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1.
黑色页岩水岩化学作用实验研究 总被引：2，自引：0，他引：2
水岩作用是黑色页岩化学风化的重要途径,并与岩体矿物组分、工程性质及地质环境有着密切的联系。利用自制的流通实验装置对取自三江县团结电站附近的寒武系清溪组黑色页岩与富含溶解氧去离子水的化学反应进行试验模拟研究,并利用离子分析仪、电感耦合等离子体质谱仪对反应后溶液离子浓度进行分析,使用扫描电子显微镜观察反应前后岩样微观特征,结合岩样渗透系数的变化监测,对岩样中黄铁矿氧化动力学速率以及受黄铁矿氧化影响形成的酸性环境下硅元素释放速率进行计算分析。结果表明,黄铁矿氧化行为使得岩体渗透率降低约70%,在黑色页岩自身矿物化学组分和岩石物理性质的共同影响下,所含黄铁矿氧化速率与纯黄铁矿颗粒的氧化速率非常接近,同时黄铁矿氧化形成的酸性溶液可溶蚀岩体中石英和伊利石,由于两者含量未能精确测定,因此所测得硅元素释放速率仅表示两者溶解的总反应速率。 相似文献
2.
嗜酸性氧化亚铁硫杆菌与硫化物矿石相互作用的实验研究 总被引：2，自引：0，他引：2
实验研究了嗜酸性氧化亚铁硫杆菌(Acidithiobacillus ferrooxidans,简称A.f)与硫化物矿石之间的相互作用,以观察不同矿石矿物发生微生物氧化和形成次生矿物的差异。采用ICP-OES分析了反应前后溶液成分变化,利用扫描电子显微镜(SEM)、能谱分析(EDS)和X射线衍射(XRD)等分析手段研究了矿石表面形貌的变化和沉淀物的矿物组成。分析结果表明,A.f对同一矿石中不同矿物作用强度存在明显差异,方铅矿、闪锌矿发生强烈氧化分解,而与黄铁矿的相互作用则较弱。这种差异可能与矿物晶体结构有关,在多种矿物并存的情况下,可能发生了原电池反应,作为阴极的黄铁矿受到保护,而作为阳极的闪锌矿、方铅矿的氧化作用得到促进,总体上表现为A.f对矿石硫化矿物的选择性作用。 相似文献
3.
夏方 陈国荣Allan PRING Joel BRUGGER Yung NGOTHAI Brain O＇NEILL Chris COLBY Christophe TENAILLEAU王海鹏 杨云霞 《地质学报》2007,81(10):1378-1390
本工作首次在实验室条件下对浅生区紫硫镍矿(Ni,Fe)3S4交代镍黄铁矿(Ni,Fe)9S8水热反应的机理及动力学进行了研究。起始反应矿物采用高纯自然镍黄铁矿,合成纯镍黄铁矿或合成镍黄铁矿-磁黄铁矿集合体。反应pH值采用0.2M醋酸-醋酸纳缓冲溶液控制在3～5的范围内。反应进程由X-射线衍射物相定量分析及扫描电镜观察进行跟踪。结果表明,当反应温度恒定在80℃时,交代20(4)%的镍黄铁矿需792h。相同条件下加入少量H2S可将反应速率提高一倍。当反应在125℃饱和蒸汽压水热环境下进行时,完全交代纯镍黄铁矿需约168h。此过程由于磁黄铁矿的存在而被催化,交代集合体中的镍黄铁矿仅需68h,进一步反应磁黄铁矿被交代成白铁矿。磁黄铁矿的催化作用可能源于溶解产生的微裂纹加速了流体的传质过程。当反应温度升高至145℃时,速率反而下降,不遵循Arrhenius经验规律。动力学分析得80℃速率常数介于5.8×10-8～3.0×10-7/s之间,125℃及145℃速率常数分别介于2.8×10-6～2.08×10-5/s及1×10-6～5.1×10-6/s之间,远高于同温度下固相扩散反应的速率常数,表明该反应在地质时标上为一快速反应。此外,用背散射电子显微技术对矿物表面形貌进行了分析,发现交代产物紫硫镍矿具有颗粒细小及存在微裂纹等特征,与自然界浅生矿床中的紫硫镍矿非常相似;电镜实验还表明该交代作用是一个典型的耦合溶解-再沉淀反应。其耦合机制的驱动力可能与反应界面处微空隙对流体饱和度的控制有关。 相似文献
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5.
矿物溶解的表面化学动力学机理 总被引：13，自引：0，他引：13
本文应用表面化学理论分析了矿物在水溶液中的溶解反应动力学机理。表面化学的催化作用使矿物溶解反应的活化能显著降低。矿物溶解速率受表面吸附、表面交换反应和解吸反应等表面化学过程的控制并与溶液的pH值有关，正比于溶液αH＋值的nθ次幂。受表面吸附控制时，nθ＝1，溶解速率随pH增大而减小；受表面交换反应控制时，nθ＝0，溶解速率与pH无关；受解吸反应控制时，酸性条件下nθ为0～1内的正小数，碱性条件下nθ为-1～0之内的负小数。大多数矿物的溶解作用在酸性条件下受表面吸附和／或表面交换反应控制，在碱性条件下受解吸反应的控制。 相似文献
6.
回顾了地球化学动力学这门新兴学科的产生与发展，评述了国内外矿物-水反应的地球化学动力学研究的新进展，介绍了矿物-水反应的溶解动力学及地球化学动力学模拟的新成果及应用领域。低温条件下硅酸盐和碳酸盐矿物与水的反应得到高度重视。硅酸盐矿物的溶解速率与溶液的pH值、离子强度、温度及有机酸的含量等密切相关。碳酸盐类矿物的溶解速率主要取决于温度、GO2分压、酸碱度及相关离子的活度等因素。氧化物、硫化物、及氟化物等的溶解沉淀的动力学研究开始得到关注。矿物-水反应的地球化学动力学模拟已成为一个很有前景的方向。 相似文献
7.
磁黄铁矿催化分解苯酚反应动力学及其产物特征 总被引：2，自引：0，他引：2
本文用批量实验法研究了天然磁黄铁矿在过氧化氢参与下催化分解苯酚的动力学反应。结果表明,在pH=3.81～5.88时,苯酚都可被有效的分解,分解速率k=4.0～212h-1(g/L)-1,高于氧化铁矿物类催化剂,可与Fenton试剂相比拟。同时它具有反应速率可控、催化剂与反应产物易于分离和回收等优点。对反应液中Fe(II)、Fe(Ⅲ)浓度和紫外光谱分析表明,反应过程与Fenton反应类似,苯酚先是被快速转化成多酚类化合物,接着被分解成羧酸类化合物。溶液pH不同,产物不同,总有机碳(TOC)矿化率也不同,一般可达50%～58%。 相似文献
8.
矿物吸附金的实验研究及其在红土型金矿形成中的意义 总被引：2，自引：1，他引：2
Au(Ⅲ）－氯化物和Au(Ⅰ)－硫代硫酸盐被蒙脱石、高岭石、伊利石、针铁矿、褐铁矿及黄铁矿的吸附实验研究结果表明，各种矿物对AuCl4^-的吸附作用显著大于Au(S2O3)2^3-，粘土矿物对金的吸附能力，蒙脱石＞高岭石＞伊利石；含铁矿物中，黄铁矿＞针铁矿＞褐铁矿。矿物对金的吸附作用与矿物结构和金的存在形式有关，即受矿物表面基、金组分的稳定性和位阻的影响；天然雨水中所含微量H2O2是Au、黄铁矿等不同矿物氧化－还原的催化剂，可加速地表岩（矿）石的风化氧化过程和Au的溶解与迁移。雨水对红土中的Au具有一定的淋滤浸取能力。红土型金矿形成于富Cl^-、SO4^2-的酸性、氧化的水化学环境，含金黄铁矿等硫化物的氧化不仅直接导致了Au的溶解和酸的释放，而且其反应产物Fe^3 、S2O3^2-等为Au的氧化、溶解和迁移提供了氧化剂和络合剂，并促进Au的溶解和迁移；Au主要以硫代硫酸络合物、氯化络合物及其水合物的形式进行迁移；硫代硫酸根的氧化和风化壳下部的还原作用是导致金络合物失稳、Au被其他矿物吸附和沉淀富集的主要因素。矿物对金的吸附在红土型金矿的形成过程中起了重要作用。 相似文献
9.
长江中下游火山岩盆地中金属矿床和蚀变分带的的地球化学研究表明,它们具有内带深色蚀变带和外带浅色蚀变带,形成于600℃到100℃范围。两类蚀变带分界温度大致是300℃。大金属矿床蚀变分带剖面显示出热液系统存在有明显的温度梯度。通过与背景岩石(玄武岩石)对比研究表明,自下而上的不同蚀变岩石中主要元素含量显著变化,交代作用中的代出和代入元素在空间上是演化的。25~400℃和23MPa下矿物(钠长石、阳起石、透辉石、钙铁辉石)-H2O、岩石(玄武岩)-H2O反应的化学动力学实验表明,金属元素释放速率是温度的函数。在恒压升温过程中,从20℃到400℃,硅酸盐矿物、玄武岩中Si溶解速率不断上升;在300~350℃时,Si、Al溶解速率到最大数值。随后,温度再上升导致溶解速率下降。在300℃时,大部分矿物中Ca、Mg、Fe、Na溶解速率较高,溶液里的Ca/Si、Mg/Si、Fe/Si、Na/Si等都高于矿物中对应元素的计量比。矿物反应后的表面存在富集硅的淋失层,或有富硅铝矿物(粘土矿物)出现。在300℃时,Si溶解快于其他金属元素,溶液中金属元素与硅摩尔浓度比(Ca/Si、Mg/Si、Fe/Si、Na/Si)等都低于矿物中的计量比。矿物反应后的表面缺少硅的淋失层,或者有贫硅矿物和铁氧化物出现。作者还进行23~35MPa、20~550℃玄武岩与水反应实验。上述高温高压下矿物在水溶液中的溶解反应动力学实验和流体-玄武岩相互作用实验,对于理解金属矿床及蚀变分带形成机制提供新的依据。 相似文献
10.
蚯蚓肠道内小分子有机酸与摄入的土壤矿物相互作用,加速矿物溶解。摄入的土壤在蚯蚓肠道内平均停留时间约为12 h,不足以使土壤矿物产生显著的溶解特征,因此这一过程难以在蚯蚓体内进行评估。本研究通过体外实验控制pH值和有机酸浓度,模拟蚯蚓肠道中有机酸对土壤中常见矿物的溶解反应,探讨了方解石和钾长石在蚯蚓肠道环境中的初始溶解动力学。研究发现,矿物在混合有机酸中的溶解速率比在纯水中高一个数量级,说明有机配体和质子促进了矿物溶解。溶解速率及粒度分析表明,方解石(CaCO3)溶解速率不受溶解过程中粒度变化的影响,而钾长石(KAlSi3O8)粒度在溶解期间未出现显著变化。在此基础上,采用初始速率法模拟了钾长石的初始溶解动力学,计算得出的溶解速率表明钾长石在溶解初期主要为表面K~+的释放。使用缩核模型(shrink core model)和Hixson-Crowell模型对方解石溶解过程进行动力学解析,发现方解石的溶解主要受溶液中反应物内扩散的速率影响。这定量描述了两种矿物在有机酸溶液和纯水中的溶解差异。现有研究表明,有机配体和质子协同促... 相似文献
11.
The bioleaching behaviors and surface properties of pyrites in two metallogenic conditions by Sulfoba- cillus thermosulfidooxidans were investigated by adsorption tests, zeta-potential measurements and bioleaching ex- periments. It is found that there were significant differences in the microorganism adsorption capacity, electrokinetic properties and bioleaching behaviors for the two pyrites. The S. thermosulfidooxidans adsorption capacity on high temperature hydrothermal （hy high_temp） pyrite is larger than that on sendimentary coal （sed_coal） pyrite. It may be that more extracellular polymeric substances （EPS） is produced when it is difficult for microorganism to make use of hy high temp pyrite as source of energy, and get leaching bacteria attached to pyrite by means of EPS. The zeta-potential measurements indicated that zeta-potential value of hy_high_temp pyrite was higher than that of seal_coal pyrite in pH range of 2-10. After interacting with cells, the IEP （Iso-Electric Point） of hy_high_temp pyrite shifted obviously to that of bacterial. In contrast, the IEP of sed coal pyrite remained unchanged nearly. The bioleaching results showed that hy high_temp pyrite did not dissolve and the leaching extent was only 0.82%, while that of sed_coal pyrite was 34.59%. Attempts were taken to illustrate the remarkable difference between bioleaching results of two pyrites from a semiconductor energy band theory perspective. 相似文献
12.
Ik Woo Jae Gon Kim Gyoo Ho Lee Hyuck Jin Park Jeong Gi Um 《Environmental Earth Sciences》2013,69(6):1821-1829
Pyrite is a common and abundant sulfidic mineral subject to oxidation. The weathering characteristics of rock-bearing pyrite sometimes impose serious influences on the surrounding environment as the oxidation of pyrite (FeS2) generates acid drainage that results in the acceleration of rock weathering and the discharge of heavy metals into the environment. Such an accelerated weathering of rocks can reduce its mechanical properties and therefore menace the stability of rock structures, such as excavated slopes and tunnels. The evolution of physical properties of rocks and the chemical composition of drainage were evaluated in this study by a weathering test using a double Soxhlet extractor for 1 month in a laboratory setting. Three groups of biotite gneiss classified according to their pyrite content were used for the Soxhlet extraction experiment (group A with less than 0.1 wt% of pyrite; group B with about 3.3 wt% of disseminated pyrite; group C with about 5.65 wt% of vein type pyrite). The massive groups A and B had limited weathering on the surface; however, group C with the pyrite vein experienced weathering on the surface as well as along the pyrite vein. The weathering type regulated by the occurrence of pyrite apparently controlled the mechanical properties of the rock samples and the chemistry of the drainage. Groups A and B showed no significant quick absorption ratio after the 1-month experiment; however, group C had about 10 % increase in value. The uniaxial compressive strength of the three groups decreased about 20, 10 and 45 % for groups A, B and C, respectively. The mechanical properties of the samples and the chemical compositions of the drainage indicate that the oxidation of pyrite contained in the samples accelerated weathering, resulting in deterioration of mechanical properties of the rocks, and could result in the discharge of heavy metals and acid into the environment with the drainage. 相似文献
13.
矿物材料对废水厌氧处理及厌氧污泥改性具有十分重要的作用,而微生物代谢产物是生物处理系统的重要组分,在提高污染物去除率和甲烷产量等方面也起到非常重要的作用。本研究对矿物材料石墨和厌氧微生物共存体系内溶解性微生物产物(soluble microbial product,SMP)和胞外聚合物(extracellular polymeric substances,EPS)进行了分析表征。结果表明,石墨对EPS和SMP的组成和含量影响显著,主要是由于石墨的吸附作用及其对石墨颗粒的环境毒性所致。红外光谱分析表明,添加石墨体系内SMP与EPS的基团种类并未发生明显改变,但含量有所改变。三维荧光分析结果显示,SMP的主要荧光类物质为色氨酸类似物和腐殖质(辅酶NADH),而EPS的主要荧光类物质为色氨酸类似物和腐殖酸,石墨能明显降低色氨酸类似物及腐殖酸类物质的产生。石墨会减弱微生物的相对疏水性,提高表面自由能,有利于微生物团聚体的形成。 相似文献
14.
通过对黄铁矿在阳山高岭土矿床阳东矿区的分布、产状及与其共生矿物的生成关系分析,并根据矿物成因学原理,对阳东矿区中黄铁矿的化学成分、晶胞参数、晶体形态等矿物的标型特征的研究,得出该矿区黄铁矿属中低温热液成因,可分为5个世代,热液活动是多期次的,至少5期;黄铁矿的形成为高岭土形成提供酸性介质的条件;高岭土中的黄铁矿不含砷。 相似文献
15.
《International Journal of Mineral Processing》2005,77(3):154-164
The adsorption of ethyl, propyl and butyl xanthates on pyrite has been studied through electrokinetics, batch adsorption tests, and quantification of Fe2+ ions in solution. Adsorption isotherms for the three alkyl xanthates indicate that their adsorption to dixanthogen produces Fe2+ ions in solution and decreases the pyrite zeta potential negatively. It seems that the oxidation reaction of xanthates to dixanthogen on pyrite is coupled with the reduction reaction of surface-ferric hydroxide to ferrous ions, leading to the dissolution of hydrophilic ferric hydroxide and growth of hydrophobic dixanthogen on the surface of pyrite. Flotation of pyrite is presented as a function of pH using various ethyl xanthate concentrations. The floatability results are explained in terms of the surface coverage relationship between ferric hydroxide and dixanthogen, which is pH dependent. 相似文献
16.
金属硫化物矿物之间的原电池反应对于酸性矿山排水的形成、硫化物矿床的次生富集作用、地球电化学勘探以及湿法冶金过程等都有很重要的影响。通过改变溶液中氧化剂组分F e3 的浓度、pH值、溶液的流动状况以及溶液的盐度(如N a2SO4的浓度),采用精密的电流计和电位计,对作为阳极的黄铁矿与作为阴极的方铅矿所形成的原电池反应的电流密度和整个原电池的混合电位进行研究,结果表明:溶液中[F e3 ],pH值以及溶液的流动状况对黄铁矿和方铅矿之间原电池反应的影响很大,而溶液的盐度对反应的影响不是很显著。实验还发现,当黄铁矿电极表面存在微小裂纹时,其电极电位可降低至同条件下方铅矿的电极电位以下。这一实验结果在混合电位理论和Bu tler-V o lm er方程中得到了理论上的解释。 相似文献
17.
A.M. WidlerT.M. Seward 《Geochimica et cosmochimica acta》2002,66(3):383-402
The adsorption of gold by pyrite, pyrrhotite, and mackinawite from solutions containing up to 40 mg/kg (8 μm) gold as hydrosulphidogold(I) complexes has been measured over the pH range from 2 to 10 at 25°C and at 0.10 m ionic strength (NaCl, NaClO4). The pH of point of zero charge, pHpzc, has been determined potentiometrically for all three iron sulphides and shown to be 2.4, 2.7, and 2.9 for pyrite, pyrrhotite, and mackinawite, respectively. In solutions containing hydrogen sulphide, the pHpzc is reduced to values below 2. The surface charge for each sulphide is therefore negative over the pH range studied in the adsorption experiments. Adsorption was from 100% in acid solutions having pH < 5.5 (pyrite) and pH < 4 (mackinawite and pyrrhotite). At alkaline pH’s (e.g., pH = 9), the pyrite surface adsorbed 30% of the gold from solution, whereas the pyrrhotite and mackinawite surfaces did not adsorb.The main gold complex adsorbed is AuHS°, as may be deduced from the gold speciation in solution in combination with the surface charge. The adsorption of the negatively charged Au(HS)2− onto the negatively charged sulphide surfaces is not favoured. The X-ray photoelectron spectroscopic data revealed different surface reactions for pyrite and mackinawite surfaces. While no change in redox state of adsorbent and adsorbate was observed on pyrite, a chemisorption reaction has been determined on mackinawite leading to the reduction of the gold(I) solution complex to gold(0) and to the formation of surface polysulphides. The data indicate that the adsorption of gold complexes onto iron sulphide surfaces such as that of pyrite is an important process in the “deposition” of gold from aqueous solutions over a wide range of temperatures and pressures. 相似文献
18.
铜陵矿山酸性排水及固体废弃物中的重金属元素 总被引：8，自引：0，他引：8
在调查中国铜陵凤凰山铜矿和新桥硫铁矿两种不同类型矿山固体废弃物特征的基础上,研究了矿山尾矿和废石产生酸性排水的可能性及其差异以及矿山固体废弃物中重金属元素的赋存形式。结果表明,凤凰山铜矿的尾矿基本不产生矿山酸性排水,而新桥硫铁矿采矿废石产生矿山酸性排水,并且凤凰山铜矿的尾矿和新桥硫铁矿采矿废石中重金属元素的赋存形式也有差异,前者重金属Cu、Pb、Zn、Cd、As、Hg主要赋存于硅酸盐态中,而后者在还原态中有较高的含量,这反映了在地表条件下尾矿中大量重金属元素已经发生了迁移,而采矿废石已经开始氧化,且酸性排水的存在更有利于废石中重金属元素的迁移和扩散,进而导致矿区周围环境的污染。 相似文献
19.
Jun Hao Curtis Cleveland Eelin Lim Daniel R Strongin Martin AA Schoonen 《Geochemical transactions》2006,7(1):8-9
The chemolithoautotrophic bacterium, Acidithiobacillus ferrooxidans, commonly occurs in acid mine drainage (AMD) environments where it is responsible for catalyzing the oxidation of pyrite
and concomitant development of acidic conditions. This investigation reports on the growth of this bacterial species on the
pyrite surface and in the aqueous phase at a pH close to 2 as well as the role of adsorbed lipid in preventing pyrite dissolution.
Both acid washed pyrite and acid-washed pyrite coated with lipids were used as substrates in the studies. The choice of lipid,
1,2-bis(10,12-tricosadiynoyl)-sn-Glycero-3-Phosphocholine lipid (23:2 Diyne PC), a phosphocholine lipid, was based on earlier work that showed that this lipid
inhibits the abiotic oxidation rate of pyrite. Atomic force microscopy showed that under the experimental conditions used
in this study, the lipid formed ~4–20 nm layers on the mineral surface. Surface-bound lipid greatly suppresses the oxidation
process catalyzed by A. ferrooxidans. This suppression continued for the duration of the experiments (25 days maximum). Analysis of the bacterial population on
the pyrite surface and in solution over the course of the experiments suggested that the pyrite oxidation was dependent in
large part on the fraction of bacteria bound to the pyrite surface. 相似文献
20.
Further knowledge as to the nature of the structure of a terrestrial sample of troilite, FeS [stoichiometric iron(II) sulfide] is revealed by a combination of XPS studies and dissolution studies in acid. The XPS analysis of a pristine troilite surface (the sample being cleaved under high vacuum) is compared to that of a surface polished in an inert atmosphere and a surface after reaction in deoxygenated acid. Further comparison is made with polished and acid-reacted surfaces of pyrrhotite (Fe1-xS) and pyrite (FeS2). The pristine troilite S2p spectrum comprises mainly monosulfide 161.1 eV, within the reported range of monosulfide, together with evidence of an unsatisfied monosulfide surface state arising from S-Fe bond rupture. Small, higher oxidation state sulfur contributions, including a disulfide-like state are also present, which suggest the presence of defects due to some nonstoichiometry. The dissolution studies showed that the troilite, in addition to dissolving in acid as an ionic solid to produce H2S, also exhibits some oxidation of sulfur in the surface layers. In addition, a study of the dissolution behavior of troilite under the influence of cathodic applied potential supported the existence of a proportion of the sulfur within troilite needing reduction before dissolution forming HS− or H2S can occur. A significant increase in the dissolution rate was observed with application of −105 mV (SHE), but further stepped decreases in potential to −405 mV and −705 mV resulted in a decreased rate of dissolution, a response typical of an ionic solid. The results of the studies emphasise the viewing of iron(II) sulfides as a continuum. Pyrrhotite has been reported previously to dissolve in acid both oxidatively (like pyrite) and nonoxidatively (like troilite) on the same surface. Dissolution studies using troilite, in Ar-purged acid, indicate that dissolution of this material may not be uniformly nonoxidative. XPS evidence of restructuring of the surface of troilite to pyrrhotite and the surface of pyrrhotite towards a FeS2 type structure, after exposure to Ar-purged acid, is presented. 相似文献