Re-equilibration of CO2 fluid inclusions at controlled hydrogen fugacities

Abstract Natural, pure CO₂ inclusions in quartz and olivine (c. Fo₉₀) were exposed to controlled f_H2 conditions at T= 718–728°C and P_total= 2 kbar; their compositions were monitored (before and after exposures) by microsampling Raman spectroscopy (MRS) and microthermometry. In both minerals exposed at the graphite–methane buffer (f_H2= 73 bar), fluid speciations record the diffusion of hydrogen into the inclusions. In quartz, room-temperature products in euhedral isolated (EI type) inclusions are carbonic phases with molar compositions of c. CO₂(60) + CH₄(40) plus graphite (Gr) and H₂O, whereas anhedral inclusions along secondary fractures (AS type) are Gr-free and contain H₂O plus carbonic phases with compositions in the range c. CO₂(60) + CH₄(40) to CO₂(10) + CH₄(90). EI type inclusions in olivine evolved to c. CO₂(90–95) + CH₄(5–10) without Gr, whereas AS type inclusions have a range of compositions from CO₂(90) + CH₄(10) ± Gr to CH₄(50) + H₂(50) ± Gr; neither H₂O nor any hydrous species was detected by optical microscopy or MRS in the olivine-hosted products. Differences in composition between and among the texturally distinct populations of inclusions in both minerals probably arise from variations in initial fluid densities, as all inclusions apparently equilibrated with the ambient f_H2. These relations suggest that compositional variability among inclusions in a given natural sample does not require the entrapment of multiple generations of fluids. In addition, the absence of H₂O in the olivine-hosted inclusions would require the extraction of oxygen from the fluids, in which case re-equilibration mechanisms may be dependent on the composition and structure of the host mineral. Many of the same samples were re-exposed to identical P–T conditions using Ar as the pressure medium, yielding ambient f_H2= 0.06 bar. In most inclusions, the carbonic fluids returned to pure CO₂ and graphite persisted in the products. Reversal of the mechanisms from the prior exposure at f_H2= 73 bar did not occur in any inclusions but the AS types in olivine, in which minor CO₂ was produced at the expense of CH₄ and/or graphite. The observed non-reversibility of previous mechanisms may be attributed to: (1) slower fluid–solid reactions compared to reactions in the homogeneous fluid phase; (2) depressed activities of graphite due to poor ordering; and/or (3) low ambient f_O2 at the conditions of the second run.     

Calculated fluid evolution path versus fluid inclusion data in the COHN system as exemplified by metamorphic rocks from Rogaland, south-west Norway

Abstract Fluid evolution paths in the COHN system can be calculated for metamorphic rocks if there are relevant data regarding the mineral assemblages present, and regarding the oxidation and nitrodation states throughout the entire P-T loop. The compositions of fluid inclusions observed in granulitic rocks from Rogaland (south-west Norway) are compared with theoretical fluid compositions and molar volumes. The fluid parameters are calculated using a P-T path based on mineral assemblages, which are represented by rocks within the pigeonite-in isograd and by rocks near the orthopyroxene-in isograd surrounding an intrusive anorthosite massif. The oxygen and nitrogen fugacities are assumed to be buffered by the coexisting Fe-Ti oxides and Cr-carlsbergite, respectively. Many features of the natural fluid inclusions, including (1) the occurrence of CO₂-N₂-rich graphite-absent fluid inclusions near peak M2 metamorphic conditions (927° C and 400 MPa), (2) the non-existence of intermediate ternary CO₂-CH₄-N₂ compositions and (3) the low-molar-volume CO₂-rich fluid inclusions (36–42 cm³ mol^?1), are reproduced in the calculated fluid system. The observed CO₂-CH₄-rich inclusions with minor N₂ (5 mol%) should also include a large proportion of H₂O according to the calculations. The absence of H₂O from these natural high-molar-volume CO₂-CH₄-rich inclusions and the occurrence of natural CH₄-N₂-rich inclusions are both assumed to result from preferential leakage of H₂O. This has been previously experimentally demonstrated for H₂O-CO₂-rich fluid inclusions, and has also been theoretically predicted. Fluid-deficient conditions may explain the relatively high molar volumes, but cannot be used to explain the occurrence of CH₄-N₂-rich inclusions and the absence of H₂O.     

Noble Gas and Stable Isotopic Constraints on the Origin of the Ag–Cu Polymetallic Ore Deposits in the Baiyangping Area,Yunnan Province,SW China

The Lanping basin, Yunnan province, SW China, is located at the juncture of the Eurasian and Indian Plates in the eastern part of the Tibetan Plateau. The Lanping basin, in the Sanjiang Tethyan metallogenic province, is a significant Cu–Ag–Zn–Pb mineralized belt in China that includes the largest sandstone‐hosted Zn–Pb deposit in the world, the Jinding deposit, as well as several Ag–Cu deposits (the Baiyangping and Jinman deposits). These deposits, with total reserves of over 16.0 Mt Pb + Zn, 0.6 Mt Cu, and 7,000 t Ag, are mainly hosted in Meso‐Cenozoic clastic rocks and are dominantly controlled by two Cenozoic thrust systems developed in the western and eastern segments of the basin. The Baiyangping, Babaoshan, and Hetaoqing ore deposits are representative of the epithermal base metal deposits in the Lanping basin. The microthermometric data show that the ore‐forming fluids for these deposits were low temperature (110–180 °C) and had bimodal distribution of salinity at moderate and mid to high salinities (approximately 2–8 wt.% and 18–26 wt.% NaCl equivalent). The C and O isotope data indicate that the ore‐forming fluids were related to hot basin brines. We present new He and Ar isotope data on volatiles released from fluid inclusions contained in sulfides and in barite in these three deposits. ³He/⁴He ratios of the ore‐forming fluids are 0.01 to 0.14 R/Ra with a mean of 0.07 Ra (where R is the ³He/⁴He ratio and Ra is the ratio for atmospheric helium). This mean value is intermediate to typical ³He/⁴He ratios for the crust (R/Ra = 0.01 to 0.05) and the ratio for air‐saturated water (R/Ra = 1). The mean ratio is also significantly lower than the ratios found for mantle‐derived fluids (R/Ra = 6 to 9). The ⁴⁰Ar/³⁶Ar ratios of the ore‐forming fluids range from 298 to 382 with a mean of 323. This value is slightly higher than that for the air‐saturated water (295.5). The ³He/⁴He ratios of fluids from the fluid inclusions imply that the ore‐forming fluid for the Baiyangping, Babaoshan, and Hetaoqing deposits was derived from the crust and that any mantle‐derived He was negligible. The content of the radiogenic Ar ranges between 0.2 to 20.4%, and the proportion of air‐derived ⁴⁰Ar averages 94.1%. This indicates that atmospheric Ar was important in the formation of these deposits but that some radiogenic ⁴⁰Ar was derived from crustal rocks. Based on these observations coupled with other geochemical evidence, we suggest that the ore‐forming fluids responsible for the formation of the Ag–Cu–Pb–Zn polymetallic ore deposits in the Baiyangping area of the Lanping basin were mainly derived from crustal fluids. The fluids may have mixed with some amount of air‐saturated water, but there was no significant involvement of mantle‐derived fluids.     

辽宁青城子矿集区金银矿成矿流体特征和成矿物质来源示踪

青城子矿集区地处辽东-吉南裂谷带西端,是金银多金属的重要矿集区,其成矿作用复杂,为了深入揭示其成矿流体特征和成矿物质来源,近期作者对矿集区内典型的金银矿床(高家堡子银矿、小佟家堡子金矿、杨树金矿和林家三道沟金矿)的地质特征研究的基础上,开展了流体包裹体测温和激光拉曼成分分析,H、O、C、S、Pb同位素的分析,进行了多元同位素体系的综合示踪。青城子矿集区金银矿床最为发育富液相包裹体,局部发育气相包裹体,个别石英脉中少量发育H_2O-CO_2三相包裹体和CO_2两相包裹体,成矿温度范围大,是多阶段成矿作用发展演化的反映,主成矿温度在120~210℃之间。成矿流体为中温低盐度低密度的水盐流体。激光拉曼成分特征,成矿流体总体属于含H_2的H_2O-NaCl-CH_4-CO_2体系,属于还原性流体,具有深源的特征。氢氧同位素结果显示,成矿热液主要来源于岩浆水和大气降水。碳氧同位素结果显示,成矿流体起源或流经含有大量有机质的地层,地层中的有机质可能参与了金的富集成矿。硫同位素特征表明,矿体中的硫来自海水硫酸盐还原硫与深部岩浆热液来源的混合,可能主要来自海水硫酸盐的还原。铅同位素结果表明,金银矿石中铅是地层与岩浆岩的混合铅。     

安徽池州马头钼铜矿床成因与成矿模式

马头钼铜矿床是长江中下游皖南地区新探明的一个中型多金属矿床,成矿受东西向古特提斯构造体系向北东向古太平洋构造体系转换机制制约。文章通过对矿床流体包裹体、稳定同位素地球化学特征进行研究,厘定了矿床成因,并构建了矿床成矿模式。研究结果表明:矿区内石英脉中流体包裹体均一温度范围为91℃~398℃、盐度范围为0.88%~37.4%、密度范围为0.18g/cm3~1.10g/cm3,属中温、中等盐度、中低密度流体,成矿流体演化经历了钾长石化、石英-绢云母化和青磐岩化三个阶段,石英-绢云母化阶段成矿规模最大;矿石与围岩全岩Pb同位素组成均一,在~(208)Pb/~(204)Pb-~(206)Pb/~(204)Pb图中呈线性分布趋势,表明成矿物质具有多源性,花岗闪长斑岩参与成矿的特征更为显著;黄铁矿中硫同位素组成介于-1.00‰~+7.00‰,近似塔型分布,辉钼矿硫同位素组成高于黄铁矿,表明矿石矿物中硫同位素组成均一且达到平衡,硫主要来源于深部地幔,并受到地壳物质的混染;无矿、含矿两类石英脉氧同位素组成范围为9.80‰~13.0‰,二者为同源热液作用的产物,流体中δ18 O水值为-1.21‰~+1.99‰,接近大气降水值,推测在成矿过程中原始含矿热液受到不同程度大气降水的混合。马头钼铜矿床为一具有斑岩型矿床围岩蚀变分带特征的次火山-热液矿床,属斑岩成矿系统,花岗闪长斑岩是区内最主要的成矿母岩,粉砂岩也为成矿提供了一定的物质条件,但钾长花岗岩脉与成矿关系不大。     

新疆蒙其古尔铀矿床成矿流体特征及其与铀成矿的关系

蒙其古尔铀矿床为大型层间氧化带砂岩型铀矿床,前人对其成矿流体来源的研究相对较少。为探讨其成矿流体的性质和来源,笔者利用显微测温学和激光拉曼光谱方法,对其流体包裹体的温度、盐度、密度和成分进行了系统的分析研究,并对其成矿流体的氢、氧同位素及含矿目的层砂岩方解石胶结物的碳、氧同位素组成特征进行了研究。研究表明,该矿床流体包裹体主要有气烃包裹体、液烃包裹体和盐水包裹体,成群分布于砂岩粒间方解石胶结物中,或沿切穿石英颗粒的微裂隙呈线状或带状分布,均一温度为56~76℃,盐度w(NaCleq)为1.23%~19.84%,密度为0.99~1.12 g/cm~3,气体成分以CH_4为主;成矿流体的δD(H_2O)V_SMOW=-93.0‰~-48.3‰,δ~(18)O(H_2O)V_SMOW=-10.3‰~-5.1‰,方解石胶结物的δ~(13)CV_PDB=-10.9‰~-7.2‰,δ~(18)OV_SMOW=17.6‰~24.9‰。上述特征揭示出蒙其古尔铀矿床成矿流体是由大气降水性质的地表水和煤系地层有机质脱羧基作用产生的有机酸及伴生的CH_4等还原性气体(煤型气)两部分组成,具有低温、盐度跨度大、中等密度及多期叠加等特点,明显有别于深部油气大规模充注。地表含铀含氧水层间渗入与煤系地层产生煤型气等还原性渗出流体的共同作用,形成了蒙其古尔铀矿床。     

氧化镁烧结-电感耦合等离子体质谱法测定砂岩型铀矿中的痕量铼

砂岩型铀矿中铀的平均含量为635μg/g,而铼的含量仅为0.3~1.9μg/g,由于铼的含量低,准确测定高含量铀矿样中的低含量铼仍是分析化学的一个难题。本文建立了电感耦合等离子体质谱法测定砂岩型铀矿中痕量铼的方法。样品经过氧化镁烧结,热水浸提以及采用103Rh作内标元素等方式消除了铀、钼及其他基体元素对测定铼的干扰。在最佳条件下,痕量铼的检出限可低至0.12 ng/g,回收率达99.8%。本方法通过多种标准样品验证,铼的测定值与标准值吻合,对铼含量在0.06~180.57μg/g范围内的实际样品进行测定,相对标准偏差均小于1.5%,能够满足砂岩型铀矿等高含量铀矿中痕量铼的测定需求。     

四川雪宝顶钨锡铍矿床流体包裹体研究及其意义

四川雪宝顶钨锡铍矿床产于花岗岩体与三叠系地层大理岩的接触带,赋矿石英脉受大理岩中的劈理破碎带控制。绿柱石与白钨矿中的包裹体可分为熔融包裹体、流体熔融包裹体和流体包裹体3类。流体包裹体又可分为H2O包裹体、CO2包裹体和CO2-H2O包裹体,其中,绿柱石中以富含CO2-H2O包裹体为显著特征。加热时,富H2O相CO2-H2O包裹体完全均一至H2O相,富CO2相CO2-H2O包裹体完全均一至CO2相,而二者的完全均一温度和均一压力一致,表明它们是同期捕获的CO2-低盐水不混溶包裹体组合。与绿柱石相比,白钨矿中CO2-H2O包裹体数量明显减少,H2O包裹体数量增多,成矿压力与成矿温度均有所降低。含CO2流体在花岗岩体与大理岩接触带附近发生流体不混溶和相分离,CO2的出溶使成矿流体中pH值升高,f(O2)降低,导致钨的溶解度降低而沉淀,这是形成白钨矿的主要原因。     

长江中下游成矿带铜陵新桥矿床Re-Os同位素及流体包裹体研究

新桥Cu-Au-Fe-S矿床位于安徽铜陵矿集区,是长江中下游成矿带中非常典型的多金属硫化物矿床。本文在双目镜下手工挑选黄铁矿单矿物并进行Re-Os同位素测试,首次得到了两组等时线年龄,分别为138±26Ma和393±40Ma。二者的初始Os同位素具有明显的区别,前者较高,具有明显的地壳来源特征,而后者则呈现了一定的地幔物质贡献的特征。138±26Ma的等时线年龄与该地区侵入体石英闪长岩140.4±2.2Ma的年龄一致。这些结果显示:新桥矿床可能存在两期成矿作用,分别为燕山期岩浆热液成矿和古生代海底喷流沉积成矿。在对与燕山期岩浆热液成矿相关的流体包裹体进行了相关研究之后发现,流体包裹体主要为Na Cl-H2O体系,没有发现富CO2等其他类型的包裹体,显微测温结果显示其盐度变化范围为4.2%~50.7%Na Cleqv,而均一温度(Th)变化范围为140~432℃。说明成矿流体可能主要是来自岩浆的含Na Cl的水溶液,而结合岩相学观察及显微测温结果我们可以发现成矿流体可能在250℃左右经历了微弱的沸腾作用,这些结果同时也显示出岩浆水与大气降水的混合作用的特征,说明新桥矿床该期次成矿的成矿流体可能经受了以上两种作用的共同影响并最终导致成矿物质沉淀成矿,成矿的温度为250℃左右。