广西龙头山金矿床黄铁矿特征与金矿化的关系

通过对广西龙头山金矿床黄铁矿的显微镜下特征、化学成分特征和微量元素含量特征与金矿化关系进行的研究发现,黄铁矿与金矿化密切相关;黄铁矿的颜色、晶粒受力破碎程度和被后期矿物交代、氧化程度均与金矿化有较大的关系;金矿化还与铋的关系密切,说明金矿化的多期次、多阶段性;黄铁矿的Co/Ni比值均大于1;As的含量较高,平均为863×10-6;Fe/S质量分数比值均小于0.871,表现为铁亏损;随着Fe/S比值的增大,金品位有增加的趋势;且S、Fe原子比不是严格的2∶1,而是略微偏大,并随S/Fe原子比的减小,金品位有所增加。光片统计结果表明,单体金矿物占73.57%,包裹于黄铁矿中的金矿物占26.43%,这种嵌布关系有利于金矿物的回收。     

水热法合成黄铁矿微观形貌和结构的观测与表征

模拟热液型金矿床中黄铁矿生成的地质条件,采用硫酸亚铁(FeSO4)和硫代乙酰胺(CH3CSNH2)为铁源和硫源,在Fe/S比为1∶3、温度180~200 ℃、加热时间24 h条件下考察黄铁矿的结晶情况。用SEM扫描电镜观察在不同水热条件下合成黄铁矿的形态及成分;用多晶X射线衍射仪(XRD)确定了产物物相组成;用透射电子显微镜(TEM)观测表征了黄铁矿晶体的形态和结构。结果表明：在200 ℃时黄铁矿为粒状,粒度较均匀,粒径1 μm左右。在180 ℃时黄铁矿除有尺寸在1 μm左右粒状黄铁矿外,还有不规则带状黄铁矿晶体,带宽为200 nm左右。认为水热条件中,随着结晶温度的逐步升高,黄铁矿的形貌逐步由不规则形状向规则形状的转变。所以在实验温度较高阶段,形成规则的粒状形貌;在低温阶段,则会出现不规则带状形貌。     

金川铜镍硫化物矿床磁黄铁矿矿物学特征及成因意义

金川铜镍硫化物矿床矿石类型主要为浸染状矿石、海绵陨铁状矿石及块状矿石。采用矿相显微镜观察、磁性胶体浸润与电子探针分析等方法,对3种类型矿石中磁黄铁矿的结构状态、共生组合与成分特征作了研究,探讨了矿石成因及成矿过程。在浸染状矿石与海绵陨铁状矿石中,磁黄铁矿为单纯的六方(NC型)磁黄铁矿,或者六方与单斜(4C型)磁黄铁矿构成的不规则状交生体。这2类矿石中磁黄铁矿的成因很可能是岩(矿)浆中S含量低,且高温结晶后缓慢降温,后期又受到了富硫和/或高氧逸度流体的交代作用。在Ⅱ矿区块状矿石中,单斜与六方磁黄铁矿构成平行叶片状交生体,表明六方磁黄铁矿在高温下结晶后温度曾快速下降,这期间仅出溶了微量的黄铁矿,而当温度下降到254℃以下时,发生了六方磁黄铁矿中单斜磁黄铁矿出溶作用。磁黄铁矿的结晶类型、金属原子(Fe、Ni、Cu、Co)与硫原子比值M/S演化等佐证了块状矿石晚期贯入成因。依据Fe-S系统相图拟合曲线计算得到块状矿石中六方磁黄铁矿结晶温度为743~518℃,且在结晶过程中,硫逸度logf(S2)曾从0.427降至-3.767。     

紫硫镍矿交代镍黄铁矿的水热反应机理及动力学

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。     

自然燃烧对增强土壤磁赤铁矿含量的影响实验

根据前人关于自然燃烧作用生成磁赤铁矿的两阶段模式,模拟自然燃烧作用形成磁赤铁矿的过程和条件。实验分2阶段进行,第一阶段氢气氛围300℃煅烧针铁矿2 h,煅烧产物为纳米磁铁矿;第二阶段70℃空气条件下氧化煅烧成因的纳米磁铁矿70 d。对实验两阶段样品的矿物学和磁学特性进行系统测定,结果表明,本研究的煅烧条件可获得接近理想成分的多孔纳米磁铁矿,晶粒及聚集体的粒径分别在30 nm和57 nm左右;在70℃空气氛围下磁铁矿快速向磁赤铁矿转化,70 d的实验时间里2价铁/全铁比值(Fe2+/TFe)由初始31.4%降至5.4%;纳米磁铁矿向磁赤铁矿转化伴随着矿物结晶颗粒的减少和样品总体积的增大,磁铁矿结晶学粒径缩小约17%~19%;磁化率和频率磁化率随氧化时间逐渐降低,前者主要受制于矿物物相变化,而后者与矿物粒径变化相关。模拟结果表明,第一阶段的关键是具有生成晶粒尺寸为亚微米-纳米量级的磁铁矿煅烧条件,第二阶段的关键为具备一个合适的温度条件,以能够快速、高效氧化磁铁矿为磁赤铁矿。     

湘黔地区下寒武统黑色岩系中镍-钼矿床黄铁矿的成因

重点研究了贵州遵义中南村和湖南张家界三岔镍-钼多金属矿床的黄铁矿,矿床成因为热水喷流沉积型。黄铁矿样品S/Fe比值的平均值为2.0093~2.048,成分特征均属于铁亏损型,说明其形成温度低。Co/Ni变化范围为0.077~4.5,均值为2.197,据Co/Ni的比值可以判断本区的黄铁矿主要为热液成因,矿化物质来源为热水喷流体系内的热液。成分图解标型显示,黑色岩系中高ω(Co+Ni)/ω(Fe)的黄铁矿和高ω(As+Se+Te)/ω(S)的黄铁矿均大量出现,可能与热水喷流沉积的温差变化范围较大有关,而并非正常沉积的产物。S/Se比值为950.8~1059.9,说明生成环境均一程度较高,而且海水温度比较高。由中南村镍-钼矿床的Se/Te值也能判明其为热液成因。关于黄铁矿的研究对本区镍-钼矿床的寻找有重要意义。     

紫金山金铜矿黄铁矿化学成分标型特征及其意义

紫金山金铜矿属典型的高硫化型浅成低温热液矿床。黄铁矿的电子探针(EPMA)测试和S同位素分析显示,该区黄铁矿总体表现为亏Fe富S型,S/Fe原子比从浅部到深部呈现升高的趋势,表明深部成矿是高氧—高硫化环境;黄铁矿的Ni-Co图解、As-Co-Ni三角相图解及w(Se),w(S)/w(Se)标型特征显示,其是与火山作用有关的热液成因;该区黄铁矿是原生金的主要载金矿物,Au是以纳米级自然金(Au0)的形式存在的;黄铁矿的w(Cu+Pb+Zn)从浅部到深部呈逐渐增加的趋势;黄铁矿微量元素的lga-lgb成正相关关系;黄铁矿的微量元素综合比值Ф从浅部到深部呈逐渐降低的趋势;黄铁矿的S同位素结果表明,其δ34S值介于-3.0‰~3.5‰之间,极差为6.50‰,平均值为-0.18‰,S主要来源于深部岩浆。根据其化学成分标型特征,总结该矿床的产出环境、热液及成矿物质来源等成因信息,并对高硫化型浅成低温热液矿床中黄铁矿的化学成分标型提供一定的研究基础。     

冀北张家口地区汉诺坝玄武岩中麻粒岩捕虏体的硫化物相

捕虏体麻粒岩是了解下地壳形成和演化的重要样品.汉诺坝新生代玄武岩中的二辉麻粒岩捕虏体样品中富含各种硫化物相,主要类型有:①孤立产出的球状出溶硫化物;②矿物颗粒之间或颗粒内的粗晶硫化物;③次生硫化物包裹体群;④裂隙充填硫化物.电子探针分析表明,硫化物的矿物成分均为贫镍磁黄铁矿,(Ni Co Cu)/Fe(原子比)远小于0.2;(Fe Cu Co Ni)/S(原子比)比地幔岩的磁黄铁矿小,多小于0.875,反映了一种S过饱和环境.各种产状的磁黄铁矿中Au、Ag都有一定的含量,其平均值分别为0.19%～0.22%(Au)、0.01%～0.02%(Ag),反映下地壳的麻粒岩化与金矿化的成因联系.磁黄铁矿的Ni、Co、Cu含量与S正相关,说明微量重金属元素与S具有同源的关系,由于地幔去气伴随S而进入下地壳.     

冀北张家口地区汉诺坝玄武岩中麻粒岩捕虏体的硫化物相

捕虏体麻粒岩是了解下地壳形成和演化的重要样品。汉诺坝新生代玄武岩中的二辉麻粒岩捕虏体样品中富含各种硫化物相,主要类型有:①孤立产出的球状出溶硫化物;②矿物颗粒之间或颗粒内的粗晶硫化物;③次生硫化物包裹体群;④裂隙充填硫化物。电子探针分析表明,硫化物的矿物成分均为贫镍磁黄铁矿,(Ni+Co+Cu)/Fe(原子比)远小于0.2;(Fe+Cu+Co+Ni)/S(原子比)比地幔岩的磁黄铁矿小,多小于0.875,反映了一种S过饱和环境。各种产状的磁黄铁矿中Au、Ag都有一定的含量,其平均值分别为0.19%～0.22%(Au)、0.01%～0.02%(Ag),反映下地壳的麻粒岩化与金矿化的成因联系。磁黄铁矿的Ni、Co、Cu含量与S正相关,说明微量重金属元素与S具有同源的关系,由于地幔去气伴随S而进入下地壳。     

陕西八卦庙金矿床NE向黄铁矿-石英成矿期成矿物质来源和成矿机制探讨:原位硫同位素证据

八卦庙金矿床位于秦岭造山带凤太铅锌多金属矿田北部,是陕西省规模较大的金矿床之一,已探明金储量约106 t.赋矿围岩是上泥盆统星红铺组浅变质泥质碎屑岩和碳酸盐岩,其成矿过程可划分为3期,分别是①顺层磁黄铁矿-石英成矿期;②NE向黄铁矿-石英成矿期;③裂隙硫化物-方解石成矿期.目前关于NE向黄铁矿-石英成矿期成矿物质来源和成矿机制仍存在争议.本文通过矿相学观察,将NE向黄铁矿-石英成矿期划分为自形磁黄铁矿-黄铁矿-粗粒石英阶段(Ⅰ)、他形黄铁矿-银金矿-细粒石英阶段(Ⅱ)、他形磁黄铁矿-自然金-方解石阶段(Ⅲ)和黑云母阶段(IV),并在此基础上采用激光剥蚀-多接收等离子体质谱(LA-MC-ICP-MS)分析方法对千枚岩围岩中以及不同阶段形成的硫化物进行了原位S同位素测试,结果显示围岩中原生磁黄铁矿的δ34 S值集中于11.6‰～13.0‰之间,介于前人报道的原生黄铁矿δ34 S值变化范围(3.3‰～16.0‰);阶段I形成的黄铁矿的δ34 S值为8.4‰～10.1‰,磁黄铁矿为7.6‰～8.0‰;阶段II黄铁矿的δ34 S值相对较高,为14.0‰～15.9‰;阶段Ⅲ磁黄铁矿的δ34 S值介于6.4‰～8.3‰之间.八卦庙金矿NE向黄铁矿-石英成矿期总体相对富集重硫同位素、离散程度较大,各阶段硫化物的硫同位素值介于矿集区花岗岩和围岩硫之间,显示其具有岩浆硫与地层硫混合的特征.结合阶段I到阶段Ⅲ矿物组合的变化(黄铁矿+磁黄铁矿→黄铁矿→磁黄铁矿),推断阶段IIδ34 S值增高是水岩反应引起的硫化作用所致,而阶段Ⅲ硫同位素值降低可能与岩浆水的加入密切相关.结合成矿物理化学条件,推断该成矿期成矿热液中金主要以Au(HS)2-的形式迁移,阶段I到阶段Ⅱ由水岩反应引起的硫化作用是导致他形黄铁矿-银金矿-细粒石英阶段(Ⅱ)金矿化的主要原因,而岩浆水的混入可能是导致他形磁黄铁矿-自然金-方解石阶段(Ⅲ)金沉淀的主要机理.     

The Experimental Study of Iron Sulfide Mineral Evolution Under Thermal Sulfurization Condition

Iron sulfide minerals are widely distributed, of which characteristics had the identification significance of formation environment. Previously, there were more research on iron sulfide minerals under hydrothermal condition, and few studies under volcanism formation condition. To simulate volcanic mineralization, the study of different temperature from 250 to 410℃ , different iron sulfur ratio from Fe:S=2∶1 to 1∶8, and two different sources of iron, reduced iron powder (Fe) and ferrous sulfide (FeS), on iron sulfide mineral evolution was investigated under thermal sulfurization condition. By using scanning electron microscopy (SEM), X-ray diffraction (XRD) and other methods, the morphology, composition and structural characteristics of the products were observed and analyzed.     

Sulfide composition and phase relations in the Fe-Ni-Cu ore deposits of the Ivrea-Verbano basic complex (western Alps,Italy)

The bulk composition, mineralogy and mineral chemistry of base-metal sulfides have been investigated in the Fe-Ni-(Cu) ore deposits of the Ivrea-Verbano basic complex.The sulfide ores mostly display textural evidence of having been primarily deposited as an immiscible melt. Bulk compositions of the ores indicate that considerably low Ni/Fe and Ni/Co ratios are found in deposits developed close to metasedimentary country rocks, possibly as a result of mixing with sedimentary sulfur.Phase relations of primary sulfides indicate that early crystallization of the ore was dominated by a monosulfide solid solution (Mss) with a pyrrhotite composition, from which pentlandite and chalcopyrite were formed through subsolidus exsolution. Pentlandite from contaminated ores is typically enriched in Co. Troilite and hexagonal intermediate pyrrhotite intergrowths frequently occur due to low-temperature equilibration of metal-rich pyrrhotites, suggesting a low S fugacity of the original sulfide melt.The sulfides may be locally mobilized and redeposited along shear zones within the same host rock, giving rise to fairly massive ores having a typical cemented-breccia texture. Bulk composition and assemblages suggest that mobilization occurred at various temperatures during the cooling history of the ore, when sulfides were still in the molten state or at a lower temperature under the influence of abundant deuteric fluids. In this last case, growth of pyrite is seen as being possibly due to sulfurization and/or oxidation.     

Formation of gold–silver sulfides and native gold in Fe–Ag–Au–S system

We carried out experiments on crystallization of Fe-containing melts FeS₂Ag_0.1–0.1xAu_0.1x (x = 0.05, 0.2, 0.4, and 0.8) with Ag/Au weight ratios from 10 to 0.1. Mixtures prepared from elements in corresponding proportions were heated in evacuated quartz ampoules to 1050 ºC and kept at this temperature for 12 h; then they were cooled to 150 ºC, annealed for 30 days, and cooled to room temperature. The solid-phase products were studied by optical and electron microscopy and X-ray spectroscopy. The crystallization products were mainly from iron sulfides: monoclinic pyrrhotite (Fe_0.47S_0.53 or Fe₇S₈) and pyrite (Fe_0.99S_2.01). Gold–silver sulfides (low-temperature modifications) are present in all synthesized samples. Depending on Ag/Au, the following sulfides are produced: acanthite (Ag/Au = 10), solid solutions Ag_2–xAu_xS (Ag/Au = 10, 2), uytenbogaardtite (Ag/Au = 2, 0.75), and petrovskaite (Ag/Au = 0.75, 0.12). They contain iron impurities (up to 3.3 wt.%). Xenomorphic micro- (<1–5 μm) and macrograins (5–50 μm) of Au–Ag sulfides are localized in pyrite or between the grains of pyrite and pyrrhotite. High-fineness gold was detected in the samples with initial ratio Ag/Au ≤ 2. It is present as fine and large rounded microinclusions or as intergrowths with Au–Ag sulfides in pyrite or, more seldom, at the boundary of pyrite and pyrrhotite grains. This gold contains up to 5.7 wt.% Fe. Based on the sample textures and phase relations, a sequence of their crystallization was determined. At ~1050 ºC, there are probably iron sulfide melt L₁ (Fe,S ? Ag,Au), gold–silver sulfide melt L₂ (Au,Ag,S ? Fe), and liquid sulfur L_S. On cooling, melt L₁ produces pyrrhotite; further cooling leads to the crystallization of high-fineness gold (macrograins from L₁ and micrograins from L₂) and Au–Ag sulfides (micrograins from L₁ and macrograins from L₂). Pyrite crystallizes after gold–silver sulfides by the peritectic reaction FeS + L_S = FeS₂ at ~743 ºC. Elemental sulfur is the last to crystallize. Gold–silver sulfides are stable and dominate over native gold and silver, especially in pyrite-containing ores with high Ag/Au ratios.     

安徽省马山矿区硫化物矿石中黄铁矿与磁铁矿的后成合晶

在安徽省马山矿区的硫化物矿石中,黄铁矿与磁铁矿呈后成合晶交代磁黄铁矿的结构,是成矿系统物理化学条件向磁黄铁矿-黄铁矿-磁铁矿三相点演化的产物。系统经过三相点的几率甚小,因而这种结构在矿石中十分少见。     

Alpine metamorphism of calcareous metasediments in the Western Hohe Tauern,tyrol: mineral equilibria in COHS fluids

During Tertiary regional metamorphism in the Western Hohe Tauern, reaching maximum P, T conditions around 6 kb, 550° C in calcareous metasediments, reaction of pyrite to pyrrhotite is suggested by regional distribution and textural relations. In rocks without graphite pyrite is common at all metamorphic grades. In graphite bearing rocks, however, the dominant Fe-sulfide is pyrite at lower grade and pyrrhotite at higher grade. Furthermore, in graphite bearing high grade rocks, pyrite is restricted to assemblages with Mg-rich silicates. Several factors control pyrite-pyrrhotite relations. Increase of temperature is most effective by increase of pyrrhotite vs. pyrite stability field, shift of silicate-sulfide reactions toward the stability field of pyrrhotite, creation of sulfur free fluids from devolatilization reactions, and increase in the proportions of sulfur bearing fluid species. Presence of graphite also favours progress of pyrite to pyrrhotite reaction, as shown by different -stabilities and changes in the amount of minerals and fluid during metamorphic heating of graphite bearing and graphite free assemblages. An opposite effect is shown by assemblages with low Fe-contents in Fe-Mg silicates, due to the enlarged stability field of such minerals with increasing Mg (and F) content. Another inhibition of pyrite to pyrrhotite reaction is suggested to be due to relatively high sulfur contents of H₂O rich infiltrating fluids.     

安徽铜陵冬瓜山铜矿床的叠加改造成矿机制：来自矿石结构的证据

长江中、下游地区块状硫化物矿床普遍受到燕山期岩浆及其热液的改造与叠加.本文以铜陵冬瓜山矿床为例,探讨这类矿床的成矿机制.该矿床主要由层状硫化物矿体组成,伴有矽卡岩型和斑岩型矿体.野外地质观察及室内矿相学的研究表明,冬瓜山层状矿体中矿石遭受了强烈的热变质作用及热液交代作用.进变质过程中形成的结构主要为黄铁矿受燕山期岩浆侵...     

Chemical exchange during hydrothermal alteration of basalt by seawater—II. Experimental results for Fe,Mn, and sulfur species

Fresh mid-ocean ridge basalts of varying crystallinity and an andesite were reacted with seawater and with a Na-K-Ca-Cl solution at 200–500°C and 500–1000 bar in sealed gold capsules. $\text{Water}\text{rock}$ mass ratios of one to three were used and durations ranged from two to twenty months. The concentrations of Fe, Mn, and reduced and oxidized sulfur species in solution reached steady state in most of the experiments at 400–500°C, but not in those at 200–300°. The concentrations of Fe and Mn were a few ppm at 200–300° and increased greatly with temperature between 300 and 500°. The low values at 200–300° are probably related to the uptake of Fe and Mn by smectite at the in situ pH, which was slightly acid at 200° and slightly alkaline at 300°. The quench pH values decreased with increasing temperature above 300°. The only reliable data for the concentration of Zn in solution were obtained at 400°, where values 1–2 ppm were found. Copper was extensively leached from basalt and andesite and was deposited as part of a Cu-Au alloy in the capsule walls or, in some experiments, as chalcopyrite.Reduced sulfur was readily leached from basalt into solution, and was also produced by the reduction of seawater sulfate by ferrous iron derived from the basalts. The proportion of seawater sulfate which was reduced in the experiments with a $\text{water}\text{rock}$ ratio of one varied from 5–10% at 300°C to > 95% at 500°. The rate of sulfate reduction depended on the run temperature, on the crystallinity and initial sulfur content of the rocks used as starting materials, and on the $\text{water}\text{rock}$ ratio. The final concentration of reduced sulfur in solution increased greatly with temperature, and generally exceeded that of Fe on a molal basis.The oxide-sulfide assemblages produced in the experiments resemble those in the basalt-seawater geothermal system at Reykjanes, Iceland, and in hydrothermally altered basalts and gabbros from the oceanic crust; they include pyrite, pyrrhotite. chalcopyrite, hematite, and probably magnetite. The particular assemblage varied systematically with the temperature, rock type, and crystallinity of each run. Anhydrite precipitated in all experiments with seawater, at all temperatures from 200–500°C. However, its persistence to the end of the runs was apparently metastable, as it should have reacted with the final solutions to produce pyrite or pyrrhotite.     

Mine drainage from the weathering of sulfide minerals and magnetite

Pyrite and pyrrhotite are the principal minerals that generate acid drainage in mine wastes. Low-pH conditions derived from Fe-sulfide oxidation result in the mobilization of contaminant metals (such as Zn, Cd, Ni and Cr) and metalloids (such as As) which are of environmental concern. This paper uses data from detailed mineralogical and geochemical studies conducted at two Canadian tailings impoundments to examine the mineralogical changes that pyrite, pyrrhotite, sphalerite and magnetite undergo during and after sulfide oxidation, and the subsequent release and attenuation of associated trace elements. The stability of sphalerite in tailings impoundments generally is greater than that of pyrrhotite, but less than pyrite. Dissolved Ni and Co derived from Fe sulfides, and to a lesser extent, dissolved Zn and Cd from sphalerite, are commonly attenuated by early-formed Fe oxyhydroxides. As oxidation progresses, a recycling occurs due to continued leaching from low-pH pore waters and because the crystallinity of Fe oxyhydroxides gradually increases which decreases their sorptive capacity. Unlike many other elements, such as Cu, Pb and Cr, which form secondary minerals or remain incorporated into mature Fe oxyhydroxides, Zn and Ni become mobile. Magnetite, which is a potential source of Cr, is relatively stable except under extremely low-pH conditions. A conceptual model for the sequence of events that typically occurs in an oxidizing tailings impoundment is developed outlining the progressive oxidation of a unit of mine waste containing a mixed assemblage of pyrrhotite and pyrite.