矿物表面活性与反应性

矿物表面活性是矿物表界面反应中一个重要的指标性参数。如矿物溶解和晶体生长、矿物表面吸附和表面络合反应、矿物表面氧化还原和催化反应,都与矿物表面活性相关。甚至生物矿物界面作用过程中,常用到矿物表面反应性氧基(ROS),其释放能力也与矿物表面活性密切相     

黑色页岩水岩化学作用实验研究

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。     

纳米尺度下的生物矿物和生物矿化:基于介晶的视角

纳米地质学的兴起和发展,促使地质工作者从纳米尺度重新认识固体地球物质,将对地球科学的各个领域产生广泛而深刻的影响.作为纳米地质学的重要分支,纳米矿物学也将走出传统矿物学只把矿物看成理想晶体点阵的局限,从纳米尺度深入探究矿物包括生物矿物在内的矿物结构与性质,突破口之一是介晶.介晶是一种特殊的结晶纳米结构,近年来得到了物理学家和化学家尤其是材料化学家越来越多的关注.介晶是非经典结晶过程产物,以纳米颗粒为基本构筑单元,具备纳米颗粒的性质和宏观尺寸.现已发现,许多生物矿物如脊椎动物骨骼和牙齿、贝壳珍珠层、蛋壳、海胆骨针、有孔虫和珊瑚等都具有介晶结构.因此,从纳米尺度和介晶角度重新理解生物矿化,有助于揭示生物矿物中纳米多级结构的成因机制,拓展纳米矿物学的科学内涵.首先介绍生物矿化和生物矿物的基本概念,之后对介晶的概念和结构特征进行阐述,最后介绍生物矿物中的介晶结构及介晶形成的典型机制,涉及有机基质辅助、物理场驱动、矿物桥或有机桥连接、空间限域、取向附集和晶面选择性分子作用等多种物理化学过程,有望进一步推动纳米矿物学的发展.      

雄黄矿物表面氧化过程的量子化学计算

采用密度泛涵量子化学计算方法对雄黄矿物晶体{010}晶面进行了计算，分析了该晶面的表面化学反应活性，表明表面上不同位置As、S原子的化学活性相差不大；同时对雄黄矿物晶体{010}表面吸附H2O、O2分子时的模型进行了势能面扫描计算，发现H2O和O2分子在该表面吸附时将发生解离，同时雄黄中的As将被氧化而形成砷的氧化物。     

硫化物矿物氧化反应动力学实验研究

硫化物矿床和含硫化物矿床（如中高硫煤）在开发过程中由于氧化作用向环境释放大量的酸、硫酸盐、重金属及其它有害物质,造成一定范围内的次生地球化学异常和环境污染;而中国大陆硫化物的排放量2010年将达到39．1×10 6 t。因此,人们对硫化物矿物在表生环境下的氧化行为日益重视。硫化物矿物的氧化速率受矿物本身物理化学特性（组成、结构、表面性质）和介质条件（溶解氧DO、Fe 3＋浓度、pH、Eh、温度及微生物）等多种因素的控制。在全面分析近年来国内外文献的基础上,系统介绍了硫化物矿物氧化动力学实验研究方法、实验参数的选择、反应机理、反应产物及反应速率等的研究现状。指出今后应加强对初始阶段的氧化反应速率、反应中间产物、多因素的综合作用、分子水平上的反应机理解释等方面的研究。     

热液型金矿床中的黄铁矿矿物学研究综述

黄铁矿是热液金矿化体系中较为重要的矿物。黄铁矿精细矿物学研究是热液金矿床成矿机制研究的一个重要课题。黄铁矿的矿物学特征主要包括物理结构和化学成分特征。笔者综述了黄铁矿的形态、晶胞参数及热电性等物理结构特征和地球化学成分特征在热液金矿床的应用及其研究进展。黄铁矿的物理特征及其时空变化规律,可以定性约束成矿物理化学条件的演化过程。黄铁矿的微量和稀土元素组成、分布及演化特征,可以示踪成矿物质及成矿流体来源,进而获得有关矿床成因及金属沉淀机制等方面的信息。此外,近年来发展迅速的黄铁矿单矿物Re-Os同位素定年及原位微区稳定同位素(S、Pb)分析可以对确定金矿床精确成矿年代及精细成矿过程提供重要的参考信息。     

金矿床的矿物蚀变与矿物标型及其找矿意义

绝大多数金矿床的形成或多或少都与热液活动有关。成矿过程中伴随流体的运移和演化,流体与围岩会不断发生水-岩反应并导致金物质在适合的构造空间堆积成矿,同时在流体途经区留下蚀变产物。这一过程中形成的蚀变矿物特征和矿物组合能够指示成矿过程的物理化学条件的变化,是找矿的重要信息。这一能够标识成矿过程的矿物学特征统称为矿物标型特征。基于与金矿矿化关系密切的常见矿物蚀变现象及其时空分布规律,并以矿物标型特征参数(如载金矿物黄铁矿热电性特征、蚀变矿物短波红外光谱特征和蚀变岩磁化率特征等)为基础,通过蚀变矿物分带和矿物学填图,可以建立成矿模式和找矿模型,进而指导找矿勘查。本文通过对多个矿床实例的总结分析,认为以矿物标型特征为主要参数的矿物学填图是有效缩小找矿靶区或进行深部预测的找矿方法之一。     

无氧条件下黄铁矿表面的羟基化与自氧化

过去20年里,无氧条件下黄铁矿–水界面产生活性氧是黄铁矿表面反应性的重要发现之一。这一反应不仅对现代环境有重要影响,而且在早期地球环境演化中也扮演着重要角色。无氧条件下黄铁矿–水界面产生的活性氧具有极强的氧化性,理论上有氧化黄铁矿自身的能力。然而,无氧条件下黄铁矿–水界面产生的活性氧对其自身是否有氧化作用(即黄铁矿自氧化)及其反应机制还不得而知。本研究采用原位漫反射红外傅里叶变换光谱(in-situDRIFTS)和准原位X射线光电子能谱(quasi-in-situXPS)结合密度泛函理论(DFT)计算,探究了无氧条件下黄铁矿–水界面的自氧化初始反应过程。结果表明:(1)无氧条件下黄铁矿–水界面会发生自氧化反应,生成高价态的硫物种和铁氧化物;(2)黄铁矿–水界面的自氧化反应伴随着羟基的生成和消耗;(3)黄铁矿–水界面的羟基源于水分子在黄铁矿表面缺陷位点的解离作用,可为活性氧的产生提供物源。这些发现不仅揭示了黄铁矿–水界面的羟基化和自氧化过程,还为深入理解黄铁矿–水界面反应在早期地球环境演化中的重要作用提供了认知基础。     

热液矿床矿物微形貌与晶体生长环境研究

应用高分辨率扫描隧道显微镜(STM)和场效应扫描电镜(FEG SEM),对取自山西义兴寨金矿等4处热液矿床的黄铁矿、方铅矿、赤铁矿等矿物的表面生长微形貌进行了观察研究,并与实验合成的黄铁矿、方铅矿等矿物的微形貌特征进行对比。发现了自然矿物结晶三维成核成因的黄铁矿微球状晶,在合成和自然矿物的晶面观察到漏斗状晶和胞状结构等生长形貌。合成黄铁矿表面发育平整光滑的生长台阶,反映静态无扰动、接近平衡的晶体生长环境;而大量产于热液矿床的黄铁矿、方铅矿等晶体普遍发育胞状或拉长的胞状结构表面,并总体呈台阶状排列的表面结构,证明自然成矿热液体系的高过饱和度和流动生长环境。研究表明,热液成矿过程中矿物结晶作用有从成核、台阶状晶体生长、到形成“平衡”多面体生长的一个演化过程;形成于复杂条件的矿物晶体表面微观结构,包含丰富的成矿环境信息。     

氧化亚铁硫杆菌对黄铁矿的氧化作用初探

利用自行分离培养的氧化亚铁硫杆菌(A.f菌)为实验菌株,比较了黄铁矿化学氧化和生物氧化过程中溶液铁离子浓度的变化。研究发现,Fe3 对黄铁矿的氧化速率较低,而在细菌的作用下可以不断将Fe2 氧化成Fe3 使得黄铁矿的氧化速率明显加快,因此生物氧化具有更高的效率。经过44 d的氧化之后,利用扫描电镜对氧化后的黄铁矿表面进行了显微观察,发现Fe3 的化学氧化主要集中在化学键较弱的晶棱部位,而在生物氧化的情况下矿物表面充满了密集的溶蚀坑,溶蚀坑的形状与A.f菌的外形非常相近,且规则排列。这说明A.f菌能够吸附到黄铁矿表面,并且这种吸附具有定向排列的特点。     

Effect of sulfide impurities on the reactivity of pyrite and pyritic concentrates: a multi-tool approach

Sulfide mineral oxidation, primarily pyrite and pyrrhotite, generates acid mine drainage during weathering. Successful management of acid generating wastes entails the suppression of the initiation of oxidation reactions. The reactivity of pyrite depends on ore mineralogy, including the effects of associated sulfide impurities. The electrochemical surface characterization study using cyclic voltammetry with carbon paste electrodes containing minerals particles (CPE-Mineral) is an effective tool for demonstrating how the various mineral characteristics work together to influence the overall reactivity of the mineral. This study was supported by chemical, mineralogical and leachate chemistry data. The results show that the presence of other sulfides in contact with pyrite at the beginning of the weathering process is the most important parameter affecting pyrite reactivity, which is likely to be oxidized and passivated. In more advanced stages of leaching, mineral coatings which passivate the pyrite surfaces tend to play the most important role in defining the reactivity of pyrite. The electrochemical response of pyritic samples in conjunction with the evolution of the chemical quality of the leach solution in the simple experimental device here used, could then provide valuable information on acid mine drainage generation.     

矿物表面基团与表面作用

矿物的表面或界面过程存在于一切地质过程中,并在材料和环境科学领域得到广泛应用。矿物的表面结构、表面基团与表面作用之间存在着一定的内在联系,矿物结构的多样性决定了表面基团类型的多种性和表面作用的多样性。本文较系统地介绍了矿物表面功能基、表面配位反应、表面配合反应、表面氧化还原反应、表面异位催化反应和表面离子交换反应的类型及作用机制。     

矿物表面活性及其量度

矿物及其材料的表面活性及其表面反应性的具体表征，它是由矿物表面功能基所控制。由于矿物表面金属原子的电负性不同，以及它所处的配位环境不同，常表现出不同的极性、荷电性和Lewis酸碱性，它与溶质和溶剂分子之间反应（成键）能力也不同。在热力学上表现为反应自由能变化也不同。因此，量度矿物表面活性就是量度其表面极性、荷电性和Lewis酸碱性，它既可用化学方法，也可用热力学的方法。前者是通过反应作用量来量度，后者通过反应作用能来量度。然而现代矿物谱学的方法更能给出矿物及其材料表面反应活性的本质和详细信息。     

Cell adhesion of <Emphasis Type="Italic">Shewanella oneidensis</Emphasis>to iron oxide minerals: Effect of different single crystal faces

The results of experiments designed to test the hypothesis that near-surface molecular structure of iron oxide minerals influences adhesion of dissimilatory iron reducing bacteria are presented. These experiments involved the measurement, using atomic force microscopy, of interaction forces generated between Shewanella oneidensis MR-1 cells and single crystal growth faces of iron oxide minerals. Significantly different adhesive force was measured between cells and the (001) face of hematite, and the (100) and (111) faces of magnetite. A role for electrostatic interactions is apparent. The trend in relative forces of adhesion generated at the mineral surfaces is in agreement with predicted ferric site densities published previously. These results suggest that near-surface structure does indeed influence initial cell attachment to iron oxide surfaces; whether this is mediated via specific cell surface-mineral surface interactions or by more general interfacial phenomena remains untested.     

ToF-SIMS and SEM study on the preferential oxidation of chalcopyrite

Chalcopyrite is known to be slow reacting mineral in hydrometallurgical systems and is considered one of the most inert sulphide minerals with respect to leaching. Such character of chalcopyrite seems to be linked to a formation of a passive layer on its surface. This work reports that freshly fractured chalcopyrite surfaces exhibit highly selective reactivity depending on the exposed fracture planes. ToF-SIMS was used to qualitatively characterize various fracture planes in freshly fractured chalcopyrite particles, prior to and after hydrometallurgical treatment. It was found that, prior to treatment, certain areas exhibited pronounced contamination from atmospheric hydrocarbons; whereas, others were highly unreactive and remarkably free from adventitious hydrocarbon contamination. The positive ion spectra recorded from these areas were found to be dominated by peaks from Fe- and Cu-elements and related compounds. The negative ion spectra for the reactive areas on the other hand showed a high content of oxidized (sulphur) species.The differences between the areas of low and high reactivity, as detected after leaching, were more subtle than prior to leaching; whereas, SEM analysis showed clear evidence for selective attack of ferric sulphate to specific planes. Furthermore, it was shown that, when chalcopyrite is in intimate contact with pyrite, it experiences an enhanced oxidation compared to when there is no electric contact with pyrite.Attempts were made to explain the preferential oxidation observed based on the different chemistry of the fracture surfaces.     

An attempt to use LA-ICP-SMS to quantify enrichment of trace elements on pyrite surfaces in oxidizing mine tailings

Metals released from oxidation and weathering of sulphide minerals in mine tailings are to a high degree retained at deeper levels within the tailings themselves. To be able to predict what could happen in the future with these secondarily retained metals, it is important to understand the retention mechanisms. In this study an attempt to use laser ablation high-resolution ICP-MS (LA-ICP-SMS) to quantify enrichment of trace elements on pyrite surfaces in mine tailings was performed. Pyrite grains were collected from a profile through the pyrite-rich tailings at the Kristineberg mine in northern Sweden. At each spot hit by the laser, the surface layer was analyzed in the first shot, and a second shot on the same spot gave the chemical composition of the pyrite immediately below. The crater diameter for a laser shot was known, and by estimating the crater depth and total pyrite surface, the total enrichment on pyrite grains was calculated. Results are presented for As, Cd, Co, Cu, Ni and Zn. The results clearly show that there was an enrichment of As, Cd, Cu and Zn on the pyrite surfaces below the oxidation front in the tailings, but not of Co and Ni. Arsenic was also enriched on the pyrite grains that survived in the oxidized zone. Copper has been enriched on pyrite surfaces in unoxidized tailings in the largest amount, followed by Zn and As. However, only 1.4 to 3.1% of the Cd and Zn released by sulphide oxidation in the oxidized zone have been enriched on the pyrite surfaces in the unoxidized tailings, but for As and Cu corresponding figures are about 64 and 43%, respectively. There were many uncertainties in these calculations, and the results shall not be taken too literally but allowed the conclusion that enrichment on pyrite surfaces is an important process for retention of As and Cu below the oxidation front in pyrite rich tailings. Laser ablation is not a surface analysis technique, but more of a thin layer method, and gives no information on the type of processes resulting in enrichment on the pyrite surfaces. Although only pyrite grains that appeared to be fresh and without surface coatings were used in this study, the possibility that a thin layer of Fe-hydroxides occurred must be considered. Both adsorption to the pyrite directly or to Fe-oxyhydroxides may explain the enrichment of As, Cd, Cu and Zn on the pyrite surfaces, and, in the case of Cu, also the replacement of Fe(II) by Cu(II) in pyrite.     

黄铁矿载金的原因和特征

对102个金矿床载金矿物的统计表明,黄铁矿是最普遍最重要的载金矿物。造成黄铁矿成为主要载金矿物的原因,有三个矿物学方面的因素,即结构因素、成核因素和电化学因素。结构因素表现在黄铁矿晶体结构中存在对硫 ［S2］2－,对硫 形成过程中对金离子具还原效应。成核因素表现在自然金成核常选择原子排布与之最接近的黄铁矿表面为衬底,以降低成核能。电化学因素表现在黄铁矿的热电性导致金离子在其表面发生电化学反应而沉淀结晶。对黄铁矿载金能力的分析表明,细粒、它形、裂隙发育程度高、As和Sb含量高以及P型的黄铁矿载金能力高,自形黄铁矿中的{210}、S面{100}及其聚形晶的载金能力高。     

Interactions between sulphide minerals and xanthates,I. The formation of monothiocarbonate at galena and pyrite surfaces

The rate of decomposition of potassium ethyl monothiocarbonate has been determined at pH values between 5 and 10, and its molar absorptivity at 221 nm determined to be 1.24 · 10⁴mol/cm.A novel apparatus for use in the study of reactions between sulphide minerals, oxygen and thiol reagents has been developed, and applied to the reactions of potassium ethyl xanthate with galena and pyrite. It has been shown that both minerals react with ethyl xanthate in the presence of oxygen or oxidation products to form soluble as well as adsorbed xanthate derivatives. The soluble derivative has been identified to be ethyl monothiocarbonate. The adsorbed xanthate at a galena surface, unlike that at a pyrite surface, is gradually converted to a soluble monothiocarbonate under the action of dissolved oxygen. The effect of variables such as pH, the initial xanthate and oxygen concentrations, and the initial state of oxidation of the mineral on the formation of monothiocarbonate has been studied. It is tentatively proposed that an intermediate adsorbed mixed xanthate-hydroxide species is involved in the formation of monothiocarbonate at both galena and pyrite surfaces.The significance of the formation of monothiocarbonate to flotation practice is discussed briefly. The formation of monothiocarbonate represents a wastage of reagent, and could lead to a decrease in flotability of xanthated galena with time of exposure to aerated solutions.