Review of the systematics of CO2–H2O fluid inclusions

Aqueous solutions that contain volatile (gas) components are one of the most important types of fluid in the Earth's crust. The record that such fluids have left in the form of fluid inclusions in minerals provides a wealth of insight into the geochemical and petrologic processes in which the fluids participated. This article reviews the systematics of CO₂–H₂O fluid inclusions as a starting point for interpreting the chemically more complex systems. The phase relations of the binary are described with respect to a qualitative P–T–X model, and isoplethic–isochoric paths through this model are used to explain the equilibrium and non-equilibrium behaviour of fluid inclusions during microthermometric heating and cooling. The P–T–X framework is then used to discuss the various modes of fluid inclusion entrapment, and how the resulting assemblage textures can be used to interpret the P–T conditions, phase states, and evolution paths of the parent solutions. Finally, quantitative methods are reviewed by which bulk molar volume and composition of CO₂–H₂O fluid inclusions can be determined from microthermometric observations of phase transitions.     

Genetic significance of fluid inclusions in the CSA Cu–Pb–Zn deposit, Cobar, Australia

CSA mine exploits a ‘Cobar-type’ Cu–Pb–Zn±Au±Ag deposit within a cleaved and metamorphosed portion of the Cobar Supergroup, central New South Wales. The deposit comprises systems of ‘lenses’ that encompass veins, disseminations and semi-massive to massive Cu–Pb–Zn ores. The systems and contained lenses truncate bedding, are approximately coplanar with regional cleavage and similarly oriented shear zones and plunge parallel to the elongation lineation. Systems have extreme vertical continuity (>1000 m), short strike length (400 m) and narrow width (100 m), exhibit vertical and lateral ore-type variation and have alteration haloes. Models of ore formation include classical hydrothermalism, structurally controlled remobilisation and polymodal concepts; syntectonic emplacement now holds sway.Fluid inclusions were examined from quartz±sulphide veins adjacent to now-extracted ore, from coexisting quartz–sulphide within ore, and from vughs in barren quartz veins. Lack of early primary inclusions precluded direct determination of fluids associated with D₂–D₃ ore and vein emplacement. Similarly, decrepitation (by near-isobaric heating) of the two oldest secondary populations precluded direct determination of fluid phases immediately following D₂–D₃ ore and vein emplacement. Post-decrepitation outflow (late D₃ to early post-D₃) is recorded by monophase CH₄ inclusions. Entrained outflow of deeply circulated meteoric fluid modified the CH₄ system; modification is recorded by H₂O+CH₄ and H₂O+(trace CH₄) secondary populations and by an H₂O+(trace CH₄) primary population. The contractional tectonics (D₂–D₃) of ore emplacement was superseded by relaxational tectonics (D_4P) that facilitated meteoric water penetration and return flow.Under D₂ prograde metamorphism, entrapment temperatures (Tt) and pressures (Pt) for pre-decrepitation secondary inclusions are estimated as Tt300–330 °C and Pt1.5–2 kbar≈Plith (the lithostatic pressure). Decrepitation accompanied peak metamorphism (T350–380 °C) in mid- to late-D₃, while in late-D₃ to early post-D₃, essentially monophase CH₄ secondary inclusions were entrapped at Tt350 °C and Pt=1.5–2 kbar≈Plith. Subsequently, abundant CH₄ and entrained meteoric water were entrapped as H₂O+CH₄ secondaries under slowly decreasing temperature (Tt330–350 °C) and constant pressure (Pt1.5–2 kbar). Finally, with increasingly dominant meteoric outflow, H₂O+(trace CH₄) populations record decreasing temperatures (Tt>300 to <350 down to 275–300 °C) at pressures of Phydrostatic<Pt (1 kbar) <Plith (1.5 kbar).The populations of inclusions provide insight into fluid types, flow regimes and P–T conditions during parts of the deposit's evolution. They indirectly support the role of basin-derived CH₄ fluids in ore formation, but provide no insight into a basement-sourced ore-forming fluid. They fully support post-ore involvement of meteoric water. The poorly constrained entrapment history is believed to span 10 Ma from 395 to 385 Ma.     

Fluid unmixing/immiscibility as an ore-forming process in the giant REE–Nb–Fe deposit, Inner Mongolian, China: Evidence from fluid inclusions

The giant Bayan Obo REE–Nb–Fe deposit consists of replacement bodies hosted in dolomite marble made up of magnetite, REE fluorocarbonates, fluorite, aegirine, amphibole, calcite and barite. Two or three phase CO₂-rich, three phase hypersaline liquid–vapor–solid, and two phase liquid-rich inclusions have been recognized in mineralized fluorite and quartz samples. Microthermometry measurements indicate that the carbonic phase in CO₂-rich inclusions is nearly pure CO₂. Fluids involving in REE–Nb–Fe mineralization at Bayan Obo might be mainly of H₂O–CO₂–NaCl–(F–REE) system. Coexistences of brine inclusions and CO₂-rich inclusions with similar homogenization temperatures give evidence that immiscibility happened during REE mineralization. An unmixing of an original H₂O–CO₂–NaCl fluid probably derived from carbonatitic magma. The presence of REE-carbonates as an abundant solid in fluid inclusions shows that the original ore-forming fluids are very rich in REE, and therefore, have the potential to produce economic REE ores at Bayan Obo.     

Experimental identification of CO2–water–rock interactions caused by sequestration of CO2 in Westphalian and Buntsandstein sandstones of the Campine Basin (NE-Belgium)

Geological sequestration of CO₂ is one of the options studied to reduce greenhouse gas emissions. Although the feasibility of this concept is proven, apart from literature data on modelling still little is known about the CO₂–water–rock interactions induced by CO₂-injection.To evaluate the effect of CO₂–water–rock interactions on three sandstone aquifers in NE-Belgium an experimental setup was built. Eighteen experiments were performed in which sandstones were exposed to supercritical CO₂. CO₂–water–rock interactions were deduced from the evolution of aqueous concentrations of 25 species and a thorough characterisation of the sandstones before and after treatment. The results show that dissolution of ankerite/dolomite and Al-silicates could enhance porosity/permeability. The observed precipitation of end-member carbonates could increase storage capacity if it exceeds carbonate dissolution. Precipitation of the latter and of K-rich clays as observed, however, can hamper the injection.     

The influence of Cr on the garnet–spinel transition in the Earth''s mantle: experiments in the system MgO–Cr2O3–SiO2 and thermodynamic modelling

The position of the transition from spinel peridotite to garnet peridotite in a simplified chemical composition has been determined experimentally at high pressures and high temperatures. The univariant reaction MgCr₂O₄+2Mg₂Si₂O₆=Mg₃Cr₂Si₃O₁₂+Mg₂SiO₄, has a negative slope in P–T space between 1200 °C and 1600 °C. The experimental results, combined with assessed thermodynamic data for MgCr₂O₄, MgSiO₃ and Mg₂SiO₄ give the entropy and enthalpy of formation of knorringite garnet (Mg₃Cr₂Si₃O₁₂). Thermodynamic calculations in simplified chemical compositions indicate that Cr shifts the garnet-in reaction to much higher pressures than previously anticipated. Moreover, in Cr-bearing systems a pressure–temperature field exists where garnet and spinel coexist. The width of this divariant field strongly depends on the Cr/(Cr+Al) of the system.     

Gas–water–rock interactions in sedimentary basins: CO2 sequestration in the Frio Formation, Texas, USA

To investigate the potential for the geologic storage of CO₂ in saline sedimentary aquifers, 1600 ton of CO₂ were injected at 1500 m depth into a 24-m sandstone section of the Frio Formation — a regional reservoir in the US Gulf Coast. Fluid samples obtained from the injection and observation wells before, during and after CO₂ injection show a Na–Ca–Cl type brine with 93,000 mg/L TDS and near saturation of CH₄ at reservoir conditions. As injected CO₂ gas reached the observation well, results showed sharp drops in pH (6.5 to 5.7), pronounced increases in alkalinity (100 to 3000 mg/L as HCO₃) and Fe (30 to 1100 mg/L), and significant shifts in the isotopic compositions of H₂O and DIC. Geochemical modeling indicates that brine pH would have dropped lower, but for buffering by dissolution of calcite and Fe oxyhydroxides. Post-injection results show the brine gradually returning to its pre-injection composition.     

Oxygen isotope speedometry in granulite facies garnet recording fluid/melt–rock interaction (Sør Rondane Mountains,East Antarctica)

In situ analysis of a garnet porphyroblast from a granulite facies gneiss from Sør Rondane Mountains, East Antarctica, reveals discontinuous step‐wise zoning in phosphorus and large δ¹⁸O variations from the phosphorus‐rich core to the phosphorus‐poor rim. The gradually decreasing profile of oxygen isotope from the core (δ¹⁸O = ~15‰) to the rim (δ¹⁸O = ~11‰) suggests that the ¹⁸O/¹⁶O zoning was originally step‐wise, and modified by diffusion after the garnet rim formation at ~800°C and 0.8 GPa. Fitting of the ¹⁸O/¹⁶O data to the diffusion equation constrains a duration of the high‐T event (~800°C) to c. 0.5–40 Ma after the garnet rim formation. The low δ¹⁸O value of the garnet rim, together with the previously reported low δ¹⁸O values in metacarbonates, indicates regional infiltration, probably along a detachment fault, of low δ¹⁸O fluid/melt possibly derived from meta‐mafic to ultramafic rocks.     

造山型金矿中富CO_(2)高内压流体包裹体完全均一温度的有效测定实验研究——以东天山玉峰金矿床为例SCIEI北大核心CSCD

形成于中-深成条件下的造山型金矿的成矿流体属于H_(2)O-NaCl-CO_(2)体系,金矿化阶段的石英中发育大量的富CO_(2)流体包裹体。长期以来,用常规冷热台对其进行显微测温热力学研究时,较高的内压力会造成绝大多数CO_(2)充填度>0.4的包裹体在尚未达到完全均一状态前就发生爆裂或泄露,导致所测的完全均一温度值明显偏离真实值,甚至无法测得完全均一温度,这制约了对造山型金矿床成矿条件的认知。针对该问题,本文以东天山玉峰金矿床富金矿石中的H_(2)O-NaCl包裹体(A型)和H_(2)O-NaCl-CO_(2)包裹体(AC型)为研究对象,介绍了利用最新型热液金刚石压腔(HDAC-VT型号)测试富CO_(2)高内压的AC型包裹体完全均一温度的实验流程与结果,并将实验数据与Linkam THMSG600冷热台测得的A型、AC型包裹体的完全均一温度进行了对比分析。实验结果表明,热液金刚石压腔能够有效阻止富CO_(2)流体包裹体在升温过程中发生爆裂、泄露等非弹性体积改变现象的发生,从而获得有效的完全均一温度。同时,本文还提出了一个新的压力-温度拟合线两线相交法,对热液金刚石压腔所测富CO_(2)流体包裹体的完全均一温度数据进行校正,以最大程度上减少外压力造成的影响,获得更为接近真实成矿流体的完全均一温度。基于此,获得玉峰金矿床的成矿温度和成矿压力分别为312~343℃和181~268 MPa。本文的实验研究工作显示了热液金刚石压腔在中-深成造山型金矿富CO_(2)成矿流体的研究领域具有重要应用前景。