deepest layers near the shore or if water remains stagnated in sediments with low permeability. The main source of sulfate was the oxidation of sulfides, resulting in the liberation of acid, sulfate and metals. In order to assess the mechanism responsible for sulfide oxidation, the stoichiometric isotope balance model and the general isotope balance model were tested, suggesting that the oxidation via Fe³⁺ was predominant in the surface, and controlled by Acidithiobacillus ferrooxidans, while at depth, sulfate reduction occurred.     

Atmospheric weathering of Scandinavian alum shales and the fractionation of C,N and S isotopes

Subaerial exposure and oxidation of organic carbon (C_org)-rich rocks is believed to be a key mechanism for the recycling of buried C and S back to Earth's surface. Importantly, processes coupled to microbial C_org oxidation are expected to shift new biomass δ¹³C_org composition towards more negative values relative to source. However, there is scarcity of information directly relating rock chemistry to oxidative weathering and shifting δ¹³C_org at the rock-atmosphere interface. This is particularly pertinent to the sulfidic, C_org-rich alum shale units of the Baltoscandian Basin believed to constitute a strong source of metal contaminants to the natural environment, following subaerial exposure and weathering. Consistent with independent support, we show that atmospheric oxidation of the sulfidic, C_org-rich alum shale sequence of the Cambrian-Devonian Baltoscandian Basin induces intense acid rock drainage at the expense of progressive oxidation of Fe sulfides. Sulfide oxidation takes priority over microbial organic matter decomposition, enabling quantitative massive erosion of C_org without producing a δ¹³C shift between acid rock drainage precipitates and shale. Moreover, ¹³C enrichment in inorganic carbon of precipitates does not support microbial C_org oxidation as the predominant mechanism of rock weathering upon exposure. Instead, a Δ³⁴S = δ³⁴S_shale − δ³⁴S_precipitates ≈ 0, accompanied by elevated S levels and the ubiquitous deposition of acid rock drainage sulfate minerals in deposited efflorescent precipitates relative to shales, provide strong evidence for quantitative mass oxidation of shale sulfide minerals as the source of acidity for chemical weathering. Slight δ¹⁵N depletion in the new surface precipitates relative to shale, coincides with dramatic loss of N from shales. Collectively, the results point to pyrite oxidation as a major driver of alum black shale weathering at the rock-atmosphere interface, indicating that quantitative mass release of C_org, N, S, and key metals to the environment is a response to intense sulfide oxidation. Consequently, large-scale acidic weathering of the sulfide-rich alum shale units is suggested to influence the fate and redistribution of the isotopes of C, N, and S from shale to the immediate environment.     

郑州市土壤重金属污染状况和质量评价

本文采用电感耦合等离子体质谱、原子荧光光谱法对郑州市及周边地区化探扫面(1∶10万)采集的1014个表层土壤样品进行分析,结合单因子污染指数法、内梅罗指数法评价了土壤中重金属含量水平、形态特征和污染分布状况。结果表明,8种重金属的平均含量都低于《土壤环境质量标准》Ⅰ类土壤的临界值;从地表到深部重金属元素含量逐步降低;在测区1000 km2范围内,一级、二级、三级土壤面积分别占89.6%、9.4%、1.0%,土壤质量总体良好。在极个别中、重度污染区,重金属主要以难以迁移和被植物利用的残渣态、铁锰氧化态形式存在,目前对人及环境的实际危害很小。     

Oxidation and Mineralization of Mn2+ Ions Mediated by Pseudomonas putida: Insights from an Experimental Study

The formation of manganese oxides in nature is commonly mediated by microorganisms.In this study,the mineralization of biogenic manganese oxidation mediated by Pseudomanas putida has been experimentally investigated by employing various characterization techniques,including SEM,FESEM,TEM,XRD,and STXM-NEXAFS.The results indicate that Mn~(2+) ions can be oxidized into Mn(Ⅳ) minerals(birnessite and pyrolusite) and Mn(Ⅲ) minerals(hausmannite and feitknechtite),successively.The primary products(birnessite and pyrolusite) further transformed into hausmannite and feitknechtite under Mn~(2+) ion-enriched conditions.However,birnessite and pyrolusite are the endproducts of the continuous microbial oxidation processes.These biogenic Mn oxides are poorly crystallized,which provides them with a high potential for usage in environmental restoration of contaminated soils and waters contaminated with heavy metals.The approaches employed in this study will also enrich genesis research of biological oxidation of Mn(Ⅱ) species in nature.     

煤矸石-水相互作用的溶解动力学及其环境地球化学效应研究

煤矸石—水相互作用的溶解动力学及其环境地球化学效应研究党志（中国科学院地球化学研究所，贵阳５５０００２）关键词水—岩作用煤矸石地球化学动力学采煤矿区复垦环境效应收稿日期：１９９７－３－１０作者简介：党志男１９６２年生博士生环境地球化学煤矸石以其量多、...