小秦岭地区花岗岩体中CO2—H2O包裹体的找矿意义

小秦岭地区与金矿成因有关的燕山期文峪花岗岩及其派生石英脉中发育了非常丰富的ＣＯ２－Ｈ２Ｏ包裹体,其流体为富含ＣＯ２的低盐度（＜１０％ＮａＣｌ）流体,这与含金石英脉内的包裹体类型及金矿成矿流体性质上十分相似。与金矿成因无关的华山岩体内包裹体类型则为水溶液包裹体,流体性质为贫ＣＯ２的低盐度流体。与金矿有关,但其周围矿化很差的娘娘山岩体内ＣＯ２－Ｈ２Ｏ包裹体数量很少。因此,ＣＯ２－Ｈ２Ｏ包裹体可以作为与金矿成因有关的花岗岩体关联程度的判别标志,而ＣＯ２－Ｈ２Ｏ包裹体的丰度可以作为金矿床品位和规模评价及成矿前景展望的依据     

CO2-H2O流体不混溶对Au溶解度的影响——以贵州省贞丰县水银洞金矿床为例

运用热力学原理和方法,研究了CO2-H2O流体不混溶作用对Au的溶解度的影响。结果表明,贵州水银洞金矿床的成矿流体是一种富含挥发分( fCO 2=70.79MPa)、酸性(pH=3.71)、还原性(fO 2=0.50×10-36MPa)、中温(267℃)、具有超压(180MPa)性质的含Au(a∑Au=3.744×10-8mol/L)流体。当超压流体的封闭层——炭质页岩因断裂作用而被破坏时,热液体系的压力发生骤降(28.50～35.30MPa),CO2-H2O流体发生不混溶作用,并有大量CO2溢出。CO2的流失可使成矿溶液的CO2逸度和O2逸度降低(fCO 2=0.80MPa、fO 2= 2.512×10-42MPa),酸碱度升高(pH=4.32),同时伴随温度的下降(224℃),成矿热液中Au溶解度的降低(a∑Au=3.790×10-9mol/L),从而快速沉淀下来成矿。     

Synthetic Fluid Inclusions in the Systems NaCl-H2O and NaCl-CO2-H2O: Dissolution Temperatures of Halite

Abstract. This study examined the effect of CO₂ on NaCl solubility in hydrothermal fluid, with the synthetic fluid inclusion technique. Fluid inclusions of 30–40 wt% NaCl and 5 mol % CO₂ were synthesized, and their halite dissolution temperatures, T_m(halite), were measured. The solubilities of NaCl in CO₂-bearing aqueous fluid were obtained at 160–320C under vapor-saturated pressures. The T_m(halite) value in aqueous fluid with 5 mol % CO₂ obtained in this study agrees with that of Schmidt et al. (1995), showing that 5 mol % CO₂ reduces the solubility of NaCl by about 1 wt%.
Calculation of magnetite solubility suggests that 5–10 mol % CO2 decreases magnetite solubility by 4.5–8.9 % relative to the magnetite solubility in CO2-free solution. Therefore, an increase of CO2 content in ore-forming solutions may cause deposition of iron minerals and produce ore deposits.     

赣南淘锡坑钨矿床云英岩中含CO2包裹体的发现及意义

淘锡坑矿床是赣南地区一大型黑钨矿矿床,为揭示成矿流体的早期演化特征,深入认识钨元素的富集机制,本文对淘锡坑钨矿床云英岩中流体和熔体包裹体进行了岩相学、激光拉曼光谱和显微测温研究。结果表明,云英岩中的流体包裹体可以划分为富液相两相水溶液包裹体、富气相含CO_2水溶液包裹体和纯气相包裹体三类,流体为中—高温、低盐度、低密度的NaCl-H_2O-CO_2-CH_4体系。熔体包裹体主要由钠长石、石英、少量流体相和气相组成,气相部分含有CH_4和微量CO_2。在岩浆热液演化早期阶段,流体氧化还原条件可能发生了改变,发生了CH_4到CO_2的转变,致使流体中CO_2含量增高。在流体演化过程中发生的以CO_2散逸为特征的流体不混溶作用可能是淘锡坑钨矿床形成的重要机制。CO_2对于钨元素的迁移和富集具有重要作用,CO_2的散逸是诱发黑钨矿沉淀富集的重要因素之一。     

Calculated phase equilibria for a morb composition in a P–T range, 450–650 °C and 18–28 kbar: the stability of eclogite

Lower temperature eclogite (with T = 600 °C) represents a significant part of the occurrences of eclogite in orogenic belts. ‘True’ eclogite, with, for example, garnet + omphacite >70%, is well represented in such an occurrence. Calculated phase equilibria in Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O (NCKFMASHTO), for just one rock composition – that of a representative mid‐ocean ridge basalt, morb – are used to see under what circumstances ‘true’ eclogite is predicted to occur. The variables considered are not only pressure (P) and temperature (T) but also water content and oxidation state. The latter two variables are known to exert a significant control on mineral assemblage but are difficult to establish retrospectively from the observed rocks themselves. It is found that whereas oxidation state does have a strong effect on mineral assemblage, the key control on developing ‘true’ eclogite is shown to be temperature and water content. If temperature is established to be <600 °C, water content has to be low (less or much less than that for H₂O saturation) in order for ‘true’ eclogite to form. Moreover, unless pressure is at the high end in the range considered, lawsonite eclogite and ‘true’ eclogite will tend to be mutually exclusive, with the former requiring high water content at the lower temperature where it occurs, but the latter requiring low water content.     

碳酸盐倒退溶解模式的化学热力学基础——与H_2S有关的溶解介质及其与CO_2的对比

以化学热力学中的吉布斯自由能增量为基础,计算了与H2S(g)/ H2S(aq) /HS-/ H+/S2-系统有关反应在不同温度下的平衡常数,同时根据方解石和白云石在酸性条件下的溶解过程,获得了这两种碳酸盐矿物溶解过程中地层中流体pH值与PCO2、地层压力和埋藏深度的关系。在此基础上,对比了从地表到深埋藏的温度和压力条件下,与CO2和H2S有关的酸性介质对流体\[H+\]贡献的差异性,以及对于碳酸盐溶解作用的差异性。计算结果表明:1）无论以CO2还是以H2S作为溶解介质,温度增加和（或）PCO2增加,都会造成方解石和白云石溶解所需要的\[H+\]增加,在深埋藏相对高温和高压条件下,高PCO2条件会使得碳酸盐矿物的溶解更加困难,如果\[H+\]受到缓冲,CO2的增加不仅不能造成碳酸盐矿物的溶解,反而会造成碳酸盐矿物的沉淀;2）无论在何种酸性介质中,碳酸盐矿物的倒退溶解模式在化学上都是成立的,低温的成岩环境,深部地层中高温流体的向上运移、构造抬升所造成的温度降低（-ΔT）都会提高H2S和（或）CO2流体（也包括其它酸性介质）对碳酸盐矿物溶解能力;3）在地表和近地表条件下（几百米深度范围内）,在同时存在CO2和H2S的环境中,CO2对应酸的电离提供的\[H+\]略多于H2S对应酸的电离,与CO2有关的酸性流体对碳酸盐矿物溶解相对重要,而在深埋藏条件下、尤其是深度大于4 000 m的深埋藏地层中,H2S对应酸的电离提供的\[H+\]显著大于CO2,其对碳酸盐矿物的溶解更为重要,在存在硫酸盐还原作用的深埋藏地层中,碳酸盐的深部溶解作用会更为发育,这可能是川东北地区深埋藏条件下次生孔隙发育的重要原因之一。     

Osumilite–melt interactions in ultrahigh temperature granulites: phase equilibria modelling and implications for the P–T–t evolution of the Eastern Ghats Province,India

The exposed residual crust in the Eastern Ghats Province records ultrahigh temperature (UHT) metamorphic conditions involving extensive crustal anatexis and melt loss. However, there is disagreement about the tectonic evolution of this late Mesoproterozoic–early Neoproterozoic orogen due to conflicting petrological, structural and geochronological interpretations. One of the petrological disputes in residual high Mg–Al granulites concerns the origin of fine‐grained mineral intergrowths comprising cordierite + K‐feldspar ± quartz ± biotite ± sillimanite ± plagioclase. These intergrowths wrap around porphyroblast phases and are interpreted to have formed by the breakdown of primary osumilite in the presence of melt trapped in the equilibration volume by the melt percolation threshold. The pressure (P)–temperature (T) evolution of four samples from three localities across the central Eastern Ghats Province is constrained using phase equilibria modelling in the chemical system Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–Fe₂O₃ (NCKFMASHTO). Results of the modelling are integrated with published geochronological results for these samples to show that the central Eastern Ghats Province followed a common P–T–t history. This history is characterized by peak UHT metamorphic conditions of 945–955 °C and 7.8–8.2 kbar followed by a slight increase in pressure and close‐to‐isobaric cooling to the conditions of the elevated solidus at 940–900 °C and 8.5–8.3 kbar. In common with other localities from the Eastern Ghats Province, the early development of cordierite before osumilite and the peak to immediate post‐peak retrograde reaction between osumilite and melt to produce the intergrowth features requires that the prograde evolution was one of contemporaneous increasing pressure with increasing temperature. This counter‐clockwise (CCW) evolution is evaluated for one sample using inverse phase equilibria modelling along a schematic P–T path of 150 °C kbar^?1 starting from the low P–T end of the prograde P–T path as constrained by the phase equilibria modelling. The inverse modelling is executed by step‐wise down temperature reintegration of sufficient melt into the residual bulk chemical composition at the P–T point of the 1 mol.% melt isopleth at each step, representing the melt remaining on grain boundaries after each prograde drainage event, to reach the melt connectivity transition (MCT) of 7 mol.%. The procedure is repeated until a plausible protolith composition is recovered. The result demonstrates that clastic sedimentary rocks that followed a CCW P–T evolution could have produced the observed mineral assemblages and microstructures preserved in the central Eastern Ghats Province. This study also highlights the role of melt during UHT metamorphism, particularly its importance to both chemical and physical processes along the prograde and retrograde segments of the P–T path. These processes include: (i) an increase in diffusive length scales during the late prograde to peak evolution, creating equilibration volumes larger than a standard thin section; (ii) the development of retrograde mineral assemblages, which is facilitated if some melt is retained post‐peak; (iii) the presence of melt as a weakening mechanism and the advection of heat by melt, allowing the crust to thicken; and (iv) the effect of melt loss, which makes the deep crust both denser and stronger, and reduces heat production at depth, limiting crustal thickening and facilitating the transition to close‐to‐isobaric cooling.     

Reactive flow of mixed CO2–H2O fluid and progress of calc-silicate reactions in contact metamorphic aureoles: insights from two-dimensional numerical modelling

Previous models of hydrodynamics in contact metamorphic aureoles assumed flow of aqueous fluids, whereas CO₂ and other species are also common fluid components in contact metamorphic aureoles. We investigated flow of mixed CO₂–H₂O fluid and kinetically controlled progress of calc‐silicate reactions using a two‐dimensional, finite‐element model constrained by the geological relations in the Notch Peak aureole, Utah. Results show that CO₂ strongly affects fluid‐flow patterns in contact aureoles. Infiltration of magmatic water into a homogeneous aureole containing CO₂–H₂O sedimentary fluid facilitates upward, thermally driven flow in the inner aureole and causes downward flow of the relatively dense CO₂‐poor fluid in the outer aureole. Metamorphic CO₂‐rich fluid tends to promote upward flow in the inner aureole and the progress of devolatilization reactions causes local fluid expulsion at reacting fronts. We also tracked the temporal evolution of P‐T‐X_CO2conditions of calc‐silicate reactions. The progress of low‐ to medium‐grade (phlogopite‐ to diopside‐forming) reactions is mainly driven by heat as the CO₂ concentration and fluid pressure and temperature increase simultaneously. In contrast, the progress of the high‐grade wollastonite‐forming reaction is mainly driven by infiltration of chemically out‐of‐equilibrium, CO₂‐poor fluid during late‐stage heating and early cooling of the inner aureole and thus it is significantly enhanced when magmatic water is involved. CO₂‐rich fluid dominates in the inner aureole during early heating, whereas CO₂‐poor fluid prevails at or after peak temperature is reached. Low‐grade metamorphic rocks are predicted to record the presence of CO₂‐rich fluid, and high‐grade rocks reflect the presence of CO₂‐poor fluid, consistent with geological observations in many calc‐silicate aureoles. The distribution of mineral assemblages predicted by our model matches those observed in the Notch Peak aureole.     

Blueschist‐facies metapelites from the Malpica–Tui Unit (NW Iberian Massif): phase equilibria modelling and H2O and Fe2O3 influence in high‐pressure assemblages

The Malpica–Tui Unit (Galicia, NW Spain) records eclogite‐ and blueschist‐facies metamorphism during the onset of the Variscan orogeny in Europe. Petrological analysis involving pseudosections calculated using thermocalc shows that the Upper Sheet of this unit, the Ceán Schists, recorded a three‐stage metamorphic evolution involving (i) Early subduction‐related medium‐pressure/low‐temperature metamorphism (M₁) constrained at ～350–380 °C, 12–14 kbar, which is only recorded in the basal part (lower metapelites, LM) of the Ceán Schists. (ii) Subduction‐related blueschist facies prograde metamorphism (M₂) going from ～19 kbar, 420 °C to 21 kbar, 460 °C in the LM, and from 16 kbar 430 °C to 21–22 kbar, 520 °C in the structurally upper metapelites (UM). (iii) Exhumation‐related metamorphism (M₃) is characterized by a decompression to 8–10 kbar, 470–490 °C in the LM. This decompression is also recorded in the UM, but it was not possible to estimate precise P–T conditions. The calculations indicate that (i) the prograde evolution in subduction zones may occur in fluid‐undersaturated conditions due to the crystallization of lawsonite, even in metapelitic rocks. This significantly influences phase equilibria and hence the P–T estimates. (ii) The proportion of ferric iron also has a strong influence on phase equilibria, even in metapelites. However, the analysed values of Fe₂O₃ may not reflect the oxidation state during the main metamorphic evolution and are probably easily modified by superficial alteration even in apparently fresh samples. The use of P–T–X(Fe₂O₃) pseudosections together with petrographic observations is then necessary to estimate the real oxidation state of the rocks and correctly evaluate the P–T conditions.     

巴西桑托斯盆地高含CO2油气藏类型、特征及成因模式

桑托斯盆地盐下油气藏中CO₂分布广泛,局部摩尔分数极高,给勘探、开发都带来了巨大挑战。通过对典型油气藏解剖分析,并利用流体取样、闪蒸实验测试分析等资料,将盆内油气藏分为3类：类型Ⅰ,含CO₂溶解气的高气油比常规油藏;类型Ⅱ,CO₂气顶+油环型油气藏;类型Ⅲ,（含溶解烃）CO₂气藏。其中类型Ⅰ油藏和类型ⅢCO₂气藏中流体性质均匀、稳定,油-水界面、气-水界面清晰;类型Ⅱ气顶+油环型油气藏流体成分和性质不均匀、不稳定,流体界面复杂。物理热模拟实验表明盆内3种类型油气藏是地层条件下,超临界状态CO₂和烃类有限互溶,动态成藏过程不同阶段的产物。动态成藏过程中,CO₂对烃类进行抽提、萃取,烃类（原油）对CO₂进行溶解,两者相互作用存在一个动态平衡（范围）。烃类和CO₂相对量大小决定了最终的油气藏类型,温-压条件变化和油气藏开发可改变油气藏平衡状态,造成流体相态变化和3类油气藏间的相互转化。     

云南大坪韧性剪切带型金矿富CO2流体包裹体及其成矿意义

大坪金矿成矿可分为三个成矿阶段：早期成矿阶段（白钨矿石英脉）、主成矿阶段（团块状多金属硫化物含金石英脉）和晚成矿阶段（碳酸盐石英脉）。本文利用显微测温和拉曼光谱分析了大坪矿脉的流体包裹体特征,结果表明：流体包裹体基本由富液相CO2包裹体和不同CO2/H2O比例的CO2-H2O型包裹体组成,早阶段白钨矿石英脉中同时富含富气相CO2包裹体,主成矿阶段团块状多金属硫化物金矿石中富液相CO2包裹体占明显优势,只有晚成矿阶段碳酸盐石英脉中含有居次要地位的H2O溶液包裹体。流体包裹体中气相组成基本为纯CO2,早阶段者还含少量N2。早阶段CO2-H2O型包裹体的盐度为6.37%-14.64%NaCl,峰值9%-10.5%NaCl,均一温度为299.4-423.7℃,峰值320-380℃,CO2包裹体密度为0.352-0.798g/cm^3,多数在0.64-0.71g/cm^3;主成矿阶段的CO2-H2O型包裹体的盐度在3.70%-14.64%NaCl之间,峰值7.2%-9.0%NaCl,均一温度279.0-406.5℃之间,峰值320-360℃,CO2包裹体密度为0.591-0.843g/cm^3,多数大于0.8g/cm^3;晚成矿阶段CO2-H2O型包裹体的盐度为4.80%-6.54%NaCl,均一温度为287.6-337.1℃。计算表明早阶段成矿压力约为190-440MPa,主阶段成矿压力约为133.5-340.0MPa,相当的成矿深度为5.1-12.9km。这些特征揭示了该矿成矿流体为近临界的高CO2（CO2≥H2O）的中低盐度的CO2-H2O-NaCl体系流体,在成矿过程中基本不存在流体混合,但发生了明显的沸腾和相分离作用。该矿是剪切带控制下的中深中温热液金矿,成矿作用主要是减压沸腾环境下的快速沉淀。结合其它证据,作者认为该矿的成矿流体主体为深源的壳幔混合流体,而不是地壳浅部的大气降水、岩浆水或其混合流体。金在高CO2的成矿流体中可能主要以硫氢络合物形式迁移,矿质沉淀主要与压力速降条件下发生流体的相分离作用相关。     

湘西花垣地区铅锌矿床C、H、O同位素特征及其对成矿流体来源的指示

湘西花垣地区铅锌矿床是铅锌矿资源储量超过千万吨的世界级超大型矿床之一。对该矿床主矿化期的方解石和闪锌矿进行了系统的C、H、O同位素研究。分析结果显示,花垣地区铅锌矿床主成矿期方解石样品的δ~(13)C_(PDB)值范围为-2.71‰~1.21‰,δ~(18)OSMOW值范围为16.09‰~22.48‰,团结、李梅、土地坪、蜂塘和大石沟各铅锌矿床中主成矿期方解石的13C、18O同位素依次表现出逐渐降低的特征,在δ~(18)O_(SMOW)-δ~(13)C_(PDB)图上主要介于原生碳酸盐岩与海相碳酸盐岩之间,该地区铅锌矿床成矿流体中的碳主要来源于海相碳酸盐岩的溶解作用。花垣矿区围岩的δ~(13)C_(PDB)值范围为0.15‰~1.17‰,δ~(18)O_(SMOW)值范围为19.79‰~23.89‰,指示沉积成因海相碳酸盐岩的特征。方解石和闪锌矿样品中流体的δD_(SMOW)变化于-91.1‰~-15‰之间,δ18Ofluid变化范围为-4.1‰~9.25‰,在矿区范围内流体的迁移方向是由北向南,δ~(18)O_(fluid)-δD_(SMOW)图显示,矿床成矿流体的主要来源是建造水和大气降水。成矿流体与围岩间的水-岩反应是导致湘西花垣地区铅锌矿床中方解石和闪锌矿矿物发生沉淀的主要机制。     

Mineralogy,Fluid Inclusion,and Hydrogen and Oxygen Isotope Studies of the Intrusion‐Related Yangla Cu Deposit in the Sanjiang Region,SW China: Implications for Metallogenesis and Deposit Type

The Yangla deposit is an intrusion‐related Cu deposit in the Jinshajiang tectonic belt (eastern Sanjiang region, SW China). Despite extensive studies that have been conducted on this deposit, the relationship between the granitic magma and Cu mineralization is still unclear, and hence, the genesis is debated. To answer this question, we conducted an integrated study of mineralogy, fluid inclusions (FIs), and hydrogen and oxygen (H‐O) isotopes. Three mineralization stages were identified based on the ore textures, alteration zonation, and crosscutting relationships: (i) pre‐ore prograde skarn (stage I), with the garnet and pyroxene dominated by andradite and diopside, respectively; (ii) syn‐ore retrograde alteration (stage II), which is subdivided into the early syn‐ore stage (stage IIa) marked by retrograde hydrated mineral assemblages and significant Fe‐Cu‐Mo‐Pb‐Zn sulfide mineralization, and the late syn‐ore stage (stage IIb) featured by quartz‐calcite veins; and (iii) late supergene mineralization (stage III), which is characterized by secondary azurite and malachite. These results of mineralogy, FIs, and H‐O isotopes indicate that: (i) Cu mineralization has a close temporal, spatial, and genetic relationship with skarn alteration; (ii) the ore fluids were magmatic dominated with late‐stage meteoric water incursion; and (iii) Type‐S (halite‐bearing) and Type‐V (vapor‐rich) FIs coexisted in garnet and clinopyroxene of stage I, indicating that fluid boiling might have occurred during this stage. From stage I to stage IIa, the FI type transformed from Type‐S + Type‐V + Type‐L (liquid‐rich) to Type‐V + Type‐L with the conduct of mineralization and was accompanied by the disappearance of Type‐S, and homogenization temperature and salinity also tended to decrease dramatically, which may be caused by the deposition of skarn minerals. At stage IIa, boiling of the ore fluids still continued due to the change from lithostatic to hydrostatic pressure, which triggered the precipitation of abundant quartz‐Cu‐Mo‐Fe sulfides. Furthermore, fluid mixing between a high‐temperature magmatic fluid and a low‐temperature meteoric water might cause a considerable drop in temperature and the deposition of Cu‐bearing quartz/calcite veins during stage IIb. Hence, we consider the Yangla deposit to be of a skarn type, genetically related to the Mesozoic magmatism in the Sanjiang region.     

白云凹陷第三系储层中铁白云石的成因机理及与CO2活动的关系

白云凹陷第三系储层中发育大量的铁白云石,受研究区热流背景的影响,铁白云石主要见于高地温梯度地区埋深1000～3000m、地层温度60～130℃的浅—中部地层中及CO_2热流体活动区域。铁白云石的δ~(13)C值(-2.83‰～-1.83‰)具有无机成因的特征,与研究区气藏中幔源岩浆成因CO_2的δ~(13)C值较为一致,铁白云石的δ~(18)O值(-9.45‰～-5.37‰)和~(87)Sr/~(86)Sr值(0.7101～0.7161)也反映了其沉淀受到深部热流体活动的影响。以两口典型CO_2气井为例,储层中流体包裹体均一温度及蒙脱石向伊利石的演化特征证明储层经历了热流体侵入;CO_2热流体活动区域不仅是铁白云石集中分布地带,并出现片钠铝石+铁白云石+菱铁矿等示踪CO_2运移、聚集的自生矿物组合。地层中铁白云石、高岭石含量与气藏中CO_2的含量呈正相关关系,绿泥石含量与CO_2、铁白云石含量呈反消长关系。高地温梯度地区丰富的CO_2热流体活动是该地区储层中铁白云石沉淀与含量高的重要原因,无机岩浆成因CO_2是铁白云石沉淀的主要碳源,CO_2热流体充注造成绿泥石等黏土矿物异常转化,为铁白云石沉淀提供了所需的Fe~(2+)、Mg~(2+)离子。     

Calculated mineral equilibria for eclogites in CaO–Na2O–FeO–MgO–Al2O3–SiO2–H2O: application to the Pouébo Terrane, Pam Peninsula, New Caledonia

The high- P , medium- T  Pouébo terrane of the Pam Peninsula, northern New Caledonia includes barroisite- and glaucophane-bearing eclogite and variably rehydrated equivalents. The metamorphic evolution of the Pouébo terrane is inferred from calculated P–T  and P–T  – X H2O pseudosections for bulk compositions appropriate to these rocks in the model system CaO–Na₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O. The eclogites experienced a clockwise P–T  path that reached P ≈19  kbar and T  ≈600  °C. The eclogitic mineral assemblages are preserved because reaction consequent upon decompression consumed the rocks' fluid. Extensive reaction occurred only in rocks with fluid influx during decompression of the Pouébo terrane.     

CO2-rich fluid inclusions in the Whitestone Anorthosite: implications for the retrograde history of the Parry Sound Shear Zone, Grenville Province, Canada

The Whitestone Anorthosite (WSA), located in southern Ontario, underwent granulite facies metamorphism during the Grenville orogeny at 1.16 Ga. During the waning stages of metamorphism fluids infiltrated the outer portions of the anorthosite and promoted the formation of an envelope comprised of upper amphibolite facies mineral assemblages. Also, this envelope corresponds to portions of the anorthosite that underwent deformation related to movement along a high-grade ductile shear zone. Samples from this portion of the anorthosite (the margin) contain CO₂-rich inclusions in plagioclase porphyroclasts (relict igneous phenocrysts), matrix plagioclase and garnet. These inclusions have features which normally are interpreted as indicating that they are texturally primary, but they have relatively low CO₂ densities (0.61–0.95 g cm^-3). Plagioclase from the anorthosite interior contains texturally secondary inclusions with relatively high CO₂ densities (generally from 0.99 to 1.10 g cm^-3). The high CO₂ densities suggest that the inclusions in the plagioclase of the anorthosite core formed prior to inclusions in porphyroclast minerals of the outer portions of the anorthosite, an interpretation that is apparently inconsistent with inclusion textures. This apparent paradox indicates that most fluid inclusions from the anorthosite margin were formed during, or were modified by, the dynamic recrystallization that affected this portion of the WSA. In either case, late formation or modification, the texturally primary fluid inclusions do not contain pristine samples of the peak metamorphic fluid. Furthermore, because shear-related deformation is apparently associated with entrapment of the lowest fluid densities, some strain localization persisted to relatively low temperatures (e.g. less than approximately 500° C). These results constrain a part of the retrograde P–T path for this portion of the Grenville Orogen to temperatures of approximately 400–500° C at pressures of approximately 1–2 kbar.     

Melting of albite and dehydration of brucite in H2O–NaCl fluids to 9 kbars and 700–900°C: implications for partial melting and water activities during high pressure metamorphism

 The melting reaction: albite_(solid)+ H₂O_(fluid) =albite-H₂O_(melt) has been determined in the presence of H₂O–NaCl fluids at 5 and 9.2 kbar, and results compared with those obtained in presence of H₂O–CO₂ fluids. To a good approximation, albite melts congruently at 9 kbar, indicating that the melting temperature at constant pressure is principally determined by water activity. At 5 kbar, the temperature (T)- mole fraction (X _(H2O) ) melting relations in the two systems are almost coincident. By contrast, H₂O–NaCl mixing at 9 kbar is quite non-ideal; albite melts ∼70 ^°C higher in H₂O–NaCl brines than in H₂O–CO₂ fluids for X _(H2O) =0.8 and ∼100 ^°C higher for X _(H2O) =0.5. The melting temperature of albite in H₂O–NaCl fluids of X _(H2O)=0.8 is ∼100 ^°C higher than in pure water. The P–T curves for albite melting at constant H₂O–NaCl show a temperature minimum at about 5 kbar. Water activities in H₂O–NaCl fluids calculated from these results, from new experimental data on the dehydration of brucite in presence of H₂O–NaCl fluid at 9 kbar, and from previously published experimental data, indicate a large decrease with increasing fluid pressure at pressures up to 10 kbar. Aqueous brines with dissolved chloride salt contents comparable to those of real crustal fluids provide a mechanism for reducing water activities, buffering and limiting crustal melting, and generating anhydrous mineral assemblages during deep crustal metamorphism in the granulite facies and in subduction-related metamorphism. Low water activity in high pressure-temperature metamorphic mineral assemblages is not necessarily a criterion of fluid absence or melting, but may be due to the presence of low a _(H2O) brines. Received: 17 March 1995/Accepted: 9 April 1996     

Dawsonite fixation of mantle CO2 in the cretaceous Songliao Basin,Northeast China: a natural analogue for CO2 mineral trapping in oilfields

Abundant crude oil and CO₂ gas coexist in the fourth member of the Upper Cretaceous Quantou reservoir in the Huazijing Step of the southern Songliao Basin, China. Here, we present results of a petrographic characterization of this reservoir based on polarizing microscope, X-ray diffraction, fluid inclusion, and carbon–oxygen isotopic data. These data were used to identify whether CO₂ might be trapped in minerals after the termination of a CO₂-enhanced oil recovery (EOR) project, and to determine what effects might the presence of CO₂ have on the properties of crude oil in the reservoir. The crude oil reservoir in the study area, which coexists with mantle-derived CO₂, is hosted by dawsonite-bearing lithic arkoses and feldspathic litharenites. These sediments are characterized by a paragenetic sequence of clay, quartz overgrowth, first-generation calcite, dawsonite, second-generation calcite, and ankerite. The dawsonite analysed during this study exhibits δ¹³ C (Peedee Belemnite, PDB) values of ?4.97‰ to 0.67‰, which is indicative for the formation of magmatic–mantle CO₂. The paragenesis and compositions of fluid inclusions in the dawsonite-bearing sandstones record a sequence of two separate filling events, the first involving crude oil and the second involving magmatic–mantle CO₂. The presence of prolate primary hydrocarbon inclusions within the dawsonite indicates that these minerals precipitated from oil-bearing pore fluids at temperatures of 94–97°C, in turn suggesting that CO₂ could be stored as carbonate minerals after the termination of a CO₂-EOR project. In addition, the crude oil in the basin would become less dense after deposition of bitumen by deasphalting the injection of CO₂ gas into the oil pool.     

Nature and role of CO2 in some hot and cold HCO3/Na/CO2-rich Portuguese mineral waters: a review and reinterpretation

 At the northern part of the Portuguese mainland, the upflow zone of several hot and cold HCO₃/Na/CO₂-rich mineral waters is mainly associated with important NNE–SSW faults. Several geochemical studies have been carried out on thermal and non-thermal hydromineral manifestations that occur along or near these long tectonic alignments. The slight chemical differences that exist between these meteoric hot and cold HCO₃/Na/CO₂-rich mineral waters seem to be mainly caused by CO₂. δ¹³C_(TIDC) values observed in these groundwaters range between –6.00 and –1.00‰ versus V-PDB (V denotes Vienna, the site of the International Atomic Energy Agency; PDB originates from the CaCO₃ of the rostrum of a Cretaceous belemnite, Belemnitella americana, collected in the Peedee formation of South Carolina, USA) indicating a deep-seated (mantle) origin for most of the CO₂. Nevertheless, in the case of the heavier δ¹³C_(TIDC) values, the contribution of metamorphic CO₂ or the dissolution of carbonate rock levels at depth cannot be excluded. Concerning the hot waters, the lack of a positive ¹⁸O-shift should be attributed to water-rock interaction in a low temperature environment, rather than to the isotopic influence of CO₂ on the δ¹⁸O-value of the waters. Received: 9 August 1999 · Accepted: 8 March 2000