气体（CH4、H2S、CO2）在水溶液中的溶解度模型

本文介绍一个通过状态方程和特定粒子相互作用理论建立起来的气体在水溶液中的溶解度模型,用以计算气体(CH4、H2S、CO2)在纯水和含盐水溶液中的溶解度、流体包裹体的均一条件、成矿热液沸腾、流体不混溶性、水合物形成条件、CO2地质储藏量等.该模型不仅重现了上百套实验数据(约8000多个数据点),而且具有很强的外延能力.因...     

混合气体在水溶液中的溶解度计算模型

该文将段振豪及合作者建立的单气体溶解度模型推广到混合气体系,建立了能够计算CO2-CH4-N2-C2H6-H2S混合气 体在电解质水溶液中溶解度的热力学模型。本模型将DMW92方程扩展到上述多组分混合气体系并使用其计算气体组分的 逸度系数,采用Pitzer活度系数模型描述液相并沿用段振豪及合作者以前确定的纯CO2、CH4、C2H6和H2S的溶解度模型参 数,而纯N2的溶解度模型参数由本研究确定。由于本模型不包含依赖混合气体溶解度实验数据确定的参数,因此对混合气 体溶解度的计算是预测性的。通过与实验数据的对比,证实了本模型能够在宽广的温度、压力范围内准确预测 CO2-CH4-N2-C2H6-H2S混合气体在水溶液中的溶解度（对于CO2和CH4的摩尔百分数超过90%的混合气体,本模型适用于 273~523 K和0~2000×105 Pa的温压范围）。本模型的计算表明,相对于纯CO2气相,少量CH4、N2或H2S的加入会降低CO2的溶解度。对于CO2-H2O-NaCl型流体包裹体,少量CH4的加入会增大流体包裹体的均一压力。相关的计算程序可从通讯作者 处获得。     

胶东半岛大磨曲家金矿床成矿流体物理化学条件演化

胶东大磨曲家金矿床流体包裹体包括水溶液包裹体、富CO2包裹体和高盐卤水包裹体3种类型,前两者发育较多,高盐卤水包裹体发育极少。流体包裹体显微测温及盐度、密度、压力估算显示,水溶液包裹体均一温度为98~376℃,据冰点温度估算,盐度为0.53%~8.28%,水溶液包裹体均一压力低于50×105Pa;富CO2包裹体完全均一温度为255~348℃,盐度为2.42%~11.43%,均一压力为1 000×105~2 500×105Pa;富CO2包裹体中CO2均一温度为23.0~32.4℃,指示该类包裹体可能含有数量不等的CH4或H2S。静水压力体制下,根据纯CO2包裹体均一压力估算成矿深度约为1 km。在270℃左右,均一压力从富CO2包裹体到水溶液包裹体急剧降低,指示成矿流体在270℃左右可能发生过一次减压沸腾过程,成矿流体盐度和密度在270℃左右也有显著的变化。因此,沸腾作用及其引起的成矿流体物理化学条件的急剧变化可能是导致大磨曲家金矿床成矿物质沉淀的重要机制。     

小秦岭文峪金矿床流体包裹体研究及矿床成因

文峪金矿位于小秦岭矿田南部,其产出受脆-韧性剪切带控制,赋矿围岩为太华群变质杂岩.根据脉体穿切关系和矿物交代关系,可以将文峪金矿流体成矿过程分为早、中、晚三个阶段,其热液石英中发育CO2-H2O型、纯CO2型和H2O溶液型三种类型流体包裹体.平阶段石英中原生包裹体主要是CO2-H2O型和纯CO2型,其成分为CO2+H2O±N2±CH4,均一温度集中在290～330℃,盐度为1.02％～9.59％ NaCleqv;中阶段为主成矿阶段,该阶段石英中包含了所有3种类型的包裹体,其中以CO2-H2O型包裹体为主,获得CO2-H2O和水溶液包裹体均一温度集中在250～290℃,盐度为0.02％～12.81％NaCleqv;晚阶段石英仅发育水溶液型包裹体,具有较低的均一温度(114～239℃)和盐度(4.18％～8.95％ NaCleqv).根据CO2-H2O型包裹体计算早、中阶段压力分别为130 ～ 178MPa和85 ～ 150MPa,对应的成矿深度分别为4.7～6.5km和3.1～5.5km.总体而言,文峪金矿的初始流体具有中高温、富CO2、低盐度的变质流体特征,晚成矿阶段流体演化为低温、低盐度水溶液流体,流体的不混溶导致了主成矿期矿质的大量沉淀,文峪金矿为中浅成的造山型矿床.     

四川阿坝州党坝伟晶岩型锂辉石矿床流体包裹体特征及地质意义

四川省阿坝州党坝伟晶岩型锂辉石矿床是可尔因稀有金属矿集区内的典型矿床。通过对党坝锂辉石矿物流体包裹体研究结果表明:1)锂辉石矿物中富集气液两相水溶液包裹体、含CO2三相包裹体,见少量含子矿物三相包裹体;流体包裹体均一温度为260℃-314℃,盐度为w(NaCl,eqv)=2.96%~9.08%,指示党坝矿床成矿流体具中温、低盐度特征。2)激光拉曼光谱分析气相成分主要为H2O,CO2次之,见少量的CH4、N2;液相成分以H2O为主,含少量CO2、CH4;含子矿物包裹体的子晶矿物为方解石。3)成矿流体应属H2O-NaCl±CO2±CaCl2±CH4±N2体系,流体密度为0.72~0.88g/cm3,认为在成矿流体主要来源于岩浆热液。4)气液两相水溶液包裹体、含CO2三相包裹体以及含子矿物三相包裹体共存于同一视域中,且均一温度相近,表明流体发生沸腾或不混溶作用导致相分离并发生锂辉石聚集沉淀是党坝锂辉石矿床形成的主要原因。     

内蒙古浩尧尔忽洞金矿床流体包裹体特征

成矿流体来源与矿床成因的关系一直是矿床学研究的重点与难点。通过流体包裹体显微测温、原位激光拉曼光谱分析和包裹体化学成分分析,对浩尧尔忽洞金矿床成矿流体进行了较系统的研究。测试结果表明:该矿床石英中流体包裹体分为气液包裹体、气体包裹体、纯气体包裹体和纯液相包裹体四类。大部分流体包裹体均一为液相,少量气体包裹体均一为气相。伟晶岩脉石英流体包裹体均一温度峰值260～340℃,炭质板岩内含矿石英细脉内石英流体包裹体均一温度峰值260～380℃。石英流体包裹体气相成分为H2O、CO2、CH4、N2和C2H6,液相成分为Cl-、SO2-4、Na+、K+、Mg2+和Ca2+。炭质板岩中石英流体包裹体的氢氧同位素(δD H2O=-96.20‰～-82.80‰,δ18O H2O=3.97‰～7.93‰)靠近原生岩浆水。认为浩尧尔忽洞金矿床成矿与海西期岩浆活动有关,属中高温低压浅成热液矿床。     

河南祁雨沟金矿床成矿流体演化特征

祁雨沟隐爆角砾岩金矿床产于太古宇太华群中,金矿化分为6个成矿阶段,其中第Ⅰ,Ⅲ,Ⅴ阶段石英39Ar 40Ar坪年龄分别为130 31±0 86,122 61±0 61和(109 20±0 70)Ma。对各成矿阶段石英、方解石中流体包裹体均一温度、盐度、化学成分、氢氧同位素组成分析结果表明,早阶段流体为岩浆水,其后逐渐有大气降水的混合;第Ⅰ阶段高温(301 2～465 4℃)、中等盐度(9 1%～18 6%)的流体曾发生沸腾,形成较多以气相为主的包裹体;从第Ⅱ成矿阶段开始,流体沸腾减弱而出现不混溶现象;在第Ⅲ成矿阶段,不混溶作用增强,形成富CO2的低盐度流体与富H2O高盐度流体;在第Ⅳ—Ⅴ成矿阶段,大气降水的混合作用趋于增强,流体总体盐度降低。流体包裹体气相成分以CO2,H2S,CH4为主,含少量CO,N2,H2等,并且早阶段流体CO2含量较高,在第Ⅲ—Ⅴ成矿阶段,H2S,CH4,CO浓度增高,金属矿物大量出现。减压作用造成初始高温流体沸腾,其后温度降低以及盐析效应可能造成富CO2流体与富H2O流体的不混溶,而Au的大量沉淀则主要与大气降水的混合作用有关。     

山东省平度市大庄子金矿流体包裹体研究

山东省平度市大庄子金矿含金硅化体及石英脉中流体包裹体发育程度一般,且粒度偏小,包裹体大小多为6～12μm,包裹体类型主要为气液二相包裹体、液相包裹体(LH2O LCO2),见少量三相包裹体(LH2O LCO2 GCO2).化学成分属K (Na )-SO4-2(Cl-)型,气相成分以H2O、CO2为主,含一定量CH4、CO、H2S等还原性气体.均一温度表明金矿的成矿温度为中温(200℃～260℃),成矿流体盐度低(1.05%～4.96%).成矿流体主要来源于岩浆水、变质水,并有大气降水的混合.     

西藏甲玛铜多金属矿床流体包裹体特征及地质意义

甲玛矿床是位于西藏冈底斯成矿带中段的超大型铜多金属矿床。成矿相关岩体和主矿体中的流体包裹体岩相学、显微测温、激光拉曼探针及扫描电镜/能谱分析结果表明:与成矿有关的流体包裹体主要有富液相、富气相和含子矿物三相包裹体;流体包裹体均一温度变化范围为225～500℃,流体盐度(w(NaCl))平均值为36.2%,成矿流体主要为一种中高温、高盐度的NaCl-H2O体系;气相成分除H2O外,富含CH4、H2S、CO2、N2等不混溶体系。CH4、C2H4、C3H6等有机质的出现,说明成矿物质形成于还原环境中。据成矿压力估算成矿深度为2.2～8.3km,流体密度平均为0.89～0.98g/cm3。结合包裹体中的氢氧同位素测试结果认为,成矿流体主要来源于岩浆水,后期有大气降水的参与。含子矿物多相包裹体与不同气相充填度的液相包裹体、气相包裹体共存,且均一温度相近,而盐度相差很大,表明成矿流体经历了沸腾作用。     

新疆东准噶尔南明水金矿床成矿流体特征：流体包裹体及氢氧同位素证据

新疆东准噶尔南明水金矿床位于卡拉麦里成矿带东段,矿体受NW—NWW向韧-脆性断裂控制,赋矿围岩为下石炭统姜巴斯套组的浅变质海相火山碎屑-沉积岩。以流体包裹体和氢、氧同位素为研究手段,查明了矿床成矿流体性质、来源及其演化特征与金成矿的关系。其热液成矿过程可划分早、中、晚3个阶段,石英中原生包裹体主要有CO2-H2O包裹体、水溶液包裹体和纯CO2包裹体3种类型。早阶段石英中以CO2-H2O包裹体和纯CO2包裹体为主,均一温度变化于257~339 ℃,盐度为04%~22%;中阶段石英中3种类型包裹体均发育,CO2-H2O包裹体和水溶液包裹体均一温度为196~361 ℃,盐度为04%~60%;晚阶段石英中仅见水溶液包裹体,均一温度相对较低,为174~252 ℃,盐度为14%~32%。由CO2-H2O包裹体计算的早、中阶段捕获压力分别为214~371 MPa、236~397 MPa,对应的成矿深度分别为81~140 km、89~150 km。成矿流体由早、中阶段的CO2-H2O-NaCl±CH4体系演化至晚阶段贫CO2的H2O-NaCl体系,成矿温度和流体密度呈逐渐降低趋势,盐度变化不大。流体包裹体和氢、氧同位素研究表明,主成矿阶段成矿流体主要来源于变质水,CO2-H2O-NaCl流体的不混溶是导致Au富集成矿的重要机制,南明水金矿属于中深成造山型金矿床。     

Stability of the assemblage orthopyroxene-sillimanite-quartz in the system MgO-FeO-Fe2O3-Al2O3-SiO2-H2O

The stability of coexisting orthopyroxene, sillimanite and quartz and the composition of orthopyroxene in this assemblage has been determined in the system MgO-FeO-Fe₂O₃-Al₂O₃-SiO₂-H₂O as a function of pressure, mainly at 1,000° C, and at oxygen fugacities defined mostly by the hematite-magnetite buffer. The upper stability of the assemblage is terminated at 17 kbars, 1,000° C, by the reaction opx+Al-silicate gar+qz, proceeding toward lower pressures with increasing Fe/(Fe+Mg) ratio in the system. The lower stability is controlled by the reaction opx+sill+qz cord, which occurs at 11 kbars in the iron-free system but is lowered to 9 kbars with increasing Fe/(Fe+Mg). Spinel solid solutions are stabilized, besides quartz, up to 14 kbars in favour of garnet in the iron-rich part of the system (Fe/(Fe+Mg)0.30). Ferric-ferrous ratios in orthopyroxene are increasing with increasing ferro-magnesian ratio. At least part of the generally observed increase in Al content with Fe²⁺ in orthopyroxene is not due to an increased solubility of the MgAlAlSiO₆ component but rather of a MgFe³⁺AlSiO₆ component. The data permit an estimate of oxygen fugacity from the composition of orthopyroxene in coexistence with sillimanite and quartz.     

The stability of merwinite in the system CaO-MgO-SiO2-H2O-CO2 with CO2-poor fluids

The stability of merwinite (Mw) and its equivalent assemblages, akermanite (Ak)+calcite (Cc), diopside (Di)+calcite, and wollastonite (Wo)+monticellite (Mc)+calcite was determined at T=500–900° C and P _f=0.5–2.0 kbar under H₂O–CO₂ fluid conditions with X _{CO 2}=0.5, 0.1, 0.05, and 0.02. Merwinite is stable at P _f=0.5 kbar with T>700° C and X _{CO 2}<0.1. At P _f=2.0 kbar, the assemblage Di+Cc replaces merwinite at all T and X _{CO 2} conditions. At intermediate P _f=1 kbar, the assemblage Ak+Cc is stable above 707° C and Wo+Mc+Cc is stable below 707° C. The univariant curve for the reaction Di+Cc=Wo+Mc+CO₂ is almost parallel to the T axis and shifts to low P _f with increasing X _{CO 2}, with the assemblage Di+Cc on the high-P _f side. The implications of the experimental results in regard to contact metamorphism of limestone are discussed using the aureole at Crestmore, California as an example.     

Phase equilibria in the system K2O-FeO-MgO-Al2O3-SiO2-H2O-CO2 and the stability limit of stilpnomelane in metamorphosed Precambrian iron-formations

The phase relations of Al- and Fe-bearing silicates in the system K₂O-FeO-MgO-Al₂O₃-SiO₂-H₂O-CO₂, in the presence of quartz and magnetite, are discussed on the basis of mineralogic and petrologic data from Precambrian iron-formations and blueschist facies meta-ironstone from the Franciscan Formation, California. These relations allow an estimation of the physiochemical conditions during low-grade metamorphism of iron-formations. Petrologic data together with available experimental and predicted thermodynamic data on the associated minerals place the upper stability limit of stilpnomelane in iron-formations at about 430–470° C and 5–6 kilobars. Fe-end member stilpnomelane can persist to a maximum temperature of 500° C and pressures up to 6–7 kilobars, although it is unlikely to occur in metamorphosed iron-formations. In iron-formation occurrences the stilpnomelane stability field is bordered by four equilibrium reactions with the assemblages stilpnomelane-zussmanite-chlorite-minnesotaite, stilpnomelane-zussmanite-chlorite-grunerite, stilpnomelane-biotite-chlorite-grunerite, and stilpnomelane-biotite-almandine-grunerite. The stability field is reduced by increasing X(CO₂) and X _Mg ^Stil , and is also a function of a(K ⁺)/ a(H ⁺) in the metamorphic fluid. If the value of a(K ⁺)/ a(H ⁺) is smaller than that defined by the above assemblages, stilpnomelane decomposes to chlorite, but if larger, it is replaced by biotite. At pressures less than 4 kilobars, the zussmanite field is restricted to a very high value of a(K ⁺)/a(H ⁺) (> 5.0 in log units at 1.0 kilobar) where iron-formation assemblages are not stable.     

地下咸水中Ca~(2+)和Mg~(2+)对CO_2溶解度的影响

获得CO2在地下咸水中的溶解度是CO2地质储存研究中亟待解决的问题,然而不同离子对CO2溶解度的影响却鲜有文献提及。为了填补实验数据的空缺,本研究设计了一套高压条件下CO2溶解度测量装置,克服了传统高压釜取样不便和实验重现性差的缺点;通过测定纯水中CO2的溶解度验证了实验装置和方法的精准性;测定了地质埋存条件下0.1 mol/L、0.2 mol/L和0.5 mol/L Ca Cl2、Mg Cl2溶液中CO2的溶解度。与文献结果不同,实验发现Ca2+对超临界CO2溶解度的影响小于Mg2+,并且CO2在两种溶液中的溶解度差异会受到温度和压力的影响。在本实验范围内,不同离子溶液中溶解度的最大差别高达18.53%,而几乎所有CO2溶解度模型文献都没有提及此变化。最后对溶解度随温度、压力以及离子种类变化的现象进行了理论分析。     

Stability of the assemblage cordierite—Corundum in the system MgO-Al2O3-SiO2-H2O

The assemblage Mg-cordierite — corundum is formed stably through the reaction chlorite+Al-silicate=cordierite+corundum+H₂O at 535° C, 2kb; 615°, 5 kb; and 665° C, 7 kb water pressure. In the order of increasing pressure andalusite, sillimanite, and kyanite participate as stable phases in this equilibrium. A spinel-Al-silicate tie-line is only stable at high temperatures not likely to be attained in rocks. The natural assemblage spinel-Al-silicate is, however, to be explained by the additional presence of FeO in these rocks.     

Gehlenite stability in the system CaO-Al2O3-SiO2-H2O-CO2

P, T, \(X_{{\text{CO}}_{\text{2}} }\) relations of gehlenite, anorthite, grossularite, wollastonite, corundum and calcite have been determined experimentally at P _f =1 and 4 kb. Using synthetic starting minerals the following reactions have been demonstrated reversibly

1. 2 anorthite+3 calcite=gehlenite+grossularite+3 CO₂.
2. anorthite+corundum+3 calcite=2 gehlenite+3 CO₂.
3. 3anorthite+3 calcite=2 grossularite+corundum+3CO₂.
4. grossularite+2 corundum+3 calcite=3 gehlenite+3 CO₂.
5. anorthite+2 calcite=gehlenite+wollastonite+2CO₂.
6. anorthite+wollastonite+calcite=grossularite+CO₂.
7. grossularite+calcite=gehlenite+2 wollastonite+CO₂.

In the T, \(X_{{\text{CO}}_{\text{2}} }\) diagram at P _f =1 kb two isobaric invariant points have been located at 770±10°C, \(X_{{\text{CO}}_{\text{2}} }\) =0.27 and at 840±10°C, \(X_{{\text{CO}}_{\text{2}} }\) =0.55. Formation of gehlenite from low temperature assemblages according to (4) and (2) takes place at 1 kb and 715–855° C, \(X_{{\text{CO}}_{\text{2}} }\) =0.1–1.0. In agreement with experimental results the formation of gehlenite in natural metamorphic rocks is restricted to shallow, high temperature contact aureoles.     

Synthesis of Ca-tourmaline in the system CaO-MgO-Al2O3-SiO2-B2O3-H2O-HCl

Summary. ?Ca-tourmaline has been synthesized hydrothermally in the presence of Ca(OH)₂ and CaCl₂-bearing solutions of different concentration at T = 300–700 °C at a constant fluid pressure of 200 MPa in the system CaO-MgO-Al₂O₃-SiO₂-B₂O₃-H₂O-HCl. Synthesis of tourmaline was possible at 400 °C, but only above 500 °C considerable amounts of tourmaline formed. Electron microprobe analysis and X-ray powder data indicate that the synthetic tourmalines are essentially solid solutions between oxy-uvite, CaMg₃- Al₆(Si₆O₁₈)(BO₃)₃(OH)₃O, and oxy-Mg-foitite, □(MgAl₂)Al₆(Si₆O₁₈)(BO₃)₃(OH)₃O. The amount of Ca ranges from 0.36 to 0.88 Ca pfu and increases with synthesis temperature as well as with bulk Ca-concentration in the starting mixture. No hydroxy-uvite, CaMg₃(MgAl₅)(Si₆O₁₈)(BO₃)₃(OH)₃(OH), could be synthesized. All tourmalines have < 3 Mg and > 6 Al pfu. The Al/(Al + Mg)-ratio decreases from 0.80 to 0.70 with increasing Ca content. Al is coupled with Mg and Ca via the substitutions Al₂□Mg₋₂Ca₋₁ and AlMg₋₁H₋₁. No single phase tourmaline could be synthesized. Anorthite ( + quartz in most runs) has been found coexisting with tourmaline. Other phases are chlorite, tremolite, enstatite or cordierite. Between solid and fluid, Ca is strongly fractionated into tourmaline ( + anorthite). The concentration ratio D = Ca(fluid)/Ca(tur) increases from 0.20 at 500 °C up to 0.31 at 700 °C. For the assemblage turmaline + anorthite + quartz + chlorite or tremolite or cordierite, the relationship between Ca content in tourmaline and in fluid with temperature can be described by the equation (whereby T = temperature in °C, Ca(tur) = amount of Ca on the X-site in tourmaline, Ca( fluid) = concentration of Ca²⁺ in the fluid in mol/l). The investigations may serve as a first guideline to evaluate the possibility to use tourmaline as an indicator for the fluid composition.

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Zusammenfassung. ?Synthese von Ca-Turmelin im System CaO-MgO-Al ₂ O ₃ -SiO ₂ -B ₂ O ₃ -H ₂ O-HCl Im System CaO-MgO-Al₂O₃-SiO₂-B₂O₃-H₂O-HCl wurde Ca-Turmalin hydrothermal aus Ca(OH)₂ and CaCl₂-haltigen L?sungen bei T = 300–700 °C und einem konstanten Fluiddruck von 200 MPa synthetisiert. Die Synthese von Turmalin war m?glich ab 400 °C, aber nur oberhalb von 500 °C bildeten sich deutliche Mengen an Turmalin. Elektronenstrahl-Mikrosondenanalysen und R?ntgenpulveraufnahmen zeigen, da? Mischkristalle der Reihe Oxy-Uvit, CaMg₃Al₆(Si₆O₁₈)(BO₃)₃(OH)₃O, und Oxy-Mg-Foitit, □(MgAl₂)Al₆(Si₆O₁₈)(BO₃)₃(OH)₃O gebildet wurden. Der Anteil an Ca variiert zwischen 0.36 und 0.88 Ca pfu und nimmt mit zunehmender Synthesetemperatur und zunehmender Ca-Konzentration im System zu. Hydroxy-Uvit, CaMg₃(MgAl₅) (Si₆O₁₈)(BO₃)₃(OH)₃(OH), konnte nicht synthetisiert werden. Alle Turmaline haben < 3 Mg und > 6 Al pfu. Dabei nimmt das Al/(Al + Mg)- Verh?ltnis mit zunehmendem Ca-Gehalt von 0.80 auf 0.70 ab. Al ist gekoppelt mit Mg und Ca über die Substitutionen Al₂□Mg₋₂Ca₋₁ und AlMg₋₁H₋₁. Einphasiger Turmalin konnte nicht synthetisiert werden. Anorthit (+ Quarz in den meisten F?llen) koexistiert mit Turmalin. Andere Phasen sind Chlorit, Tremolit, Enstatit oder Cordierit. Ca zeigt eine deutliche Fraktionierung in den Festk?rpern Turmalin (+ Anorthit). Das Konzentrationsverh?ltnis D = Ca(fluid)/Ca(tur) nimmt von 0.20 bei 500 °C auf 0.31 bei 700 °C zu. Für die Paragenese Turmalin + Anorthit + Quarz mit Chlorit oder Tremolit oder Cordierit gilt folgende Beziehung zwischen Ca-Gehalt in Turmalin und Fluid und der Temperatur: (wobei T = Temperatur in °C, Ca(tur) = Anteil an Ca auf der X-Position in Turmalin, Ca(fluid) = Konzentration von Ca²⁺ im Fluid in mol/l). Die Untersuchungen dienen zur ersten Absch?tzung, ob Turmalin als Fluidindikator petrologisch nutzbar ist.

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Received July 24, 1998;/revised version accepted October 21, 1999