富CO2深部流体对碳酸盐岩的溶蚀-充填作用的热力学分析

由于广泛而强烈的岩浆作用,我国东部的松辽、渤海湾、莺歌海以及西部的塔里木等盆地中都有富CO₂深部流体的活动。富CO₂深部流体与碳酸盐岩相互作用可用Duan and Li(2008)所建立的CO₂-H₂O-CaCO₃-NaCl体系的热力学模型来进行模拟计算。计算结果表明,富CO₂深部流体在自深部向浅部运移过程中对CaCO₃的溶解度会逐渐增加,到达一定深度后溶解度达到最大值,再向浅部溶解度开始逐渐降低; 也就是深部流体具有深部溶蚀碳酸盐岩-浅部沉淀碳酸盐矿物的规律。与浅部地层中的流体发生混合会使流体的CO₂含量和盐度降低,会导致CaCO₃的沉淀充填; 深部流体进入开启性断裂/裂缝体系中时,由于压力的降低,也会发生CaCO₃的沉淀充填。深部流体的CO₂含量、盐度、温度和压力的变化影响着实际的溶蚀-充填过程。塔中地区钻井也揭示了深部下奥陶统碳酸盐岩中发育有丰富的溶蚀孔隙,而在相对浅部的奥陶系灰岩和志留系砂岩中见有大量方解石的充填,这是富CO₂流体深部溶蚀-浅部充填的一个较好的实例。基于理论和实际分析,本文认为在岩浆火山作用广泛发育的塔里木等盆地中下古生界深部优质碳酸盐岩储层存在的可能性。     

高温高压下CO2在水中溶解度实验及理论模型

利用自行研制的高温高压反应釜,在不同温度、压力和矿化度条件下测试CO₂在地层水中的溶解度。实验结果表明:温度一定的条件下,CO₂在水中的溶解度随压力的增加而增加;压力一定的条件下,CO₂在水中溶解度的主要变化趋势为随温度的增加而降低,当温度大于100℃、压力在22 MPa左右时,CO₂在地层水中的溶解度将发生异常,出现低压(小于22 MPa)时随温度的增加而降低,高压(大于22 MPa)时随温度的增加而略微升高;在温度压力都一定的条件下,CO₂在水中的溶解度随矿化度的增加而降低。并且,在新测得的实验数据和已有的实验数据的基础上,通过修正PR-HV状态方程中的参数,建立了一个能够精确计算CO₂在水中溶解度的模型;并将该模型与其他模型对比。对比结果表明,该模型计算精度最高,平均相对误差仅为2.69%。     

吉林安图海沟金矿成矿流体特征及成矿机制

海沟金矿流体包裹体为3种类型：富CO₂三相、气液两相和纯气相。流体盐度集中在7.44％～8．67％NaCleqv,8.54％～8.94％NaCleqv和9.84％～10.87％NaCleqv三个区间;流体密度为0.54～0.88 g/cm3;成矿温度主要集中在298.4℃～313.5℃和258.2℃～264.6℃。研究表明成矿早期阶段流体为低盐度、富CO₂的高温流体,且富CO₂型和富气相包裹体共存。成矿中晚期阶段流体盐度和温度明显降低,CO₂、H₂O等气体能够大量逃逸,流体体系由封闭状态转化为较开放状态,大气降水、层间水等大量进入与岩浆流体发生混合,并引起流体内金络合物的溶解度减小而直接导致金和金属矿物的沉淀和富集。成矿压力范围为110～146 MPa,成矿深度为8.7～10.1 km。通过与典型的造山型金矿特征对比,该矿床成因类型为中成造山型金矿,动力学背景为早一中侏罗世华北板块与西伯利亚板块碰撞的持续汇聚力和古太平洋板块俯冲欧亚大陆的作用力引起的远程效应联合作用的结果。     

利用热液金刚石压腔开展黑钨矿结晶实验的初步研究

钨是一种工业用途广泛的稀有金属,主要产于热液型矿床。确定钨元素迁移和沉淀的物理化学条件对于揭示热液型钨矿床的形成机制具有重要意义。本文应用新型热液金刚石压腔(HDAC-VT)开展了(Fe,Mn)WO_4-Li_2CO_3-H2O体系的原位观测结晶实验,9组实验结果表明,黑钨矿晶体的结晶温度集中在560~500℃,结晶压力主要集中在400~200MPa。黑钨矿的溶解度随体系内CO_2组分相对含量的增加而增加;碳酸锂的结晶导致CO_2组分的减少,诱发黑钨矿的快速结晶,这指示出CO_2组分对钨的迁移和沉淀具有重要作用。含矿流体中CO_2组分的散逸可能是黑钨矿沉淀富集成矿的重要因素之一。     

江西省崇义县淘锡坑钨锡矿床流体包裹体特征及矿床成因

为研究赣南淘锡坑钨锡矿床的成矿物理化学条件和流体来源,对不同中段黑钨矿-石英脉矿体中包裹体进行了岩相学、显微测温、激光拉曼探针和氢、氧同位素分析。岩相学观察和显微测温表明：该矿区发育气相包裹体、液相包裹体、富液相包裹体、富气相包裹体、含液相CO₂的三相包裹体等5种类型原生包裹体;存在2个流体演化阶段,即早期硅酸盐-氧化物成矿阶段（310～390 ℃）和晚期氧化物-硫化物成矿阶段（180～270 ℃）。7个典型包裹体的气相和液相激光拉曼探针成分分析显示：包裹体中气相属富含CO₂的NaCl-H₂O系列,液相属贫CO₂的NaCl-H₂O系列。5件黑钨矿-石英脉矿石中石英流体包裹体的δD为－64‰～－79‰,δ¹⁸O水为5.51‰～6.53‰,表明成矿流体来源于深部岩浆水。结合区域最新研究成果,认为该矿床属与陆壳改造型花岗岩有关的岩浆热液型钨矿床。     

高盐度卤水对CO2地质封存的影响: 以江汉盆地潜江凹陷为例

江汉盆地潜江凹陷卤水资源十分丰富,潜江组泥膏岩、泥岩和砂岩交替沉积,构成CO₂地质储存的潜在场所.但是潜江组卤水层矿化度非常高,平均值高达283.25 g/L.以高盐度卤水为对象,探讨了高盐度卤水对CO₂封存过程中产生的物理化学影响.结果表明,往高盐度卤水层中单纯地注入CO₂会造成CO₂溶解量和矿物捕集量的显著降低,不利于CO₂的储存安全.高盐度会造成注入井附近发生盐岩大量沉淀,不利于CO₂的持续注入,同时造成近井周围压力严重积累,降低了封闭安全系数.采用CO₂与卤水联合注采模式,可有效缓解CO₂单纯地注入过程中的压力严重积累和盐岩沉淀问题,实现资源和地下空间最大化利用,收获经济和环保的双重效益.      

接触变质条件下变碳酸岩CO2释放与定量计算——以郯庐断裂南段肥东县双山为例

为了探讨接触变质带内变碳酸盐岩变质过程CO₂释放的数量和排放CO₂的物理、化学及地质条件,根据递进变质反应和时间积分流体通量模型,定量分析和定量计算了双山地区变碳酸盐岩在接触变质作用中释放CO₂的通量。计算结果得到CO₂的通量值为0.729×104~2.446×104 mol/cm2,CO₂的来源以接触变质反应释放为主;CO₂的生成释放与变质程度呈正相关关系。自白云石带至方解石带变质流体中X_CO2不断升高,但钙铝榴石带由于岩浆水影响,流体通量最高而X_CO2急剧下降。      

方解石与含硅流体的水-岩反应实验及其对“硅化碳酸盐岩”储层成因的启示

近年来的油气勘探表明, 含硅热液是碳酸盐岩层系中一种重要的溶蚀性流体, 查明其与碳酸盐岩的水-岩反应机理是揭示“硅化碳酸盐岩”储层发育机制并实现储层分布预测的基础和关键问题之一。文章采用熔融毛细硅管和水热反应釜为反应腔,开展了200~375℃范围内方解石和含硅流体的水岩反应实验。利用原位拉曼光谱技术在线描述反应过程中体系组成的变化,对于淬火后的固相样品,则采用扫描电镜—能谱分析进行形貌观测和成分鉴定。首先,查明了含硅流体与方解石脱碳反应发生的温度条件。方解石和含硅流体在275℃以上反应形成CO₂,固相为非硅灰石的钙硅酸盐,其结构有待进一步揭示。该结果表明单纯的硅质组分难以在储层温度条件下与灰岩发生反应;其次,提出高盐度、富CO2流体作用是造成灰岩溶蚀的重要因素;最后, CO₂的存在能够促进硅质（含石英）沉淀。在上述实验认识的基础上,结合前人研究结果探讨了塔里木盆地顺托果勒地区“硅化碳酸盐岩”储层的发育机制。含硅热液沿深大断裂上移,途径震旦系—下奥陶统白云岩层系,其中的硅质组分将与白云石反应形成富镁硅酸盐和CO₂。CO₂是重要的酸性组分,有利于鹰山组碳酸盐的溶蚀和孔隙的保存。流体温度和压力的降低以及CO₂的存在促进了石英沉淀,并形成了大量的石英晶间孔隙。     

CO2分压条件下煤中矿物质溶解度数值模拟

查明煤中矿物质在不同温度和CO₂分压条件下溶解度变化规律,能为注入CO₂过程中煤储层渗透率分析提供重要依据。借助水文地球化学模拟软件PHREEQC对在不同温度和CO₂分压条件下煤中各矿物的溶解度进行了水化学模拟,得出不同温度和CO₂分压条件下矿物质溶解度的变化规律。结果表明:在无CO₂分压时,随着温度的升高各矿物的溶解度增加;当溶液中CO₂分压增加到一定程度时,随着温度的升高各矿物的溶解度降低（石英除外）;在温度相同时,随着CO₂分压的增加,所有矿物（石英除外）溶解度均增加,方解石的溶解度随着CO₂分压的升高呈现出迅速增加的趋势,其他矿物随着CO₂分压的升高,溶解度增加的速率较为缓慢。      

基性、超基性岩: 二氧化碳地质封存的新途径

CO₂地质封存是控制全球CO₂净排放量的有效手段.自然界存在大量基性、超基性岩石的碳酸盐风化作用, 与CO₂反应生成稳定的碳酸盐矿物.影响基性、超基性岩石与CO₂反应速率的因素有温度、压力、pH值、流体流动速率以及与矿物接触的表面积等.矿物在反应过程中放热可以使碳酸盐化体系进入自我加热的良性循环, 同时控制流体的流动速率可以保持最佳温度并使反应速率最大化.蛇绿岩中的橄榄岩、大陆玄武岩和深海玄武岩在地球表层广泛分布, 可贮存大量CO₂.目前研究表明此方法在技术上可行, 经济成本上有优势.因此, 基性、超基性岩石具有封存CO₂的巨大潜力, 可以作为地质封存CO₂的新途径.      

江西黄沙石英脉型钨矿床流体包裹体研究

黄沙钨矿床是赣南地区一大型石英脉型钨多金属矿床。本文采用"流体包裹体组合"的研究方法,对黄沙钨矿床主成矿阶段早期的黑钨矿-石英脉和晚期的硫化物-(黑钨矿)-石英脉石英中的流体包裹体进行了显微测温和拉曼探针的分析。研究表明,黑钨矿-石英脉中包裹体主要为水溶液包裹体和含CO₂水溶液包裹体,硫化物-(黑钨矿)-石英脉中主要发育水溶液包裹体。黑钨矿-石英脉中包裹体的均一温度明显高于硫化物-(黑钨矿)-石英脉中的包裹体,但两者水溶液包裹体的盐度相差不大。激光拉曼探针测试表明,两期矿脉中水溶液包裹体的组分主要为水,在黑钨矿-石英脉中的含CO₂水溶液包裹体,除CO₂外,还检测到CH₄和N₂组分。研究表明,以CO₂逸失为特征的流体不混溶作用是早期黑钨矿-石英脉含矿流体中的金属络合物分解并沉淀成矿的主要机制,晚期硫化物-(黑钨矿)-石英脉中矿质的沉淀则主要是流体的混合作用导致。     

Fluid Inclusions and Stable Isotopic Characteristics of the Yaoling Tungsten Deposit in South China: Metallogenetic Constraints

The Yaoling tungsten deposit is a typical wolframite quartz vein‐type tungsten deposit in the South China metallogenic province. The wolframite‐bearing quartz veins mainly occur in Cambrian to Ordovician host rocks or in Mesozoic granitic rocks and are controlled by the west‐north‐west trending extensional faults. The ore mineralization mainly comprises wolframite and variable amounts of molybdenite, chalcopyrite, pyrite, fluorite, and tourmaline. Hydrothermal alteration is well developed at the Yaoling tungsten deposit, including greisenization, silicification, fluoritization, and tourmalinization. Three types of primary/pseudosecondary fluid inclusions have been identified in vein quartz, which is intimately intergrown with wolframite. These include two‐phase liquid‐rich aqueous inclusions (type I), two‐ or three‐phase CO₂‐rich inclusions (type II), and type III daughter mineral‐bearing multiphase high‐salinity aqueous inclusions. Microthermometric measurements reveal consistent moderate homogenization temperatures (peak values from 200 to 280°C), and low to high salinities (1.3–39 wt % NaCl equiv.) for the type I, type II, and type III inclusions, where the CO₂‐rich type II inclusions display trace amounts of CH₄ and N₂. The ore‐forming fluids are far more saline than those of other tungsten deposits reported in South China. The estimated maximum trapping pressure of the ore‐forming fluids is about 1230–1760 bar, corresponding to a lithostatic depth of 4.0–5.8 km. The δD_H2O isotopic compositions of the inclusion fluid ranges from ?66.7 to ?47.8‰, with δ¹⁸O_H2O values between 1.63 and 4.17‰, δ¹³C values of ?6.5–0.8‰, and δ³⁴S values between ?1.98 and 1.92‰, with an average of ?0.07‰. The stable isotope data imply that the ore‐forming fluids of the Yaoling tungsten deposit were mainly derived from crustal magmatic fluids with some involvement of meteoric water. Fluid immiscibility and fluid–rock interaction are thought to have been the main mechanisms for tungsten precipitation at Yaoling.     

Geology and Genesis of the Ta'ergou Skarn - Quartz Vein Tungsten Deposit in the North Qilian Caledonian Orogenic Belt, Northwest China

Abstract. The Ta'ergou tungsten deposit in Gansu province, northwestern China, is located in the western part of the North Qilian Caledonian orogen, and consists of scheelite skarn bodies and wolframite quartz veins. The tungsten‐bearing skarn developed by the replacement of carbonate layers intercalated in the Precambrian schist and amphibolite whereas wolframite‐quartz ore veins developed along a group of fractures that cut through horizontal skarns. The Ta'ergou tungsten deposit is genetically related to the Caledonian Yeniutan granodiorite intrusion and occurs ca. 500 m wide in the exo‐contact zone 300 ～ 500 m apart from the intrusion. The granodiorite displays a lower grade of differentiation, low content of SiO₂ and high contents of mafic components. There are three types of fluid inclusions in the wolframite‐quartz vein systems, i. e. aqueous, CO₂‐H₂O and CO₂‐rich. The homogenization temperature of aqueous inclusion ranges from 140 to 380d?C and their salinities from 6.4 to 17.4 equivalent wt% NaCl. Laser Raman spectroscopy shows that the inclusions contain a relatively high content of CO₂. The δ³⁴S values of skarn type sulfides range from +8.1 to +12.7 per mil and those of quartz vein sulfides from +9.3 to +14.9 per mil, similar to sulfides of the granodiorite with from +6.0 to +11.7 per mil. The δ¹⁸O values of quartz are between +10.5 and +13.3 per mil and those of wolframite between +3.4 and +5.1 per mil. The δ¹⁸O water values of ore forming fluids range from +0.6 to +6.4 per mil and suggest the mixture of magmatic fluids with meteoric water formed the ore‐forming fluids. It has been proved that Precambrian strata in the west sector of North Qilian region are enriched in tungsten. We propose the strata were remelted to be tungsten‐granitoid during subduction. The polymetallic tungsten was gradually accumulated into the roof pendants of the granite intrusion by fractional crystallization and then was deposited by hydrothermal fluids during metasomatism and infilling along fractures. On the other hand, the granite intrusion also acted as “heating machine” to make hydrothermal fluids leach out the metals from Precambrian strata and these metals joined the ore‐forming hydrothermal system.     

新疆巴里坤小加山钨矿地质特征与成因

小加山钨矿区位于东准噶尔成矿区中部南缘,处于博格达-哈尔里克构造带上。构造位置上矿区处于哈尔里克复式背斜中,构造线方向以EW向为主。矿区出露地层主要为中泥盆统大南湖组第一亚组第一段(D_2d_1~1)、和第二段(D_2d_1~2)。主要岩浆岩有石英闪长岩、黑云母二长花岗岩、钾长花岗岩及少量中酸性花岗闪长岩脉。矿体赋存于邻近海西晚期花岗岩侵入体附近的中泥盆统大南湖组第一亚组第二段(D_2d_1~2)的变质晶屑凝灰岩中。矿石类型为石英脉型黑钨矿石,有用金属主要为黑钨矿,黑钨矿石英脉分为灰色含钨石英脉和白色含钨石英脉2种。四极质谱分析法测得矿床流体包裹体气相成分以H_2O、CO_2为主,次为N_2、CH_4,此外还含有少量的Ar、C_2H_6,液相成分以Cl~-、Na~+为主,次为Ca~(2+),表明成矿流体主要为H_2O-CO_2-NaCl体系。矿床成因类型属于高温热液石英脉型黑钨矿床,矿体主要位于围岩裂隙构造。钨主要由侵入围岩地层中的地幔热液迁移富集而来,W元素迁移过程中,含钨络合物成矿流体分解进而沉淀成矿。     

斑岩型钨矿床研究进展

斑岩型钨矿床是全球第三重要的钨矿类型,但对其研究较为薄弱、零散.文章基于团队近年来对斑岩钨矿床的研究并系统搜集了全球的相关资料,然后对其进行梳理与总结.研究表明,斑岩型钨矿主要分布于环太平洋成矿带与阿尔卑斯—喜马拉雅成矿带,岩浆弧、板内及陆-陆碰撞等多种环境均有矿床产出.矿床绝大多数形成于中生代、少量形成于古生代.斑岩...     

江西大吉山钨多金属矿床流体包裹体研究

大吉山钨矿床是赣南地区的一个大型钨多金属矿床,由石英脉型钨矿体和花岗岩浸染型钨、钽、铌、铍矿体构成.在详细的岩相学观察的基础上,文章采用“流体包裹体组合”法,对石英脉型矿体和花岗岩浸染型矿体石英中的流体包裹体进行了显微测温和拉曼探针分析.研究表明,与石英脉型矿体成矿相关的流体为中-高温、中-低盐度的NaCl-H2O-CO2-CH4±N2体系,与花岗岩浸染型矿体成矿相关的流体为高温、中-低盐度的NaCl-H2O±CO2±CH4体系,两者流体的性质不同.笔者认为,在流体体系冷却过程中,所发生的以CO2逸失为特征的流体不混溶作用是石英脉型矿体的主要形成机制,而花岗岩浸染型矿体中金属元素的沉淀则主要由流体体系的冷却作用所致,这两类矿体的成矿流体的来源可能不同.     

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。     

Phase equilibria of several tungsten deposits in southern China

This paper reviews the features of several tungsten ore deposits in southern China, including the Shizhuyuan, Yaogangxian, Xihuashan, Dangping, Piaotang and Dajishan mines. The authors think that the formation depth of the greisen-type deposits is intermediate between the pegmatite-and porphyry-type deposits. Using phase diagrams of the model system K₂O-Al₂O₃-SiO₂-H₂O-HF, the formation mechanism of greisens has been argued. The variation of mineral assemblages from K-feldspar, muscovite to topaz reflects a gradual increase in acidity. This variation can be used as a criterion to appreciate the depth of mineralization. Phase equilibria of tungsten minerals in grcisen and skarn deposits can be depicted on chemical potential diagrams of the model system CaO-FeO-WO₃-CO₂-F₂O_?1. The assemblage wolframite + fluorite is shown to have ben transformed to scheelite + magnetite with decreasingμ _HF. Depending on CO₂ activity in the fluids, there are two distinct phase diagrams. One shaws that wolframite is incompatible with calcite, and the other demonstrates that scheelite is incompatible with rhodochrosite. On the phase diagrams of the model system FeO-MnO-WO₃-F₂S_?1, huebnerite is transformed to ferberite with increasingμF₂O_?1 orμF₂S_?1. During the replacement of wolframite by scheelite, the wolframite residue must have been enriched in Mn.     

Solubility of CO2 in a Ca-rich leucitite: effects of pressure,temperature, and oxygen fugacity

The solubility of carbon dioxide in a Ca-rich leucitite has been investigated as a function of pressure (0.1–2.0 GPa), temperature (1200–1600°C), and oxygen fugacity. The experiments were done in a rapid-quench internally-heated pressure vessel (0.1 GPa) and a piston cylinder (0.5–2.0 GPa). The leucitite glass, previously equilibrated at NNO, and silver oxalate were loaded in Fe-doped Pt capsules (oxidized conditions) and graphitelined Pt capsules (reduced conditions). Secondary Ion Mass Spectrometry and bulk carbon analyses were used to determine the amount of dissolved carbon. Speciation of carbon was characterized by Fourier transform microinfrared spectroscopy. At oxidized conditions, only CO₃ ^2- is observed as a dissolved species. The solubility is high with CO₂ contents in the melt attaining 6.2 wt% at 2.0 GPa and 1350°C. The solubility increases with pressure and shows a significant negative temperature dependence. An excellent correlation is obtained when the data are fit to a model, based on the simplified solubility reaction CO₂ ^(vapor)+O^2-(melt)CO₃ ^2-(melt), which describes the solubility of CO₂ as a function of pressure, temperature and fCO₂. At reduced conditions, the amount of carbon dissolved is significantly lower, and CO₃ ^2- is still the only species present in the melt. If the solubility model established at oxidized conditions is applied, the carbon dissolved appears to be essentially a function of fCO₂ alone although divergence increases in a consistent manner with pressure and temperature. This could suggest a low but significant solubility of CO with a positive temperature dependence or a departure of the calculated fluid compositions determined by the equation of state from the actual ones. The strong preferential solubility of carbon in its oxidized C⁴⁺ form, even at reduced conditions, implies that ascending melts with high CO₂ solubility can experience significant oxidation through degassing. This could reconcile the oxidized nature of some Ca-rich alkaline magmas with more reduced mantle source regions.