河南祁雨沟金矿流体包裹体及矿床成因类型研究

河南祁雨沟金矿位于华北克拉通南缘的熊耳地体．产于燕山期火山隐爆角砾岩筒内。流体包裹体研究表明．祁雨沟金矿不同成矿阶段的石英中的流体包裹体有3种类型：水溶液包裹体、含子矿物包裹体和含CO2包裹体。成矿早期流体为高温（〉350℃）、高盐度（〉30wt％NaCl．eqv）、高氧逸度、富CO2的岩浆流体,经流体减压沸腾、挥发分逸失、氧逸度降低、温度降低演化为导致大量金属硫化物及金沉淀的还原性流体．再经大气降水的混入和降温等过程．演化为晚阶段低温、低盐度的大气降水热液。祁雨沟金矿的地质和成矿流体特征指示其应为爆破角砾岩型．而非浅成低温热液型．     

新疆阿勒泰海相火山岩铁矿带中流体包裹体特征和成矿作用的热力学条件

由海相火山岩铁矿带划分的五个成矿作用阶段,进行矿物流体包裹体的系统研究。阐述了四种类型的流体包裹体在不同成矿阶段中的分布特征。计算出不同阶段成矿溶液的热力学条件:温度、压力、氧逸度、流体成分、密度、含盐度。对该成矿带铁质来源、成矿方式、矿床成因进行了探讨。从而、初步建立了本矿带成矿模式。     

江西留龙金矿床含矿流体特征研究

论述了江西南部留龙金矿床中石英的流体包裹体形态及成分;测定了流体包裹体的温度、盐度;计算了含矿流体的压力、逸度〔ｆ（Ｏ２）,ｆ（ＣＯ２）〕、成矿深度;并对含矿流体演化过程进行了探讨分析。     

广西德保矽卡岩型铜锡矿床成矿流体演化特征

位于右江盆地的德保铜锡矿床是广西最大的铜矿床,目前仅有少量年代学和矿物学等方面的研究,对于该矿床流体特征、流体环境、矿床元素组成等所知甚少。通过矿石矿物的探针分析、流体包裹体岩相学和显微测温、平衡热力学计算约束了该矿床成矿流体的地球化学参数,分析了成矿阶段的流体环境。与典型矽卡岩型铜锡矿床不同的是,德保铜锡矿的石榴子石以镁铝榴石和钙铝榴石为主,含少量钙铁榴石;锡主要以类质同象富集在黄铜矿、黄铁矿等硫化物中,含量达96×10-6～627×10-6;石榴子石的流体包裹体均一温度182～249℃,平均值219℃;方解石包裹体均一温度109～215℃,平均值157℃;平衡热力学计算模拟表明,德保铜锡矿床硫逸度和氧逸度范围分别是:logf_S2>-20,-44O₂<-25。早期成矿流体温度的降低为黄铜矿沉淀提供了有利条件,锡元素伴随黄铜矿沉淀;成矿流体的氧逸度高于世界典型锡矿的氧逸度,这种高氧逸度的成矿流体环境不利于锡元素的运移及再富集,这可能是德保铜锡矿中锡较少以锡石存在的重要原因...     

三种类型烃-烃不混溶包裹体组合的特征和热力学条件的计算

在自然界广泛分布着烃-烃不混溶体系中捕获的流体包裹体,由于这些包裹体具有复杂的组成和相态,因此不混溶包裹体组合的判别和热力学参数的计算常常难以进行。根据烃-烃不混溶体系中两个端员组分流体包裹体室温下的相态特征和在温度-压力平面图上等容线交点显示的位置,划分成三种类型流体包裹体组合,本介绍了三种类型流体包裹体组合特征,叙述了不混溶烃-烃包裹体组合的测定和判别方法,并且阐述均一化包裹体相态方程和气-液平衡常数原理和方法与此同时列举了自然界简单的三种类型不混溶烃-烃包裹体组合的测定、判别和计算的几个实例,利用相态方程和气-液平衡常数,不但精确地计算出包裹体均一压力,并且精确地计算出流体密度和体积等热力学参数。最后,利用均一成气相和液相的两种包裹体在 p-T 平面图上等容线交点同样计算出流体包裹体组合的捕获温度和压力。     

金厂峪金矿床成矿物理化学条件初探

通过研究金厂峪金矿含金石英的流体包裹体特征,阐明了金矿床形成的物理化学条件,确定了成矿温度、成矿压力以及成矿溶液的性质。对矿床形成时的硫逸度、氧逸度及二氧化碳逸度进行了阐述,并且结合地质地球化学特征探讨了金矿床的成因。     

西拉木伦多金属成矿带鸡冠山斑岩钼矿富氟高盐度高氧逸度流体包裹体研究

鸡冠山斑岩钼矿床位于西拉木伦多金属成矿带南侧、内蒙古赤峰市北东约35km处,大地构造位置属于华北板块北缘造山带中段。辉钼矿化主要呈浸染状、细脉浸染状分布在花岗斑岩中,部分成细脉浸染状分布在流纹质角砾凝灰岩中,同时,在矿区出露的辉绿岩和流纹岩中也有少量的细网脉状钼矿化。矿石矿物主要有辉钼矿、黄铁矿和少量黄铜矿、闪锌矿、磁铁矿,脉石矿物主要有石英、长石、绢云母和少量方解石、萤石。矿脉穿插关系和矿物组合显示了早、中、晚3个阶段的矿化:(1)石英-辉钼矿阶段;(2)萤石-(石英)-辉钼矿多金属硫化物阶段;(3)贫矿萤石阶段。各阶段广泛发育流体包裹体,包裹体类型众多,包括气液两相水溶液包裹体(W型),H2O-CO2包裹体(C型)及含子矿物多相包裹体(S型),其中以大量发育含子矿物多相包裹体为特征。子矿物种类有石盐、钾盐、赤铁矿、石膏、辉钼矿、方解石等及其他未鉴别透明、不透明子矿物,有时一个包裹体含有多达4～5个子矿物。包裹体大量的赤铁矿、石膏和金属子矿物的出现,说明含矿流体具有高的氧逸度和很强的金属携带能力。包裹体岩相学、激光拉曼和显微测温结果表明,成矿流体主要为来自高温、高盐度、高氧逸度的岩浆流体和部分天水与岩浆热液混合所形成的中低温、低盐度流体两个端员组份。高温、高盐度流体以含子矿物多相包裹体为代表,其形成温度大于440℃,盐度变化范围为:28%～76%NaCleqv,部分高于76%NaCleqv。中低温、低盐度流体主要源自矿化后期天水与岩浆热液的混合,温度在322℃以下,盐度变化范围为:0.9%～20.3%NaCleqv。实验结果表明鸡冠山矿区含矿硫化物主要沉淀温度区间在310～400℃之间,其次为210～320℃,钼矿化主要形成于高温、高盐度、高氧逸度及富氟元素的H2O-NaCl流体体系,温度降低、流体沸腾作用及流体混合是该钼矿床的主要成矿机制。     

大兴安岭岔路口斑岩钼矿床流体成分及成矿意义

岔路口超大型斑岩型钼矿床位于大兴安岭北段,以网脉状和角砾岩型矿化为主.该矿床经历了4个成矿阶段:Ⅰ.石英-钾长石;Ⅱ.石英-辉钼矿;Ⅲ.石英-多金属硫化物;Ⅳ.石英-萤石-方解石.包裹体的岩相学及激光拉曼研究揭示,石英斑晶内的熔体-流体包裹体中熔体成分有更长石和钠长石,为岩浆出溶作用形成;子矿物多相包裹体(S型)中含有钾盐、石盐、赤铁矿和石膏等子矿物,显示出成矿流体为高氧逸度.第Ⅰ成矿阶段包裹体有气液两相(L+V型)、富CO₂三相(C型)和含石盐、钾盐、赤铁矿及硬石膏等子矿物的多相(S型)等类型,第Ⅱ成矿阶段除了有L+V型、C型以及含钾盐、石盐、黄铜矿和辉钼矿等子矿物多相(S型)外,还可以见到S型包裹体与气相包裹体(V型)共存;第Ⅲ成矿阶段以L+V型和含方解石的S型包裹体为主;第Ⅳ成矿阶段除见到L+V型包裹体外,还可以见到液相包裹体(L型).显微测温结果显示从早到晚,流体包裹体均一温度从530 ℃变为120 ℃、盐度从66.7% NaCl equiv变为1.2% NaCl equiv,呈现逐渐降低的趋势.群体包裹体成分显示各阶段均含有气相CO₂,液相成分中Na+,K+,Ca2+,SO₄2-,Cl-含量很高,而F-含量极少.成矿流体总体属于富含CO₂的高盐度、高氧逸度的NaCl-H₂O-CO₂体系,在流体演化过程中温度、氧逸度、盐度和CO₂含量逐渐降低.温度、盐度、CO₂含量逐渐降低及绢云母化影响了矿石沉淀.      

白云鄂博地区碳酸岩墙及岩墙旁侧石英岩中的包裹体研究

白云鄂博的碳酸岩墙中包裹体类型有多子晶包裹体、两相水溶液包裹体、含CO_2三相包裹体和含子晶三相包裹体,岩相学和显微测温结果表明,这些包裹体与国外典型的碳酸岩中的包裹体具有很大程度的一致性,反映了其岩浆成因特点;碳酸岩墙中旁侧的白云鄂博H2石英岩中含有大量的流体包裹体,主要类型为NaCl-H_2O包裹体、CO_2包裹体和H_2O±CO_2±固体的包裹体。包裹体的岩相学、显微测温、阴极发光特征、包裹体成分ICP-MS测定,激光拉曼研究等,揭示出石英岩中的包裹体捕获了来自碳酸岩墙的碳酸岩浆流体,提供了一种不可多得的直接研究碳酸岩流体的手段。     

山西中条山铜矿峪斑岩型铜矿床成矿流体特征

铜矿峪铜矿床位于中条山铜多金属成矿带,是目前中国最古老的斑岩型铜矿床之一。基于详尽的野外地质调查,结合流体包裹体岩相学、显微测温、群包裹体成分和碳、氢、氧、硫同位素分析等研究,探讨铜矿峪铜矿床成矿流体来源、性质及其演化和成矿物质来源。铜矿峪铜矿床的成矿阶段可划分为红钠化(石英-钠长石)阶段,钾长石-石英阶段,石英-硫化物阶段,石英-碳酸盐阶段(石英-方解石-硫化物阶段和石英-铁白云石-硫化物阶段)和碳酸盐阶段。流体包裹体类型主要有富液相气液两相包裹体(Ⅰ型)、含子晶包裹体(Ⅱ型)和CO2包裹体(Ⅲ型),还有少量的富气相包裹体(Ⅳ型)和液相包裹体(Ⅴ型),成矿流体系统早期为中高温、高氧逸度、富CO2的岩浆热液,中阶段经过流体沸腾、温度降低、氧逸度降低、CO2逸失等过程演化为还原性流体,使得大量金属硫化物沉淀,最后由于大气降水的不断加入和降温等过程,形成晚期的低温、中低氧逸度、低盐度、贫CO2的大气降水热液。氢、氧同位素组成(δ18OH2O值变化范围为6.5‰～-1.10‰,δD值变化范围为-99‰～-58‰)显示,从早阶段到晚阶段,成矿流体从以原生岩浆水为主,到晚期大气降水为主。9件硫化物样品δ34S值变化于1.1‰～4.8‰,平均值为2.44‰。表明成矿物质具有深源的特征。     

Titaniferous magnetite–ilmenite thermometry and titaniferous magnetite–ilmenite–orthopyroxene–quartz oxygen barometry in granulite facies gneisses, Bamble Sector, SE Norway: implications for the role of high-grade CO2-rich fluids during granulite genesis

Oxygen fugacities have been estimated for a wide distribution of samples from the granulite facies terrane (region C) of the Bamble Sector, SE Norway using both the titaniferous magnetite–ilmenite and orthopyroxene–titaniferous magnetite–quartz oxygen barometers. These oxygen fugacities are estimated using temperatures calculated from the titaniferous magnetite–ilmenite thermometer of Ghiorso and Sack (1991) and are both internally consistent with each other as well with the thermometer. In samples for which the estimated temperature is high, the two oxygen barometers show good agreement whereas agreement is poor for low temperature samples. In these low temperature samples, oxygen fugacities estimated from titaniferous magnetite–ilmenite are considerably less than those estimated from orthopyroxene–titaniferous magnetite–quartz. An increase in this discrepancy with decrease in temperature appears to reflect preferential resetting of the hematite component in the ilmenite grains without significant alteration of the more numerous titaniferous magnetite grains. This is due, in part, to greater re-equilibration of the ilmenite grains during retrograde interoxide resetting between the ilmenite grains and the titaniferous magnetite grains. The mean temperature for the non-reset samples, 791?±?17?°C (1σ), is in good agreement with temperatures obtained from garnet–orthopyroxene K_D exchange thermometry in the same region, 785–795?°C (1σ) (Harlov 1992, 2000a). Most non-reset oxygen fugacities range from log₁₀?f?O₂=?14 to ?11.8 or approximately 0.5–1.5?log units above quartz–fayalite–magnetite at 7.5?kbar. Both these temperatures and the range of oxygen fugacities are in good agreement with those estimated using the titaniferous magnetite–ilmenite thermometer/oxygen barometer of Andersen et?al. (1991). The QUIlP equilibrium (quartz–ulvöspinel–ilmenite–pyroxene) is used to project self-consistent equilibrium temperatures and oxygen fugacities for samples reset due to hematite loss from the ilmenite grains. These projected temperatures and oxygen fugacities agree reasonably well with the non-reset samples. The mean projected QUIlP temperature is 823?±?6?°C (1σ). This result supports the conclusion that low titaniferous magnetite–ilmenite temperatures (down to 489?°C) and accompanying low oxygen fugacities are the result of hematite loss from the ilmenite grains. Non-reset oxygen fugacities lie approximately 1.5?log₁₀ units above the upper graphite stability curve indicating that the stable C–O–H fluid phase interacting with these gneisses, whether regionally or locally, was CO₂. This is borne out by the presence of numerous CO₂-rich fluid inclusions in these rocks.     

Preferential water loss from synthetic fluid inclusions

A fundamental question in most fluid inclusion studies is whether inclusions behave as compositionally closed systems after trapping, and, thus, represent samples of the fluid phase(s) present in the system at the time of their formation. This question was addressed in high-temperature laboratory experiments with synthetic fluid inclusions in quartz and it was found that at 825°C the inclusions exhibited open-system behavior with respect to water. Synthetic salt-water fluid inclusions in quartz were reequilibrated for 12 hours to 35 days at 825° C in a dry argon atmosphere under 1.5 kbar confining pressure. These conditions created initial internal overpressures (P _int> P _conf) of 1.5–4 kbar in the inclusions and differential water fugacities in the same sense i.e., fH₂OfH₂O. After 108 hours of reequilibration, preferential water loss had resulted in salinity increases as large as 22 wt% salt (e.g., from 57 to 79 wt% NaCl, as determined from measured temperatures of salt dissolution). Also, following reequilibration, a strong inverse correlation between salinity and inclusion volume was observed, and this trend became more pronounced with increasing reequilibration time. These observations, together with a lack of evidence for selective H₂O removal via hydration reactions, suggest that water loss occurred by a diffusion-related mechanism. Fluxes of 4x10^-11 g/cm²-s and diffusion coefficients on the order of 10^-9 cm²/s are calculated for water loss from the inclusions. The calculated H₂O diffusion coefficient is consistent with the determination of Blacic (1981) derived from hydrolytic weakening experiments, but is much larger than the value obtained by Giletti and Yund (1984) for volume diffusion of oxygen in isotope exchange experiments. These observations suggest that the mechanism of water loss from our synthetic fluid inclusions may have been pipe diffusion along dislocations, subgrain boundaries or other structural defects rather than bulk volume diffusion.The results of this study are relevant to the interpretation of fluid inclusions in quartz from several natural high-temperature environments where water fugacities of included and ambient fluids are known to have evolved along separate paths over geologic time.     

Methane-bearing,aqueous, saline solutions in the Skaergaard intrusion,east Greenland

Solutions of H₂O–NaCl–CH₄ occur in fluid inclusions enclosed by quartz, apatite and feldspar from gabbroic pegmatitites, anorthositic structures and intercumulus minerals within the Skaergaard intrusion. The majority of the fluid inclusions resemble 10 m diameter sub-to euhedral negative crystals. A vapour phase and a liquid phase are visible at room temperature, solids are normally absent. The salinity of the fluids ranges from 17.5 to 22.8 wt.% NaCl. CH₄, which comprises less than six mole percent of the solution, was detected in the vapour phase of the fluid inclusions with Raman microprobe analysis. Homogenization of the fluid inclusions occurred in the liquid phase in the majority of the fluid inclusions, though 10% of the inclusions homogenized in the gas phase. Thermodynamic consideration of the stability of feldspars + quartz, and the C–O–H system, indicates that the solutions were trapped at temperatures between 655 and 770°C, at oxygen fugacities between 1.5 and 2.0 log units below the QFM oxygen buffer. Textural evidence and the composition of the solutions suggest that the fluids coexisted with late-magmatic intercumulus melts and the melts which formed gabbroic pegmatites. These solutions are thought to have contributed to late-magmatic metasomatism of the primocryst assemblages of the Skaergaard intrusion.     

Characteristics and origin of ore-forming fluids of Jinchangqing gold （copper） ore deposit （s） in Xiangyun, Yunnan Province

On the basis of results of the studies of primary fluid inclusions, and the hydrogen and oxygen isotope data, the authors concluded that the early-stage ore-forming fluid from the Jinchangqing gold(copper) ore deposit is a kind of sulfate type hot brine characterized by medium temperature and salinity,genetically related to the late-stage ore-forming fluid derived from an acidic and more reduetive environment. However, the late-stage ore-forming fluid is a sort of low temperature and low salinity chloride-type hot brine which originated from a lower pressure, acidic and more oxidative environment. In general, the ore fluids were derived from the late-stage, or largely from the early-stage groundwater-derived meteoric water, which has a 12‰-17‰ heavier oxygen isotopic composition than the original rain water (δ^18O=- 15.3‰), and were formed during gold mineralization as a product of oxygen isotope exchange during the reaction between ore-forming fluid and wall rocks under a lower water/rock ratio condition.     

FeO activity and oxygen potential in magnesian magmas

An equation for the excess free energy of melts containing all major components is derived from published experimental data on equilibria between silicate liquids with either metallic iron or spinel at controlled oxygen partial pressure. The FeO activities in mafic and ultramafic magmas calculated with this equation were used to develop an oxygen barometer (geoxometer) for the association spinel + melt. Data derived with the application of the geoxometer confirm that meymechite magmas in the Siberian trap province had oxygen fugacities higher than in other magmatic systems. The origin of lower lithospheric domains with elevated redox potential can be explained by the intense diffusion of hydrogen from zones in which water-rich near-solidus melts from asthenospheric sources were emplaced into harzburgites, which had lost water and other incompatible elements in the course of earlier large-scale melting.     

简单体系水溶液包裹体pH和Eh的计算

流体包裹体pH和Eh参数的计算一直处于探索阶段。已经发表的计算公式,由于缺少高压(＞1bar)环境下化学组分反应平衡常数,常常利用常压(1大气压)下化学组分反应平衡常数代替而推导出的,对于大多数自然界捕获的包裹体,不可避免地产生较大计算误差。根据水溶液包裹体中离子反应热力学特征,结合前人推导的计算公式,我们分别建立简单体系水溶液包裹体pH和Eh计算公式。由于利用较高压(＞1bar)化学反应平衡常数,基本上解决不同条件下、特别在较高温度、压力下捕获的水溶液包裹体pH和Eh的计算难题。4种简单体系水溶液包裹体pH计算公式:① H₂O包裹体:pH=pK_w② CO₂-H₂O包裹体: ³－(m_CO2K_a,1+K_W)· －2mCO₂K_a,1K_a,2=0③ NaCl-H₂O包裹体: ²= ④ CO₂-H₂O-NaCl包裹体: ³+ ²－(m_CO2·K_a,1+K_w)· －2mCO₂·K_a,1·K_a,2－ =0计算数值精度分析表明:CO₂-H₂O和NaCl-H₂O包裹体的pH值按照公式计算,相同或接近于实际测定的天然酸雨、海水pH数值范围。CO₂-H₂O-NaCl包裹体与Crerar(1978)公式计算误差不超过10%。4种简单体系水溶液包裹体Eh的计算,引用Ryzhenko and Bryzgalin (1984)年推导的Eh公式。文中列举了3个实例,详细叙述不同类型包裹体捕获温度、压力下pH和Eh计算过程。自然界中水溶液包裹体成分十分复杂,本文涉及的只是自然界几种简单体系水溶液包裹体,给出的pH和Eh公式只对特定组分组合反应平衡条件有效,它不适合另外一种组分组合平衡条件下的关系,因此使用时务必注意平衡的组分组合条件。     

Thermodynamic constraints on the formation conditions of winonaites and silicate-bearing IAB irons

Silicate inclusions in IAB irons and related winonaite meteorites have textures, mineralogies and mineral chemistries that indicate a complex formation history of heating, followed by brecciation and metamorphism. Using olivine-orthopyroxene-chromite assemblages in five IAB iron silicate inclusions (Caddo County, Campo del Cielo, Copiapo, Lueders, and Udei Station) and one winonaite (Winona), we calculated closure temperatures and oxygen fugacities for these meteorites. Calculated olivine-chromite Fe-Mg exchange temperatures are compared to two-pyroxene temperatures. Olivine-chromite closure temperatures range from ∼590°C to ∼700°C, while two-pyroxene temperatures range from ∼900°C to ∼1200°C. Oxygen fugacities of these meteorites, determined for the first time in this study, range from 2.3 to 3.2 log units below the Fe-FeO buffer and define a line between the Fe-FeO and Cr-Cr₂O₃ buffers. Highly variable temperatures were experienced by these rocks on the hand sample, and sometimes even the thin section, scale consistent with the idea that the winonaite-IAB iron parent body experienced collisional fragmentation and reassembly after peak temperatures were reached. Although modest reduction likely occurred during cooling, the oxygen fugacities and mineral compositions recorded at peak metamorphic temperatures suggest that the chondritic precursor for this parent body was initially more reduced than ordinary chondrites.     

Multistage ore genesis in the New Zealand geosyncline a history of post-metamorphic lode emplacement

Epigenetic gold-quartz and scheelite-quartz lodes in Otago and other parts of the New Zealand geosyncline crosscut quartzofeldspathic and metavolcanic rocks of the pumpellyite-actinolite and greenschist facies. The lodes, which commonly strike north-west, are spatially associated with a 30 km wide belt of metavolcanic schists, with associated piemontite and sideritic schists, which parallels the axis of the geosyncline. Oxygen isotope and uncorrected fluid inclusion data for Glenorchy and Bendigo material give the range 230–350°C for lode formation, over 100°C lower than the metamorphic temperature of the country rock, and this indicates that substantial uplift and unloading had occurred prior to the hydrothermal emplacement of the lodes. A model is developed to account for the origin of the lode mineralization. A recent oxygen isotope study of the Glenorchy lodes suggested that the ore-bearing fluid was derived from rocks at depth over 150°C hotter than the lode formation temperature, and this is consistent with an origin by dehydration reactions at the greenschist to amphibolite transition. Hydraulic fracturing, induced by rapid uplift and unloading of the pile, allowed fluid migration to higher crustal levels where ore-deposition occurred. The spatial association of the lodes with the metavolcanic suite suggests that metals were derived by trace-leaching from the volcanic suite at the water source, or during migration, whilst tungsten may have been leached from associated manganiferous metasediments which commonly contain high anomolous concentrations of tungsten. Ore deposition occurred in response to lowering of temperature and pressure during fluid migration, and wall-rock interactions, particularly where lower oxygen fugacities were imposed by wall-rocks on the hydrothermal phase.     

广东凡口铅锌(银)矿床成矿流体来源研究

在已有研究成果的基础上 ,通过对矿物流体包裹体化学成分和氢氧同位素地球化学的研究 ,认为凡口矿区成矿期热液为多源混合流体 ,其来源包括建造水和岩浆水。这种混合流体的加热驱动与岩浆事件有关。     

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.