Element mobility during pyrite weathering: implications for acid and heavy metal pollution at mining-impacted sites

Based on back scattered electron images and electron micro-probe analysis results, four alteration layers, including a transition layer, a reticulated ferric oxide layer, a nubby ferric oxide layer and a cellular ferric oxide layer, were identified in the naturally weathering products of pyrite. These layers represent a progressive alteration sequence of pyrite under weathering conditions. The cellular ferric oxide layer correlates with the strongest weathering phase and results from the dissolution of nubby ferric oxide by acidic porewater. Leaching coefficient was introduced to better express the response of element mobility to the degree of pyrite weathering. Its variation shows that the mobility of S, Co and Bi is stronger than As, Cu and Zn. Sulfur in pyrite is oxidized to sulfuric acid and sulfate that are basically released into to porewater, and heavy metals Co and Bi are evidently released by acid dissolution. As, Cu and Zn are enriched in ferric oxide by adsorption and by co-precipitation, but they would re-release to the environment via desorption or dissolution when porewater pH becomes low enough. Consequently, Co, Bi, As, Cu and Zn may pose a substantial impact on water quality. Considering that metal mobility and its concentration in mine waste are two important factors influencing heavy metal pollution at mining-impacted sites, Bi and Co are more important pollutants in this case.     

Galvanic interactions between metal sulfide minerals in a flowing system: Implications for mines environmental restoration

Managing mine water that has been contaminated with metal sulfide minerals due to galvanic corrosion is becoming an increasingly important environmental problem. Here, galvanic corrosion was investigated by studying galvanic interactions between pyrite–chalcopyrite and pyrite–galena in flowing mediums such as mine discharge water and flowing rainwater. The results showed that the corrosion current density of pyrite–galena is greater than that of pyrite–chalcopyrite under identical conditions. The corrosion current density of the galvanic cell tends to increase with increasing concentrations of strongly oxidizing ions (e.g., Fe³⁺) in the flowing medium, whereas the existence of non-oxidizing and non-reducing ions (e.g., Na⁺) have no obvious influence on the galvanic cell. In addition, the corrosion current density increases with increasing flow rate. Using the galvanic model, mixed potential theory and Butler–Volmer equation, the experimental results were explained theoretically. Because these experiments were performed under conditions very similar to those seen in mine discharge water and flowing rainwater, these results have direct implications for the future management and control of environmental pollution from mining operations.     

Galvanic interaction between galena and pyrite in an open system

1IntroductionMost sulfide minerals in nature have perfect con-ductivity and possess semiconducting properties.Gal-vanic corrosion may occur when two sulfide mineralswith different potentials are connected together in thesolution.The mineral with the highe…     

Genetic implications of pyrite chemistry from the Palaeoproterozoic Olary Domain and overlying Neoproterozoic Adelaidean sequences, northeastern South Australia

Sulphide mineralisation associated with rocks from the Palaeoproterozoic Olary Domain (OD) and overlying Neoproterozoic Adelaidean sequences has undergone a complex history of metamorphism and remobilisation. In this study, new trace element and sulphur isotopic analyses of pyrites from a large number of deposits and paragenetic generations are combined with an existing data set to build up a sequence of mineralising events linked to the tectonometamorphic evolution of the region. The typically high Co/Ni ratios (>10) indicate that early strata-bound pyrite precipitated from a volcanic-related fluid, which had fluctuating activities of the two metals during the early stages of the evolution of the Willyama basin. This period of mineralisation was followed by a diagenetic concentration of sulphide mineralisation at the horizon known as the Bimba Formation, which occurred as a result of the differing redox conditions between the upper and lower sequences in the Willyama Supergroup. During the Mesoproterozoic (1600 to 1500 Ma) Olarian Orogeny, metamorphic remobilisation of strata-bound pyrite resulted in an epigenetic signature; the trace element concentrations of this generation were controlled primarily by the proximity of mineralisation to the mafic intrusive bodies found throughout the terrane. Further reworking of existing sulphides during the Delamerian Orogeny and associated granitoid-intrusive rocks led to the formation of a new generation of epigenetic pyrite that occurs in quartz veins in the Adelaidean sequences and veins that crosscut Olarian fabrics in the Olary Domain. δ³⁴S results range from 16‰ to 11‰, but most data fall between 2‰ and 4‰. This association is suggestive of an initial uniform deep-seated crustal reservoir of sulphur, which has been repeatedly tapped throughout the metallogenic history of the region. The isotopic outliers can be explained by the input of biogenic sulphur or sulphur derived from oxidised, possibly evaporitic, sediments, respectively. Previous workers have invoked the Kupferschiefer and the Zambian Copperbelt as analogues to mineralisation processes in the Olary Domain. This study shows that δ³⁴S and trace element data are suggestive of some affinities with the aforementioned analogues, but a more likely link can be made between epigenetic remobilisation in the Olary region and the iron oxide copper gold (IOCG) style of mineralisation found at the nearby Olympic Dam deposit.     

Magnesia mixture as a regulator in the separation of pyrite from chalcopyrite and arsenopyrite

The aim of this paper is to find an effective method for the separation of the undesirable constituents, namely, chalcopyrite and arsenopyrite from pyrite used for the production of H₂SO₄. A new effective method is developed for co-depressing chalcopyrite with arsenopyrite by AsI₃, followed by the addition of magnesia mixture. This method has been shown to be based on the fact that iron sites exist in the three minerals, whereas copper and arsenic sites exist only in chalcopyrite and arsenopyrite, respectively. This is coupled with the ability of both Cu(I) and Cu(II) to precipitate As(III) in the form of insoluble copper arsenides, namely Cu₃As, Cu₃As₂. In contrast, neither Fe(II) nor Fe(III) form stable arsenides. Consequently, As³⁺ ions are selectively adsorbed onto the surface of chalcopyrite. The facility for oxidizability of As(III) is well known and hence it adsorbs oxygen from the pulp and changes to As(V) of higher valency and smaller size, with ionic potential over 10. Accordingly, it yields a stable complex anion with covalent bonding, namely, [AsO₄]^3?. These newly created arsenate sites on the surface of chalcopyrite, as well as the corresponding original arsenate sites on the surface of arsenopyrite combine with magnesia mixture to form cations leading to the formation of tightly abutting strongly hydrophilic layers of … AsO₄NH₄Mg.6H₂O. The spread of this hydrophilic film on arsenopyrite and chalcopyrite surfaces leads to the screening of their surfaces, making them difficult of access for the collector, ethyl xanthate. Since the pK_a of xanthic acid occurs at pH below 3, xanthate species predominate at pH above 8 and are adsorbed selectively on the pyrite surface in sufficient quantity for its selective flotation and hence for its separation to take place in the pH range 8–9.     

Atomistic simulation of the structure and elastic properties of pyrite (FeS2) as a function of pressure

Interatomic potential parameters have been derived at simulated temperatures of 0 K and 300 K to model pyrite FeS₂. The predicted pyrite structures are within 1% of those determined experimentally, while the calculated bulk modulus is within 7%. The model is also able to simulate the properties of marcasite, even though no data for this phase were included in the fitting procedure. There is almost no difference in results obtained for pyrite using the two potential sets; however, when used to model FeS₂ marcasite, the potential fitted at 0 K performs better. The potentials have also been used to study the high-pressure behaviour of pyrite up to 44 GPa. The calculated equation of state gives good agreement with experiment and shows that the Fe–S bonds shorten more rapidly that the S–S dimer bonds. The behaviour of marcasite at high pressure is found to be similar to that of pyrite.     

Comparison of methods for the estimation of pyrite oxidation rate in a waste rock pile at Mine Doyon site, Quebec, Canada

Several methods were evaluated and compared for the estimation of pyrite oxidation rates (POR) in waste rock at Mine Doyon, Quebec, Canada. Methods based on data collected in situ, such as the interpretation of temperature and oxygen concentration profiles (TOP) measured in the waste rock pile and pyrite mass balance (PMB) on solid phase samples were compared with the oxygen consumption measurements (OCM) in closed chamber in the laboratory. A 1-D analytical solution to a gas and heat transport equation used temperature and oxygen profiles (TOP) measured in the pile for the preliminary POR estimates at a site close to the slope of the pile (Site 6) and in the core of the pile (Site 7). Resulting POR values were 1.1 × 10^− 9 mol(O₂) kg^− 1 s^− 1 and 1.0 × 10^− 10 mol(O₂) kg^− 1 s^− 1 for the slope site and the core site, respectively. Oxidation rates based on pyrite mass balance (PMB) calculations for solid samples were 2.21 × 10^− 9 mol(O₂) kg^− 1 s^− 1 and 2.03 × 10^− 9 mol(O₂) kg^− 1 s^− 1, respectively, for the same slope and core sites, but the difference between sites was within the error margin. The OCM measurements in the laboratory on fresh waste rock samples yielded higher POR values than field methods, with average oxidation rate of 6.7 × 10^− 8 mol(O₂) kg^− 1 s^− 1. However, the OCM results on weathered and decomposed material from the rock stockpile (average oxidation rate 3.4 × 10^− 9 mol(O₂) kg^− 1 s^− 1) were consistent with results from the field-based estimates. When POR values based on fresh material are excluded, the remaining POR values for all methods range from 1.0 × 10^− 10 to 3.4 × 10^− 9 mol(O₂) kg^− 1 s^− 1. The lowest estimated value (1.0 × 10^− 10 mol(O₂) kg^− 1 s^− 1) was based on TOP estimates in the interior of the pile where oxygen transport was limited by diffusion from the surface. These results suggest that small-scale OCM laboratory experiments may provide relatively representative values of POR in the zones of waste rock piles in which oxygen transport is not dominated by diffusion.     

鄂西地区上泥盆统碳质粉砂岩及黄铁矿地球化学特征

晚泥盆世弗拉期—法门期（F-F）之交生物大灭绝事件一直是被学者关注的热点,事件的起因与机制并没有定论。前人对华南地区事件期沉积序列、地层同位素、底栖、微体生物和维管植物的类型及演化进行了研究。但对事件起始期下Kellwasser事件研究较为薄弱,对其古气候、古环境认识尚不足。针对这些问题,本文对鄂西地区上泥盆统黄家磴组碳质粉砂岩与沉积黄铁矿微量元素与硫同位素进行测试分析,探讨了下Kellwasser事件期气候与环境。研究获得下列认识：1）晚泥盆世弗拉期鄂西地区为淡水环境,气候潮湿,水温约为31 ℃;2）受陆源营养物质供给的影响,海洋中生物生产力较高,大量沉积有机质分解,厌氧带向下扩张,造成水体氧化—还原带分层;3）大气氧含量介于17.23%~21.18%,黄铁矿δ³⁴S介于-12.01‰~-4.67‰,均未见明显波动;4）下Kellwasser事件未表现出明显的火山喷发、海水缺氧与构造作用成因的特征。研究成果为理解F-F生物大灭绝事件起因提供了参考,也丰富了中-上扬子地区晚泥盆世古气候、古环境认识。

     

LA-ICP-MS trace element analysis of pyrite from the Xiaoqinling gold district, China: Implications for ore genesis

The Xiaoqinling district, the second largest gold producing district in China, is located on the southern margin of the North China Craton. It consists of three ore belts, namely, the northern ore belt, the middle ore belt and the southern ore belt. Pyrite from the Dahu gold deposit in the northern ore belt and Wenyu and Yinxin gold deposits in the southern ore belt were investigated using a combination of ore microscopy and in-situ laser-ablation inductively-coupled plasma-mass spectrometry (LA-ICP-MS). A range of trace elements was analyzed, including Au, Te, Ag, Pb, Bi, Cu, Co, Ni, Zn, Mo, Hg, As and Si. The results show that there are no systematic differences between the trace element compositions of pyrite in the three deposits from different ore belts. In general, Au concentrations in pyrite are low (from < 0.01 ppm to 2.2 ppm) but Ni concentrations are rather high (up to 8425 ppm). A four-stage mineralization process is indicated by microscopic and field observations and this can be related to the systematic trace element differences between distinct generations of pyrite. Stage I precedes the main gold mineralization stage; pyrite of this stage has the lowest Au concentrations. Stages II and III contributed most of the gold to the ore-forming system. The corresponding pyrite yielded the highest concentrations of Au and Ni. Our microscopic observations suggest that pyrite in the main gold mineralization stage precipitated simultaneously with molybdenite that has been previously dated as Indosinian (~ 218 Ma by Re–Os molybdenite dating), indicating the Indosinian as the main gold mineralization stage. The Indosinian mineralization age and the geological and geochemical features of these gold deposits (e.g., low salinity, CO₂-rich ore fluids; spatial association with large-scale compressional structures of the Qinling orogen; δ¹⁸O and δD data suggestive of mixing between metamorphic and meteoric waters; δ³⁴S and Pb-isotopic data that point to a mixed crustal-mantle source) all point to typical orogenic-type gold deposits. High Ni concentrations (up to 8425 ppm) of pyrite possibly linked to deep-seated mafic/ultramafic metamorphic rocks provide further evidence on the orogenic gold deposit affinity, but against the model of a granitic derivation of the mineralizing fluid as previously suggested by some workers. Generally low Au concentration in pyrite is also consistent with those from worldwide orogenic gold deposits. Therefore, the gold mineralization in the Xiaoqinling district is described as orogenic type, and is probably related to Indosinian collision between the North China Craton and the Yangtze Craton.     

Abundances and isotopic compositions of rhenium and osmium in pyrite samples from the Huaibei coalfield,Anhui, China

Two pyrite samples from the Shihezi Formation (Lower Permian), Huaibei coalfield, Anhui, China, have been analyzed for abundances and isotopic compositions of rhenium and osmium using negative thermal ion mass spectrometry. The Re–Os ages of the pyrites are 64.4 and 226 Ma, which are younger than the formation age of the coal seam. The pyrite samples may consist of pyrite formed at various stages during the history of coal formation. The γ_Os values of the two pyrite samples are + 17 and + 18, respectively. Such high γ_Os values are reported for the first time for recycles crustal materials from a sedimentary basin.     

湘东北横洞钴矿床钴的富集机制: 来自黄铁矿的微区结构、成分和硫同位素证据

世界上典型热液脉型钴矿床, 如五元素(Ag-Bi-Co-Ni-As±U)矿床, 因其高的钴品位(高达8%)而具有重要的经济价值和研究意义, 该类矿床以自然元素和砷化物组合为特征。不同于五元素矿床, 湘东北横洞热液脉型钴矿床(中型, 品位约0.04%)的矿石矿物组合为黄铁矿+黄铜矿+闪锌矿+方铅矿+磁黄铁矿, 目前对该矿床中含钴矿物的特征及钴的富集机制尚不清楚。本文在详细的矿相学工作基础上, 采用EPMA、EBSD、LA-ICPMS和LA-MC-ICPMS等多种分析方法, 对其黄铁矿开展了精细结构、成分和硫同位素分析。将黄铁矿划分为PyI、PyII和PyIII三个世代。其中, PyII是Co的重要载体, 常呈丝带状、不规则状或韵律环带交代PyI或呈细粒状产出, 其Co含量高达52141×10^-6, 明显高于其他世代黄铁矿。黄铁矿中Co与Fe具有较好的负相关性, 表明Co主要呈类质同象的形式置换Fe存于黄铁矿晶格中。而黄铁矿中高的Co/Ni比值(1.05~393)和Se含量(10.69×10^-6~129×10^-6)则暗示了其热液成因。此外, PyII与PyI之间具有不规则港湾状接触界面、突变的化学成分以及相近的晶体取向, 这些暗示了富钴的PyII系含钴流体与围岩及早阶段黄铁矿快速反应的产物, 溶解再沉淀的动力学过程是控制PyII的形成机制。不同世代黄铁矿的δ³⁴S_V-CDT值接近, 变化范围为-13.12‰~-8.70‰, 与围岩地层的硫同位素特征接近。结合湘东北结晶基底高的Co含量(30.4×10^-6~72.3×10^-6)和以往流体包裹体显微测温结果, 认为在晚侏罗世-早白垩世期间, NE-ENE向的长沙-平江断裂带走滑剪切活动使得深源热液流体从结晶基底连云山岩群活化萃取了金属钴, 富钴热液沿走滑断裂向上运移至成矿部位, 再因压力周期性变化引起流体发生不混溶作用进而分离, 导致钴金属络合物失稳, 最后钴沉淀富集成矿。通过与世界上典型热液脉型钴矿床成矿特征的对比, 提出流体低的盐度和低砷、高硫的特征是造成横洞钴矿床矿物组合简单的主要控制因素。

     

华北克拉通南缘卢氏多金属矿集区硫化物Rb-Sr定年及地质意义

华北克拉通南缘秦岭成矿带发育大量金矿、钼矿及铅锌多金属矿床。卢氏多金属矿集区位于东秦岭成矿带,主要矿床有夜长坪钼钨矿、八宝山铁铜矿、楼房银铜矿、柳关铅锌矿等。其中楼房银铜矿为热液脉状多金属矿床,矿床赋存于太华群角闪斜长片麻岩中,矿体受构造蚀变破碎带控制,矿床中划分出两个成矿阶段:石英-黄铁矿-黄铜矿组合和石英-黄铁矿-方铅矿-闪锌矿-方解石组合,其中前者是铜成矿阶段,后者为铅锌成矿阶段。柳关铅锌矿为矽卡岩矿床,矿体产于官道口群白云岩与花岗斑岩岩体或隐爆角砾岩接触矽卡岩化带内,矿床划分出两个成矿阶段:透辉石-透闪石-阳起石-石榴石-磁铁矿组合和方铅矿-闪锌矿-黄铁矿-绿帘石-蛇纹石-石英-方解石组合,前者为磁铁矿成矿阶段,后者是铅锌成矿阶段。金属硫化物定年结果表明,楼房银铜矿黄铜矿Rb-Sr等时线年龄为127. 8±3. 1Ma(2σ,MSWD=1. 1),初始87Rb/86Sr为0. 710998±0. 000068;柳关铅锌矿黄铁矿Rb-Sr等时线年龄为124. 8±1. 6Ma(2σ,MSWD=1. 4),初始87Rb/86Sr为0. 711074±0. 000064。研究表明卢氏多金属矿集区内热液多金属矿床形成于早白垩世,其形成与区内早白垩世岩浆活动有关。综合区域地质研究,区内多金属矿床形成于早白垩世与克拉通破坏有关的构造环境。     

钦-杭带南段坡仔营斑岩型钼矿中黄铁矿微组构及其标型意义

坡仔营钼矿是钦-杭成矿带南段最重要斑岩型矿床之一。该矿床发育典型"中心式面型蚀变"和A、B和D三种类型矿化脉。为了加深对其成矿过程的认识,本研究选取不同矿脉中黄铁矿,通过扫描电镜（SEM）、X射线粉晶衍射（XRD）和激光拉曼光谱（Raman）,研究其微组构标型特征,以期反演成矿过程的热力学及动力学信息。SEM结果显示,A脉内黄铁矿较少,呈100~200μm半自形-他形,籽晶呈扁平乳滴状;B脉黄铁矿强烈发育,呈500~1000μm自形-半自形,籽晶呈近椭圆形层状;D脉内黄铁矿呈立方体产出,粒度10~20mm左右,三组相互垂直晶纹发育,籽晶棱角状线形展布。A脉→B脉→D脉中黄铁矿粒度逐渐变大,籽晶更加规则,指示成矿早期至晚期,黄铁矿结晶速度逐渐变缓,成生环境趋于稳定。XRD结果展示,各样品谱线均发育着多组黄铁矿特征峰,但其强峰发育存在差异。A脉最强峰为28.5°,次强峰37.1°;B脉和D脉相应峰位分别为37.1°、33.1°和33.1°、56.3°。衍射峰型特征表明,A脉样品晶形应以（1 1 1）面组成的正八面体单形为主,其次为（2 1 0）晶面组成的五角十二面体,其成生温度应大于300度;B脉样品应以（2 1 0）组成的五角十二面体单形为主,其次为（1 0 0）晶面组成的立方体单形,形成温度应介于200~300℃之间或略大;D脉样品主要以（1 0 0）晶面组成的立方体为主,其形成温度应小于200℃。Raman光谱揭示,A脉样品的ν_Eg=348.0~350.7cm^-1、ν_Ag=385.2~386.5cm^-1、ν_Tg=441.9~422.8cm^-1,与之相比,B脉和D脉的对应值分别向低频偏移2~6cm^-1和5~14cm^-1;A脉样品的散射强度I_Eg=388.8~745.5、I_Ag=1532.8~2071.8、I_Tg=238.9~254.4,而B及D脉样品的散射强度依次明显增强。自A脉→B脉→D脉,拉曼位移向低频偏移,散射强度依次增强,指示三者的成生压力依次降低。本研究认为,坡仔营斑岩型钼矿的成生早期为一个高温、高压岩浆热液活动为主阶段,随着成矿温度、压力的降低,成矿系统氧逸度逐渐降低,硫及金属元素逐步转变为金属硫化物形式而成矿。     

云南武定迤纳厂Fe-Cu-REE矿床的锆石U-Pb和黄铜 矿Re-Os年代学、稀土元素地球化学及其地质意义

迤纳厂矿床是康滇地区典型的铁-铜-稀土矿床之一.因为其特殊的矿物组合(磁铁矿与黄铜矿共生)以及富含稀土矿物,这类矿床一直是矿床学家研究的热点.然而由于其围岩遭受不同程度的变质和蚀变作用,这类矿床的成矿时代与矿床成因一直存在争议.本文通过对迤纳厂组中层状凝灰岩和火山角砾岩所含锆石进行LA-ICP-MS U-Pb定年来揭示迤纳厂组的最大沉积年龄.大多数锆石具有明显的震荡环带和较高的Th/U比值(＞0.4)表明它们均是岩浆锆石,近200粒碎屑锆石的207 pb/206 Pb年龄大致可以分为四组:1.75 ～ 1.88Ga,1.90 ～2.00Ga,2.02～2.20Ga和2.30 ～2.40Ga,且最老年龄在3.0Ga左右,而最年轻年龄在1750Ma左右.这一定年结果反映了迤纳厂组的沉积上限大约为1.7Ga,并且在康滇地区可能还有更老的基底存在.通过对矿石矿物黄铜矿的Re-Os同位素定年测试,直接限定了矿床的成矿时代.6个黄铜矿样品的Re-Os同位素等时线年龄为1690±99Ma(MSWD =9.0),模式年龄的加权平均值为1685±37Ma(MSWD=3.0),表明该矿床形成于距今约1.7Ga.另外,主要类型矿石具显著的正铕异常和轻稀土富集的特点,与现代海底热液极其相似.年代学研究显示矿床的形成时代和地层的沉积时代大致相同,而REE揭示的流体特征反映其成矿作用与海底热液活动有关.这些结果暗示了该矿床为海底火山喷发-同生沉积形成.近来的较多研究证实,康滇地区存在1.7Ga左右较大范围的岩浆活动和较多同期铁-铜矿床,表明该期岩浆活动可能是制约该区铁-铜矿床形成的关键因素,且岩浆活动可能与约1.7Ga的Columbia超大陆的裂解事件有关.     

山东沂南东部土壤-玉米系统重金属元素与其他元素间相互作用及其生物有效性研究

在沂南县东部地区重金属元素高的背景状态下,为研究土壤-玉米系统中重金属元素和与人体健康关系密切的微量元素间的相互作用及其生物有效性,在研究区采集了50件玉米籽实及其根系土土壤样品。通过样品中重金属元素和微量元素含量分析,统计其含量及富集特征,探讨了玉米籽实及其根系土土壤中各元素间的相互关系。通过玉米根、茎、叶、籽实中重金属元素含量及根系土土壤中重金属元素形态分析,总结了玉米根、茎、叶、籽实以及根系土土壤中重金属元素的分布规律并对玉米籽实进行了安全性评价。结果显示: ①各元素含量在玉米根系土土壤和玉米籽实中差异明显,玉米籽实中元素富集系数间多呈显著-极显著正相关; ②玉米籽实中As、Ni、Se含量与土壤中元素含量多呈拮抗作用,玉米籽实中元素含量间多呈协同作用; ③Cu、Zn、Cd、Hg主要富集于叶中,Cr、Pb、Ni、As主要富集于根中,除1件玉米籽实样品外,其他样品均符合绿色、无公害等相关标准,研究区玉米籽实安全性较好。研究成果可为农业高质量发展、土壤污染综合治理提供支撑。     

湘中龙山大型金锑矿床成矿时代研究——黄铁矿Re-Os和锆石U-Th/He定年

龙山金锑矿床是湘中锑-金矿集区最重要的矿床之一,因缺少适合传统放射性同位素定年的矿物,其成矿时代以往未得到很好的限定,制约了对矿床成因的认识。由于分析测试技术的进步,Re-Os同位素定年技术得到了发展,可对热液矿床中形成的低Re、Os含量的硫化物进行较准确可靠的年龄测定,从而可为低温热液矿床的形成时代提供有效制约。锆石U-Th/He同位素定年,也是近年发展和成熟起来的定年技术,对低温热事件极其敏感,同样是约束低温成矿年龄的重要手段之一。本文采用矿床中黄铁矿Re-Os同位素和蚀变围岩中受成矿热事件影响的锆石U-Th/He同位素定年技术,对龙山金锑矿床的成矿时代进行了研究。定年结果显示:热液成因黄铁矿的Re-Os等时线年龄为195±36Ma,对应于印支晚期;锆石U-Th/He年龄为51.2~133.3Ma,经Ft校正后,U-Th/He年龄分布于93.78~258.29Ma之间,平均值为160.7±7.3Ma,对应于燕山早期。该矿床可能发生了200Ma和160Ma的两次成矿作用;或者矿床形成于200Ma左右,但是受到了160Ma左右岩浆热事件的改造,黄铁矿Re-Os年龄代表成矿年龄,而锆石U-Th/He年龄则代表第二期热事件发生的时间。无论是200Ma左右一次成矿,还是另有160Ma左右的成矿作用叠加,这两个年龄分别与区内两期岩浆活动的时间相当,这表明岩浆事件对驱动矿床的形成发挥了重要的作用。     

安徽铜陵新桥铜硫金矿床的成因:来自两类黄铁矿微形貌学、地球化学特征的证据

新桥矿床是长江中下游成矿带铜陵矿集区内大型铜金硫矿床。本文以矿床中的黄铁矿为研究对象,在详细的野外观察和室内鉴定的基础上,将矿床中的黄铁矿分为胶状黄铁矿(Py I)和半自形-自形黄铁矿(Py II)两种类型。通过场发射扫描电镜(FE-SEM)和等离子激光质谱(LA ICP-MS)对两类黄铁矿的矿物相、形貌、微结构和微量元素成分进行研究。FE-SEM分析结果表明,Py I基本由极细粒黄铁矿组成,以自形-半自形立方体晶形为主,粒径大约100~500nm,而Py II主要为粒度为50~100μm,以八面体和五角十二面体晶形态为主,两类黄铁矿的形貌和微结构特征明显不同。LA-ICP-MS分析测试显示,Py I中相对富含As、Se、Te等元素,而Py II中成矿元素Cu、Pb、Zn、Au、Ag的含量则比Py I型黄铁矿明显偏高,分别为792.0×10-6、2125×10-6、1.67×10-6、0.29×10-6和190.7×10-6,且Bi、Co、Ni、V、Ti、Mg、Cr、Cd、Al、Mn等微量元素含量较Py I均明显偏高1~2个数量级。在综合分析黄铁矿的结构形态和微量元素组成特征的基础上,本文认为Py I可能形成于晚古生代海底热水沉积环境,Py II形成于中生代岩浆热液环境。新桥铜金硫多金属矿床的成矿作用包括了海西期同生沉积成矿作用和燕山期与岩浆活动有关的热液成矿作用。晚侏罗世-早白垩世广泛发育的强烈岩浆侵入及与之有关的热液活动,对矿床的最终形成起了主导作用,提供了Cu、Au等主要成矿物质。     

胶西北大尹格金矿床成矿机理:载金黄铁矿标型及硫同位素地球化学约束

胶东是我国最重要的金矿集中区,破碎带蚀变岩型金矿床是区内最主要的金矿床类型,该类型金矿床已探明金资源量占全区的90%以上,其巨量金的来源是引人瞩目的关键科学问题。招平断裂带是该区内规模最大的断裂-成矿带,位于招平金矿带中段的大尹格庄金矿床是该金矿带最具代表性的破碎带蚀变岩型金矿床之一,已探明金金属量约283t。大尹格庄金矿床严格受沿胶东群与玲珑花岗岩接触带发育的NNE向招平断裂带控制,矿体赋存在招平断裂下盘黄铁绢英岩化和碎裂岩化玲珑花岗岩中,主要由Ⅰ号和Ⅱ号矿体组成,其具有相似的矿物组成,矿石主要矿物是绢云母、石英、黄铁矿,次要矿物是钾长石、斜长石、黑云母、方解石、黄铜矿、方铅矿、闪锌矿、磁黄铁矿、黝铜矿和自然金、自然银、金银矿、碲银矿等;其中黄铁矿是最主要的载金矿物。根据穿插关系和矿物共生组合,大尹格庄金矿床内成矿作用可划分为4个成矿阶段,分别是黄铁矿-石英-绢云母阶段(I)、石英-黄铁矿阶段(Ⅱ)、石英-多金属硫化物阶段(Ⅲ)和石英-方解石-多金属硫化物阶段(Ⅳ)。各个成矿阶段的黄铁矿的晶体形态标型研究表明,成矿Ⅰ阶段黄铁矿以粗粒自形立方体为主,含有少量五角十二面体;成矿Ⅱ和Ⅲ阶段黄铁矿以细粒五角十二面体为主,且具有更多五角十二面体、八面体和立方体形成的聚形;成矿Ⅳ阶段主要为细粒立方体晶形。不同矿体各个成矿阶段的硫化物的δ~(34)S值集中在4.58‰~7.54‰,具有一定的塔式效应,正向偏离陨石硫,与胶东地区胶东群变质岩、围岩花岗岩类δ~(34)S比较接近,指示大尹格庄金矿床各个成矿阶段的矿石硫源总体一致,与胶东群变质岩和中生代花岗岩间具有继承演化关系。此外,从成矿Ⅰ阶段→Ⅱ阶段→Ⅲ阶段→Ⅳ阶段,大尹格庄金矿床矿石硫化物δ~(34)S呈现出逐渐降低的趋势,反映了成矿过程中物理化学条件的演化趋势:Ⅰ阶段为较高温度(330~350℃)、快速冷却、低过饱和度、低氧逸度和硫逸度的成矿环境;Ⅱ和Ⅲ阶段黄铁矿形成于中-低温(200~300℃)、成矿流体过饱和度高、高氧逸度和硫逸度、缓慢冷却同时物质供应充分的成矿环境;Ⅳ阶段处于较低温度(200℃)、热液流体过饱和度较低、低氧逸度和硫逸度、同时物质供应不足的成矿环境。     

焦家深部金矿床成矿流体来源:来自黄铁矿微量元素及S-He-Ar同位素的约束

焦家金矿是胶东蚀变岩型金矿的典型代表，金储量超过200t。矿体受焦家主干断裂控制，呈脉状产出，发育钾化、绢英岩化、硅化和碳酸盐化等蚀变，矿石中主要载金矿物为黄铁矿。热液成矿期主要可分为四个阶段：黄铁矿-石英阶段（i）、金-石英-黄铁矿阶段（ii）、金-石英-多金属硫化物阶段（iii）和石英-碳酸盐阶段（iv）。本文选取焦家金矿床深部I号主矿体为研究对象，采集了不同标高（-600~-1100m）的钻孔岩心样品，分析了黄铁矿的微量元素和S-He-Ar同位素组成，以此讨论成矿流体的组成、性质及来源。研究发现：焦家深部I号矿体黄铁矿呈浅黄色，强金属光泽，自形-半自形粒状结构，粒度50~1000μm，呈浸染状-细脉状分布于黄铁绢英岩化碎裂岩中，为第ii成矿阶段的产物。黄铁矿的稀土元素含量较低，ΣREE为3.27×10^-6~38.5×10^-6，富集轻稀土元素，δCe值为0.81~1.05，δEu值为0.67~1.43，Th/La、Nb/La比值均小于1，指示成矿流体为富Cl的还原性流体。Co/Ni比值介于0.54~1.57之间，平均值为0.99，与变质流体相近；Y/Ho比值在21.9~35.5之间，与地幔值（25~30）和中国东部大陆地壳值（20~35）接近，指示成矿流体与壳-幔相互作用有关。Y/Ho值、Zr/Hf值和Nb/Ta值变化范围较大，表明成矿热液体系发生了交代作用或有外来热液加入。与大陆地壳相比，黄铁矿富集Cu、Pb、Zn、Cd、Co、Ni等亲硫、铁族元素，亏损高场强元素。焦家深部金矿床黄铁矿的δ³⁴S值介于7.5‰~9.8‰之间，平均值为8.7‰，低于浅部矿床δ³⁴S值，呈现出由浅到深δ³⁴S值逐渐降低的特点。胶东金矿硫同位素组成整体一致，绝大多数矿床δ³⁴S值均为正值，变化范围主要集中在6‰~12‰，其来源与古老的变质基底岩系、中生代花岗岩以及幔源流体具有继承演化关系。δ³⁴S值整体呈现出：石英脉型 < 硫化物石英脉型 < 蚀变岩型的变化规律，说明矿化类型的差异是造成硫同位素组成差别的最主要因素。黄铁矿的³He/⁴He值为1.6±0.1Ra~1.8±0.1Ra，⁴⁰Ar/³⁶Ar值为750~3106，均显示混合来源特征。幔源He所占比例为20%~22%，表明幔源流体可能参与了成矿过程。焦家金矿成矿与燕山晚期中国东部强烈的壳幔相互作用密切相关。