金属矿物的反应动力学与地球化学意义

概述了动力学实验的技术方法和金属矿物的反应动力学研究进展。动力学实验使用的三种基本化学反应装置是间歇反应器（ＢＲ）、活塞流反应器（ＰＦＲ）和混合流反应器（ＭＦＲ）,确定速率定律的数学方法包括积分法、微分法和混合法,以微分法中的初始速率法应用最广。目前主要研究了水溶液中黄铁矿氧化、黄铁矿和黄铜矿形成、晶质铀矿和磁铁矿溶解的速率定律和反应机理,发现：（１）酸性溶液中黄铁矿的氧化速率对Ｆｅ３＋和Ｏ２浓度呈分数依赖并受表面反应的控制;（２）低于３００℃时黄铁矿不能从溶液中直接成核,而需初始地通过ＦｅＳ先驱物的硫化生成,ＦｅＳ与Ｈ２Ｓ反应形成黄铁矿的速率方程为二级;（３）磁黄铁矿或黄铁矿与Ｃｕ２＋反应均可形成黄铜矿,前者经历了一系列准稳的Ｃｕ Ｆｅ硫化物的中间物,后者的速率方程为表观一级并受表面反应的控制;（４）酸性ｐＨ时磁铁矿的非线性溶解行为可采用表面反应扩散输运耦合的收缩核模型（ＳＣＭ）来描述。有关动力学实验成果完善和深化了对矿床中黄铁矿、黄铜矿的形成机理和风化壳中磁铁矿的稳定性等方面的认识。将来的实验研究将向更多的金属矿物和高温高压领域发展。     

微量元素与矿物表面反应研究进展

微量元素与矿物表面反应研究进展吴宏海吴大清（中国科学院广州地球化学研究所,广州５１０６４０）关键词矿物—水界面表面反应表面络合模式微量金属元素１研究意义与现状在地表环境中,大气圈、水圈和岩石圈之间存在着相互进行物质传输与能量交换的界面作用,其中矿物...     

草莓状黄铁矿的形成机制探讨及其对古氧化-还原环境的反演

【研究目的】草莓状黄铁矿广泛存在于现代沉积物和沉积岩中,其成因机制总体上分为有机成因和无机成因两种,尽管两种机制均有理论与实验的支撑,但尚未建立一种具有普遍意义的形成机制。【研究方法】本文对目前草莓状黄铁矿的形成机理、氧化还原环境的应用及后期环境变化的影响进行了系统的综合研究。【研究结果】不同氧化-还原环境下形成的草莓状黄铁矿在粒径、形态以及硫同位素之间均存在较大的差异,可做为反演古氧化-还原环境的指标。草莓状黄铁矿的微晶尽管与粒径具有一定的正相关性,但是两者在形态演化序列、生长模式、聚集因素等方面与古氧化-还原环境的关系尚不清楚。仅凭草莓状黄铁矿粒径与铬还原法测定的硫同位素反演古氧化-还原环境存在一定的局限性,需要其他指标综合判定,尚需进一步开展草莓状黄铁矿原位硫同位素值与粒径对古氧化-还原环境反演的研究。后期氧化可使草莓状黄铁矿表面化学成分发生变化,但粒径分布依然具有古氧化-还原环境的指示意义。【结论】草莓状黄铁矿的实验模拟、理论体系和多学科交叉的研究中仍存在一些问题,尚需进一步研究。     

硫化物矿物的表面反应及其在矿山环境研究中的应用

硫化物矿物的表面反应机理决定了以硫化物矿物为主的尾矿的重金属释放、吸附、解吸机制，其反应动力学与矿山环境污染程度存在内在联系。本文系统介绍了硫化物矿物的表面反应研究现状，包括反应机理、表面结构、表面位、反应产物、反应速率等，并指出了有待进一步研究的几个问题。     

湿-热条件下Fe-S系列矿物形成过程的实验研究

金属硫化物包括黄铁矿(FeS2)、白铁矿、磁黄铁矿(Fe1-xS)、胶黄铁矿(Fe3S4)等在多金属矿床中大量存在,能够反映矿床的成矿过程及矿体存在的物理化学条件等信息,对分析成矿地质条件和矿床地球化学环境有重要的意义。前人对     

黄铁矿晶体形貌学研究进展

介绍了黄铁矿晶体形貌学、黄铁矿晶体表面微形貌学的研究内容;黄铁矿习见晶形在金矿床研究中的标型意义;近年来黄铁矿晶须形貌学研究进展;黄铁矿形貌的生长机制研究内容等.根据前人黄铁矿习见晶形研究成果的理论实践意义,分析认为纳-微米黄铁矿晶须形貌成因和生长地质过程研究,不仅在矿物结晶生长理论研究中有意义,在认知纳米矿物,理解纳米矿化现象等方面有启示,纳-微米黄铁矿晶须形貌学研究值得重视.     

砂岩储层中有机酸对主要矿物的溶蚀作用及机理研究综述

砂岩储层中有机酸对矿物的溶解和沉淀在很大程度上影响着次生孔隙的发育。研究发现，有机酸之所以能提高石英的溶蚀速率和长石的溶解度，主要是由于在矿物的表面及溶液中形成络合物，有效地降低了矿物表面反应的活化能及溶液中硅、铝离子浓度的结果。有机酸与粘土矿物的吸附或催化反应可抑制长石等其他矿物的溶解。有机酸与CO2一起共同控制着体系中碳酸盐的溶解或沉淀。     

长石溶解模拟实验研究综述

在综合分析前人研究成果基础上,对长石溶解模拟实验研究进行了综述.研究表明,长石溶解与其成分、结构、反应的温压条件以及流体性质等有关.在相同的温压条件下,3种长石的稳定性依次为:钾长石>钠长石>钙长石,且温度升高可加强长石的溶解能力,促进长石的溶解,而压力的变化对长石的溶解影响不大.长石的溶解速率在酸性区域随pH值增大而减小、在中性区域溶解速率低且受影响小、在碱性区域随pH值增大而增大.有机酸通过提供H+、络合金属元素来提高长石的溶解度.长石的溶蚀速率与颗粒的总表面积大小以及颗粒表面粗糙度有关,总表面积越大,表面越粗糙,则反应速率越快,而且溶液的矿化度越低越有利于长石的溶解.长石的溶解过程由表面反应和扩散反应所控制,描述长石溶蚀机理的模型主要包括:表面反应模型和淋滤层扩散模型.     

矿物吸附金的实验研究及其在红土型金矿形成中的意义

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。     

黄铁矿中不可见金存在形式的实验研究—以冀东金厂峪金矿为例

不可见金存在于世界许多金矿的黄铁矿中。本文以冀东金厂峪金矿为例，对黄铁矿中不可见金的存在形式进行了多种实验方法的研究。黄铁矿金含量的多点分析和扫描电子显微镜实验研究表明，黄铁矿中不可见金大部分是呈链状排列的超显微金（粒度小于0.5μm的自然金）。黄铁矿的分步溶解实验、电子顺磁共振（EPR）及穆斯鲍尔谱研究证实黄铁矿中12.96％的不可见金以离子状态进入黄铁矿晶格代替Fe2 。     

秦岭隧道地下水水化学异常的形成机理

在分析秦岭隧道地区地质背景及水体水化学组成的变化规律的基础上,确定了平导地下水化学异常的基本特征及形成机理,研究表明水中硫根离子的审围岩中黄铁矿氧化所致钙离子的升高则归因于氧过程形成的大量氢离子促使含钙矿物水角或次生的碳酸盐矿物溶解,而两者浓度的增大导致地下水水化学类型的改变,矿化度及总硬度的异常。     

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。     

江西金山含金黄铁矿的稀土元素赋存状态研究

稀土元素在地质领域得到广泛的应用,查明稀土元素在地质体中的赋存状态,对应用稀土元素解决地学问题非常有意义。本文利用分步溶样ICP-MS测试方法对江西金山金矿含金黄铁矿中稀土元素作了详细的研究,试图弄清黄铁矿中稀土元素的赋存状态。实验表明,金山金矿与金成矿关系密切的黄铁矿的流体包裹体中稀土元素的含量很低;而具有高稀土元素含量的硫化物中的稀土元素主要赋存在硫化物所包含的富Zr微矿物中,如锆石、金红石、尖晶石、钛铁矿等。这些微矿物究竟是以包裹体子晶的形式存在,还是以捕虏晶的形式存在尚有待进一步研究。黄铁矿中包含的硅酸盐相对黄铁矿稀土元素含量及特征的影响很大,直接制约了黄铁矿的稀土元素组成。黄铁矿流体包裹体与黄铁矿矿物的稀土元素组成虽然在含量上有差异,但其配分形式相似,所以黄铁矿的稀土元素组成可以代表黄铁矿中液体包裹体的稀土元素组成,通过分析黄铁矿的稀土元素特征,可以示踪成矿流体的来源与性质,前提是实验中不要将黄铁矿样品全部溶掉,以保证黄铁矿中所包裹的硅酸盐相不参与黄铁矿REE组成的测量。     

Determination of mineralization stages using correlation between geochemical fractal modeling and geological data in Arabshah sedimentary rock-hosted epithermal gold deposit,NW Iran

This research paper aims to delineate and recognize different gold mineralization stages based on surface lithogeochemical data using factor analysis and Spectrum-Area (S-A) modeling, as well as geological data in Arabshah sedimentary rock hosted epithermal gold deposit, NW Iran. Based on the factor analysis, Au and Mn were allocated to factor 2 (F2) and then classified by the S-A fractal modeling. In addition, Au and F2 values were transformed to spectrum data, which were categorized by the S-A log-log plots. Accordingly, the main mineralization phase contains Au and F2 (Au-Mn) values greater than 800 ppb and 0.3, respectively, and is associated with the occurrence of minerals such as pyrite, arsenian pyrite, realgar, orpiment and oxidized sulfides. The first phase of gold mineralization, where Au typically ranges between 80 and 350 ppb, is associated with base metal sulfides, arsenian pyrites and F2 values between 0.1 and 0.2. The second gold mineralization phase consists of Au values from 350 to 800 ppb and F2 values between 0.2 and 0.3. Combination of the S-A modeling, factor analysis and geological data outlined three gold mineralization stages in Arabshah gold deposit. The main mineralization stage showed a strong positive correlation with the NE-SW and NW-SE trending structures, the altered intrusive rocks such as microdiorite and granodiorite, and the altered subvolcanic dacitic domes.     

Pyritization processes and greigite formation in the advancing sulfidization front in the upper Pleistocene sediments of the Black Sea

Pyritization in late Pleistocene sediments of the Black Sea is driven by sulfide formed during anaerobic methane oxidation. A sulfidization front is formed by the opposing gradients of sulfide and dissolved iron. The sulfidization processes are controlled by the diffusion flux of sulfide from above and by the solid reactive iron content. Two processes of diffusion-limited pyrite formation were identified. The first process includes pyrite precipitation with the accumulation of iron sulfide precursors with the average chemical composition of FeS_n (n = 1.10-1.29), including greigite. Elemental sulfur and polysulfides, formed from H₂S by a reductive dissolution of Fe(III)-containing minerals, serve as intermediates to convert iron sulfides into pyrite. In the second process, a “direct” pyrite precipitation occurs through prolonged exposure of iron-containing minerals to dissolved sulfide. Methane-driven sulfate reduction at depth causes a progressive formation of pyrite with a δ³⁴S of up to +15.0‰. The S-isotopic composition of FeS₂ evolves due to contributions of different sulfur pools formed at different times. Steady-state model calculations for the advancement of the sulfidization front showed that the process started at the Pleistocene/Holocene transition between 6360 and 11 600 yr BP. Our study highlights the importance of anaerobic methane oxidation in generating and maintaining S-enriched layers in marine sediments and has paleoenvironmental implications.     

锍镍试金-电感耦合等离子体质谱法测定硫铁矿中铂族元素

锍镍试金常用于富集常规地质样品中的铂族元素(PGEs);而用于富集硫铁矿中的PGEs鲜有报道。硫铁矿中硫和铁的含量较高,采用常规的试金配方不能得到较好的锍扣,影响下一步样品的溶解和过滤。本文对锍镍试金-电感耦合等离子体质谱法测定硫铁矿中PGEs的流程进行改进。针对硫铁矿中硫和铁含量高的特点,在不减少称样量的情况下,调整常规锍镍试金中的试剂配方,获得了理想的锍扣和熔渣,使锍扣富集PGEs的能力达到最佳,且避免了由于反应时间过长而造成PGEs损失。同时利用硫化铁易剥落和粉化的特点,省去了锍扣的机械粉碎工序,简化了流程,避免了碎扣时的机械损失和样品间可能的交叉污染。结果表明,高含量的铁对PGEs的测定无显著影响。加标回收试验显示PGEs全流程回收率大于94%。按10 g取样量计算,方法检出限分别为Ru 0.018 ng/g,Rh 0.017ng/g,Pd 0.18 ng/g,Os 0.019 ng/g,Ir 0.013 ng/g,Pt 0.11 ng/g。实际样品分析和加标回收试验表明,改进后的锍镍试金-电感耦合等离子体质谱测定流程可以满足大多数硫铁矿中PGEs的测定要求。     

次显微金在毒砂,黄铁矿等矿物中富集的成因研究

本文详细探讨了次显微金在毒砂、黄铁矿等矿物中富集的成因机制，指出这些矿物生长时生长面附近出现的氧化还原电位局部降低和（或）（ＡｓＳ）３－，Ｓ２－等组分的局部负异常会导致金的络合物变得不稳定和易于分解，从而引起次显微金在这些矿物中富集。由此笔者解释了次显微金龙富集于小颗粒的毒砂、黄铁矿中及特别富集于这些矿物边缘的原因。同时笔者认为普遍呈小圆球形态出现于载金矿物中的金颗粒可能是金胶体沉聚下来形成的。文中还对黄铁矿含Ａｕ量与含Ａｓ量之间具正相关关系以及黄铁矿和黄铜矿的含Ａｕ量在不同矿床中互有高低的原因予以了解释     

Pyrite oxidation in the tertiary sands of the London Basin aquifer

Possible groundwater quality changes related to pyrite oxidation during artificial groundwater recharge and its storage in the Tertiary sands of the London Basin are investigated. Pyrite textures in the Tertiary sands are examined by scanning electron microscopy while an experimental approach is used to study mechanisms of pyrite oxidation and of some associated chemical reactions. In the Tertiary sands of the London Basin aquifer, pyrite occurs as aggregates made of discrete individual crystals 0.5–5 μm in size or, in a cryptocrystalline form, often as pseudomorphs of biogenic debris. It can expose a very large specific surface area to porefluids. Although ferric iron, which can be an oxidising agent of pyrite, is abundant in the solid phase of the Tertiary sands, it does not appear to take a significant part in this case. Pyrite oxidation seems to rely on a supply of oxygen. Leaching experiments using a 0.001 M H₂SO₄ solution were carried out to examine interactions between mildly acidic groundwater resulting from pyrite oxidation at a moderate rate and the host-sediment. In the presence of CaCO₃ in the solid phase, H⁺ is rapidly buffered by CaCO₃ dissolution. Oscillations of this reaction around equilibrium appear to trigger cation-exchange reactions on clay mineral surfaces, resulting in the release of major cations (e.g. K and Mg) into solution. In the absence of CaCO₃ in the solid phase, H⁺ buffering occurs less efficiently solely through exchange of cations for H⁺ on clay minerals surfaces. If the rate of pyrite oxidation in the Tertiary sands becomes high enough for the buffering capacity of the system to be exceeded, the groundwater pH begins to fall. Interactions between low pH (2) groundwaters and the host sediments were examined by leaching solid material in 0.01 M and 0.1 M H₂SO₄ solutions. Concentrations of Fe, Mg and K increase in solution throughout the experiment, indicating partial dissolution of clay minerals. The composition of the porefluid thus depends on the geochemical composition and surface area of the different clay minerals present.     

Quantification of mineral dissolution rates and applicability of rate laws: Laboratory studies of mill tailings

Reliable quantification of mineral weathering rates is a key to assess many environmental problems. In this study, the authors address the applicability of pure mineral laboratory rate laws for dissolution of mill tailings samples. Mass-normalised sulfide and aluminosilicate mineral dissolution rates, determined in oxygenated batch experiments, were found to be different between two samples from the same ∼50-year-old, carbonate-depleted mill tailings deposit. Consideration of difference in particle surface area and mineralogy between the samples resolved most of this discrepancy in rates. While the mineral surface area normalised dissolution rates of pyrite in a freshly crushed pure pyrite specimen and a sulfide concentrate derived from the tailings were within the range of abiotic literature rates of oxidation by dissolved molecular O₂, as were rates of sphalerite and chalcopyrite dissolution in the tailings, dissolution rates of pyrite and aluminosilicates in the tailings generally differed from literature values. This discrepancy, obtained using a consistent experimental method and scale, is suggested to be related to difficulties in quantifying individual mineral reactive surface area in a mixture of minerals of greatly varying particle size, possibly due to factors such as dependence of surface area-normalised mineral dissolution rates on particle size and time, or to non-proportionality between rates and BET surface area.