Quantitative analysis of COH fluids synthesized at HP–HT conditions: an optimized methodology to measure volatiles in experimental capsules

The quantitative assessment of COH fluids is crucial in modeling geological processes. The composition of fluids, and in particular their H₂O/CO₂ ratio, can influence the melting temperatures, the location of hydration or carbonation reactions, and the solute transport capability in several rock systems. In the scientific literature, COH fluids speciation has been generally assumed on the basis of thermodynamic calculations using equations of state of simple H₂O–nonpolar gas systems (e.g., H₂O–CO₂–CH₄). Only few authors dealt with the experimental determination of high‐pressure COH fluid species at different conditions, using diverse experimental and analytical approaches (e.g., piston cylinder + capsule piercing + gas chromatography/mass spectrometry; cold seal + silica glass capsules + Raman). In this contribution, we present a new methodology for the synthesis and the analysis of COH fluids in experimental capsules, which allows the quantitative determination of volatiles in the fluid by means of a capsule‐piercing device connected to a quadrupole mass spectrometer. COH fluids are synthesized starting from oxalic acid dihydrate at P = amb and T = 250°C in single capsules heated in a furnace, and at P = 1 GPa and T = 800°C using a piston‐cylinder apparatus and the double‐capsule technique to control the redox conditions employing the rhenium–rhenium oxide oxygen buffer. A quantitative analysis of H₂O, CO₂, CH₄, CO, H₂, O₂, and N₂ along with associated statistical errors is obtained by linear regression of the m/z data of the sample and of standard gas mixtures of known composition. The estimated uncertainties are typically <1% for H₂O and CO₂, and <5% for CO. Our results suggest that the COH fluid speciation is preserved during and after quench, as the experimental data closely mimic the thermodynamic model both in terms of bulk composition and fluid speciation.     

Organic–inorganic rock–fluid interactions in stylolitic micro‐environments of carbonate rocks: a FIB‐TEM study combined with a hydrogeochemical modelling approach

Stylolites and the interfaces to the host limestone have been investigated by means of a multidisciplinary analytical approach (thin section microscopy, FIB‐TEM, organic geochemistry and petrography). Carbonate dissolution assuming different boundary conditions was simulated by applying a generic hydrogeochemical modelling approach. It is the conceptual approach to characterize and quantify traceable organic–inorganic interactions in stylolites dependent on organic matter type and its thermal maturity, and to follow stylolite formation in carbonates as result of organic matter reactivity rather than pressure solution as a main control. The investigated stylolite samples are of Upper Permian (Lopingian, Zechstein), Middle Triassic (Muschelkalk) and Late Cretaceous (Maastrichtian) age and always contain marine organic matter. The thermal maturity of the organic matter ranges from the pre‐oil generation zone (0.4–0.5% R_r) to the stage of dry gas generation (>1.3% R_r). The results of the generic hydrogeochemical modelling indicate a sharp increase of calcite dissolution and the beginning of stylolite formation at approximately 40°C, which is equivalent to a depth of less than 800 m under hydrostatic conditions considering a geothermal gradient of 30°C and a surface mean temperature of 20°C. This temperature corresponds to the pre‐oil window when kerogens release an aqueous fluid enriched in carbon dioxide and organic acids. This aqueous fluid may change the existing pore water pH or alkalinity and causes dissolution of carbonate, feldspar and quartz, and clay mineral precipitation along the stylolite. Dissolution of limestone and dolostone leads to reprecipitation of calcite or dolomite opposite of the dissolution side, which indicates only localized mass redistribution. All these integrated hydrogeochemical processes are coupled to the generation of water during organic matter maturation. In all of the calculated hydrogeochemical scenarios, H₂O is a reaction product and its formation supports the suggested hypothesis.     

FT-IR measurements of petroleum fluid inclusions: methane, n-alkanes and carbon dioxide quantitative analysis

A recent advancement in petroleum geochemistry is to model fossil oil composition using microthermometric and volumetric data acquired from individual fluid inclusion analysis. Fourier transform infrared (FT‐IR) microspectroscopy can record compositional information related to gas (CH₄ and CO₂) and alkane contents of petroleum inclusions. In this study, a quantitative procedure for FT‐IR microspectrometry has been developed to obtain, from individual fluid inclusions, mol percentage concentrations of methane, alkanes and carbon dioxide as constraints to thermodynamic modelling. A petroleum inclusion in a sample from the Québec City Promontory nappe area was used as standard to record a reference spectrum of methane. The analytical procedure is based on the measurement of CH₄/alkane and CH₄/CO₂ band area ratios. CH₄/alkane infrared band area ratio is obtained after spectral subtraction of the reference methane spectrum. This area ratio, affected by absolute absorption intensities of methane, methyl and methylene, provides a molar CH₄/alkane ratio. Methyl/methylene ratio (CH₂/CH₃) ratio is obtained following procedures established in previous work. CO₂/CH₄ concentration ratio is estimated from relative absolute absorption intensities. Application to natural inclusions from different environments shows good correlation between FT‐IR quantification and PIT (petroleum inclusion thermodynamic) modelling.     

Low‐temperature dunite hydration: evaluating CH4 and H2 production from H2O and CO2

Abiotic methane (CH₄) and hydrogen (H₂) produced after hydration of mafic/ultramafic rocks represent energy sources for microbes that may thrive in the deep subsurface regions of Earth and possibly on other planets. While H₂ is a direct product of serpentinization, CH₄ can form via Fischer–Tropsch Type (FTT) reactions (carbon reduction) that, due to potential H₂ migration, can be spatially and temporally detached from serpentinization. We tested an alternative process hypothesized by some scholars, in which CO₂ can be reduced through dunite hydration without initially added H₂, implying that CH₄ can form in the same serpentinized fluid–rock system. The experiment used natural dunite sand (Forsterite 92), CO₂ with δ¹³C ~ ?25‰ (VPDB), and a 1 mm dissolved SiO₂ solution mixed in 30 glass bottles (118 mL) stored for up to 8 months at low temperature (50°C) to simulate land‐based serpentinization systems. In addition, 30 control bottles without olivine were used as blanks. Trivial amounts of CH₄ (orders of 0.2–0.9 ppmv) were detected in both samples and blanks, likely representing analytical noise; essentially, no significant amount of CH₄ formed under the experimental conditions used in this work. Low amounts of H₂ (~2.55 ± 1.39 ppmv) were generated, with production yields that were one order of magnitude lower than in previously published experiments. Moderate concentrations of SiO₂ appeared to hinder low‐temperature H₂ production. Our experiment confirms that the low‐temperature reduction of CO₂ into CH₄ through direct olivine hydration, without initial H₂, is sluggish and not straightforward, which is consistent with previous studies. The presence of substantial amounts of H₂, as well as suitable metal catalysts, appears to be essential in the low‐temperature production of abiotic CH₄, as observed in published FTT experiments.     

Decreasing CO2 partial pressure triggered Mg–Fe–Ca carbonate formation in ancient Martian crust preserved in the ALH84001 Meteorite

We retrace hydrogeochemical processes leading to the formation of Mg–Fe–Ca carbonate concretions (first distinct carbonate population, FDCP) in Martian meteorite ALH84001 by generic hydrogeochemical equilibrium and mass transfer modeling. Our simple conceptual models assume isochemical equilibration of orthopyroxenite minerals with pure water at varying water‐to‐rock ratios, temperatures and CO₂ partial pressures. Modeled scenarios include CO₂ partial pressures ranging from 10.1325 to 0.0001 MPa at water‐to‐rock ratios between 4380 and 43.8 mol mol^?1 and different temperatures (278, 303 and 348 K) and enable the precipitation of Mg–Fe–Ca solid solution carbonate. Modeled range and trend of carbonate compositional variation from magnesio‐siderite (core) to magnesite (rim), and the precipitation of amorphous SiO₂ and magnetite coupled to magnesite‐rich carbonate are similar to measured compositional variation. The results of this study suggest that the early Martian subsurface had been exposed to a dynamic gas pressure regime with decreasing CO₂ partial pressure at low temperatures (approximately 1.0133 to 0.0001 MPa at 278 K or 6 to 0.0001 MPa at 303 K). Moderate water‐to‐rock ratios of ca. 438 mol mol^?1 and isochemical weathering of orthopyroxenite are additional key prerequisites for the formation of secondary phase assemblages similar to ALH84001’s ‘FDCP’. Outbursts of water and CO_2(g) from confined ground water in fractured orthopyroxenite rocks below an unstable CO₂ hydrate‐containing cryosphere provide adequate environments on the early Martian surface.     

Bleached mudstone,iron concretions,and calcite veins: a natural analogue for the effects of reducing CO2‐bearing fluids on migration and mineralization of iron,sealing properties,and composition of mudstone cap rocks

This study investigates the Wangfu Depression of the Songliao Basin, China, as a natural analogue site for Fe migration (bleaching) and mineralization (formation of iron concretions) caused by reducing CO₂‐bearing fluids that leak along fractures after carbon capture, utilization, and storage. We also examined the origin of fracture‐filling calcite veins, the properties of self‐sealing fluids, the influence of fluids on the compositions of mudstone and established a bleaching model for the study area. Our results show that iron concretions are the oxidative products of precursor minerals (pyrite and siderite) during uplift and are linked to H₂S and CO₂ present in early stage fluids. The precipitation of calcite veins is the result of CO₂ degassing and is related to CO₂, CH₄, and minor heavy hydrocarbons in the main bleaching fluids. In our model, fluids preferentially enter high‐permeability fracture systems and result in the bleaching of surrounding rocks and precipitation of calcite veins. The infilling of calcite veins significantly decreases the permeability of fractures and forces the fluids to slowly enter and bleach the mudstone rocks. The Fe²⁺ released during bleaching migrates to elsewhere with the solutions or is reprecipitated in the calcite veins and iron concretions. The formation of calcite veins reduces the fracture space and effectively prevents fluid flow. The fluids have an insignificant effect on minerals within the mudstone. In terms of the chemistry of the mudstone, only the contents of Fe₂O₃, U, and Mo change significantly, with the content of U increasing in the mudstone and the contents of Fe₂O₃ and Mo decreasing during bleaching.     

SO2与水分综合影响下的云冈石窟砂岩劣化研究

气体污染物SO₂是造成云冈石窟文物本体劣化的重要因素之一。为厘清SO₂与水分耦合作用下的云冈砂岩劣化规律，开展不同SO₂浓度、相对湿度以及降水条件下的室内模拟风化试验，测定试样质量、表面特征和化学成分变化。结果表明：SO₂易与砂岩中的碳酸盐矿物(如方解石)和长石发生化学反应，产物包括CaSO₄·2H₂O、MgSO₄·7H₂O和高岭石等，且随着相对湿度增加，反应程度增大，造成试样的质量、色差值、可溶盐含量上升及硅铝比下降；液态水的参与能显著加快SO₂与砂岩的相互作用过程，不但增加了各项指标的变化幅度，还加大了SO₂入侵深度。研究成果可为砂岩质文物的科学认知和预防性保护提供参考。     

Mineralogy and fluid inclusion gas chemistry of production well mineral scale deposits at the Dixie Valley geothermal field,USA

At the Dixie Valley geothermal field, Nevada, USA, fluid boiling triggered the precipitation of carbonate scale minerals in concentric bands around tubing inserted into production well 28–33. When the tubing was removed, this mineral scale was sampled at 44 depth intervals between the wellhead and 1227 m depth. These samples provide a unique opportunity to evaluate the effects of fluid boiling on the scale mineralogy and geochemistry of the vapor and liquid phase. In this study, the mineralogy of the scale deposits and the composition of the fluid inclusion gases trapped in the mineral scales were analyzed. The scale consists mainly of calcite from 670–1112 m depth and aragonite from 1125 to 1227 m depth, with traces of quartz and Mg‐smectite. Mineral textures, including hopper growth, twinning, and fibrous growth in the aragonite and banded deposits of fine grained calcite crystals, are the result of progressive boiling. The fluid inclusion noncondensable gas was dominated by CO₂. However, significant variations in He relative to N₂ and Ar provide evidence that the geothermal reservoir consists of mixed source deeply circulating reservoir water and shallow, air saturated meteoric water. Gas analyses for many inclusions also showed higher CH₄ and H₂ relative to CO₂ than measured in gas sampled from this well, other production wells, and fumaroles. These inclusions are interpreted to have trapped CH₄‐ and H₂‐enriched gas resulting from early stages of boiling.     

A comprehensive review of hydrocarbons and genetic model of the sandstone‐hosted Dongsheng uranium deposit,Ordos Basin,China

The Dongsheng uranium deposit, the largest in situ leach uranium mine in the Ordos Basin, geometrically forms a roll‐front type deposit that is hosted in the Middle Jurassic Zhiluo Formation. The genesis of the mineralization, however, has long been a topic of great debate. Regional faults, epigenetic alterations in surface outcrops, natural oil seeps, and experimental findings support a reducing microenvironment during ore genesis. The bulk of the mineralization is coffinite. Based on thin‐section petrography, some of the coffinite is intimately intergrown with authigenic pyrite (ore‐stage pyrite) and is commonly juxtaposed with some late diagenetic sparry calcite (ore‐stage calcite) in primary pores, suggesting simultaneous precipitation. Measured homogenization temperatures of greater than 100°C from fluid inclusions indicate circulation of low‐temperature hydrothermal fluids in the ore zone. The carbon isotopic compositions of late calcite cement (δ¹³C_VPDB = ?31.0 to ?1.4‰) suggest that they were partly derived from sedimentary organic carbon, possibly from deep‐seated petroleum fluids emanating from nearby faults. Hydrogen and oxygen isotope data from kaolinite cement (δD = ?133 to ?116‰ and δ¹⁸O_SMOW = 12.6–13.8‰) indicate that the mineralizing fluids differed from magmatic and metamorphic fluids and were more depleted in D (²H) than modern regional meteoric waters. Such a strongly negative hydrogen isotopic signature suggests that there has been selective modification of δD by CH₄±H₂S±H₂ fluids. Ore‐stage pyrite lies within a very wide range of δ³⁴S (?39.2 to 26.9‰), suggesting that the pyrite has a complex origin and that bacterially mediated sulfate reduction cannot be precluded. Hydrocarbon migration and its role in uranium reduction and precipitation have here been unequivocally defined. Thus, a unifying model for uranium mineralization can be established: Early coupled bacterial uranium mineralization and hydrocarbon oxidation were followed by later recrystallization of ore phases in association with low‐temperature hydrothermal solutions under hydrocarbon‐induced reducing conditions.     

Evidence of physico–chemical and isotopic modifications in archaeological bones during controlled acid etching

It has been repeatedly shown that palaeoecological inferences from the elemental and isotopic content of carbonate hydroxylapatite of fossil teeth and bones are unrecoverable without removing diagenetic overprinting by chemical pretreatments. Such pretreatments may in turn cause modification of the biogenic signature. In this paper, we focus upon optimal removal of Ca–bearing carbonates (mainly calcite). In order to control the progress with time of calcite dissolution, we perform leaching under vacuum, and we monitor the evolution of the pH, pCO₂, δ¹³C of released CO₂, %C, δ¹³C and δ¹⁸O of the remaining mineral. For a set of different Quaternary bones and teeth, mass and isotopic balances indicate that 1 hour at most is necessary for complete dissolution of calcite with an optimal conservation of carbonate hydroxylapatite. Long–lasting experiments lead to a fractionation of hydroxylapatite ¹⁸O/¹⁶O carbonates.     

Gas breakthrough experiments on pelitic rocks: comparative study with N2, CO2 and CH4

The capillary‐sealing efficiency of intermediate‐ to low‐permeable sedimentary rocks has been investigated by N₂, CO₂ and CH₄ breakthrough experiments on initially fully water‐saturated rocks of different lithological compositions. Differential gas pressures up to 20 MPa were imposed across samples of 10–20 mm thickness, and the decline of the differential pressures was monitored over time. Absolute (single‐phase) permeability coefficients (k_abs), determined by steady‐state fluid flow tests, ranged between 10^?22 and 10^?15 m². Maximum effective permeabilities to the gas phase k_eff(max), measured after gas breakthrough at maximum gas saturation, extended from 10^?26 to 10^?18 m². Because of re‐imbibition of water into the interconnected gas‐conducting pore system, the effective permeability to the gas phase decreases with decreasing differential (capillary) pressure. At the end of the breakthrough experiments, a residual pressure difference persists, indicating the shut‐off of the gas‐conducting pore system. These pressures, referred to as the ‘minimum capillary displacement pressures’ (P_d), ranged from 0.1 up to 6.7 MPa. Correlations were established between (i) absolute and effective permeability coefficients and (ii) effective or absolute permeability and capillary displacement pressure. Results indicate systematic differences in gas breakthrough behaviour of N₂, CO₂ and CH₄, reflecting differences in wettability and interfacial tension. Additionally, a simple dynamic model for gas leakage through a capillary seal is presented, taking into account the variation of effective permeability as a function of buoyancy pressure exerted by a gas column underneath the seal.     

Long‐term chemical evolution and modification of continental basement brines – a field study from the Schwarzwald,SW Germany

Highly saline, deep‐seated basement brines are of major importance for ore‐forming processes, but their genesis is controversial. Based on studies of fluid inclusions from hydrothermal veins of various ages, we reconstruct the temporal evolution of continental basement fluids from the Variscan Schwarzwald (Germany). During the Carboniferous (vein type i), quartz–tourmaline veins precipitated from low‐salinity (<4.5wt% NaCl + CaCl₂), high‐temperature (≤390°C) H₂O‐NaCl‐(CO₂‐CH₄) fluids with Cl/Br mass ratios = 50–146. In the Permian (vein type ii), cooling of H₂O‐NaCl‐(KCl‐CaCl₂) metamorphic fluids (T ≤ 310°C, 2–4.5wt% NaCl + CaCl₂, Cl/Br mass ratios = 90) leads to the precipitation of quartz‐Sb‐Au veins. Around the Triassic–Jurassic boundary (vein type iii), quartz–haematite veins formed from two distinct fluids: a low‐salinity fluid (similar to (ii)) and a high‐salinity fluid (T = 100–320°C, >20wt% NaCl + CaCl₂, Cl/Br mass ratios = 60–110). Both fluids types were present during vein formation but did not mix with each other (because of hydrogeological reasons). Jurassic–Cretaceous veins (vein type iv) record fluid mixing between an older bittern brine (Cl/Br mass ratios ~80) and a younger halite dissolution brine (Cl/Br mass ratios >1000) of similar salinity, resulting in a mixed H₂O‐NaCl‐CaCl₂ brine (50–140°C, 23–26wt% NaCl + CaCl₂, Cl/Br mass ratios = 80–520). During post‐Cretaceous times (vein type v), the opening of the Upper Rhine Graben and the concomitant juxtaposition of various aquifers, which enabled mixing of high‐ and low‐salinity fluids and resulted in vein formation (multicomponent fluid H₂O‐NaCl‐CaCl₂‐(SO₄‐HCO₃), 70–190°C, 5–25wt% NaCl‐CaCl₂ and Cl/Br mass ratios = 2–140). The first occurrence of highly saline brines is recorded in veins that formed shortly after deposition of halite in the Muschelkalk Ocean above the basement, suggesting an external source of the brine's salinity. Hence, today's brines in the European basement probably developed from inherited evaporitic bittern brines. These were afterwards extensively modified by fluid–rock interaction on their migration paths through the crystalline basement and later by mixing with younger meteoric fluids and halite dissolution brines.     

Gas breakthrough pressure for hydrocarbon reservoir seal rocks: implications for the security of long-term CO2 storage in the Weyburn field

This paper reports a laboratory study of the gas breakthrough pressure for different gas/liquid systems in the Mississippian‐age Midale Evaporite. This low‐permeability rock formation is the seal rock for the Weyburn Field in southeastern Saskatchewan, Canada, where CO₂ is being injected into an oil reservoir for enhanced recovery and CO₂ storage. A technique for experimentally determining CO₂ breakthrough pressure at reservoir conditions is presented. Breakthrough pressures for N₂, CO₂ and CH₄ were measured with the selected seal‐rock samples. The maximum breakthrough pressure is over 30 MPa for N₂ and approximately 21 MPa for CO₂. The experimental results demonstrate that the Weyburn Midale Evaporite seal rock is of high sealing quality. Therefore, the Weyburn reservoir and Midale Beds can be used as a CO₂ storage site after abandonment. The measured results also show that the breakthrough pressure of a seal rock for a gas is nearly proportional to the interfacial tension of the gas/brine system. The breakthrough pressure of a CO₂/brine system is significantly reduced compared with that of a CH₄/brine system because of the much lower interfacial tension of the former. This implies that a seal rock that seals the original gas in a gas reservoir or an oil reservoir with a gas cap may not be tight enough to seal the injected CO₂ if the pressure during or after CO₂ injection is the same or higher than the original reservoir pressure. Therefore, reevaluation of the breakthrough pressure of seal rocks for a given reservoir is necessary and of highest priority once it is chosen as a CO₂ storage site.     

Role of compressive tectonics on gas charging into the Ordovician sandstone reservoirs in the Sbaa Basin,Algeria: constrained by fluid inclusions and mineralogical data

Structure‐ and tectonic‐related gas migration into Ordovician sandstone reservoirs and its impact on diagenesis history were reconstructed in two gas fields in the Sbaa Basin, in SW Algeria. This was accomplished by petrographical observations, fluid inclusion microthermometry and stable isotope geochemistry on quartz, dickite and carbonate cements and veins. Two successive phases of quartz cementation (CQ1 and CQ2) occurred in the reservoirs. Two phase aqueous inclusions show an increase in temperatures and salinities from the first CQ1 diagenetic phase toward CQ2 in both fields. Microthermometric data on gas inclusions in quartz veins reveal the presence of an average of 92 ± 5 mole% of CH₄ considering a CH₄‐CO₂ system, which is similar to the present‐day gas composition in the reservoirs. The presence of primary methane inclusions in early quartz overgrowths and in quartz and calcite veins suggests that hydrocarbon migration into the reservoir occurred synchronically with early quartz cementation in the sandstones located near the contact with the Silurian gas source rock at 100–140°C during the Late Carboniferous period and the late Hercynian episode fracturing at temperatures between 117 and 185°C, which increased in the NW‐direction of the basin. During the fracture filling, three main types of fluids were identified with different salinities and formation temperatures. A supplementary phase of higher fluid temperature (up to 226°C) recorded in late quartz, and calcite veins is related to a Jurassic thermal event. The occurrence of dickite cements close to the Silurian base near the main fault areas in both fields is mainly correlated with the sandstones where the early gas was charged. It implies that dickite precipitation is related to acidic influx. Late carbonate cements and veins (calcite – siderite – ankerite and strontianite) occurred at the same depths resulting from the same groundwater precipitation. The absence of methane inclusions in calcite cements result from methane flushing by saline waters.     

Study of coal gas wettability for CO2 storage and CH4 recovery

To quantify and rank gas wettability of coal as a key parameter affecting the extent of CO₂ sequestration in coal and CH₄ recovery from coal, we developed a contact angle measuring system based on a captive gas bubble technique. We used this system to study the gas wetting properties of an Australian coal from the Sydney Basin. Gas bubbles were generated and captivated beneath a coal sample within a distilled water‐filled (pH 5.7) pressurised cell. Because of the use of distilled water, and the continuous dissolution and shrinkage of the gas bubble in water during measurement, the contact angles measured correspond to a ‘transient receding’ contact angle. To take into account the mixed‐gas nature (CO₂, CH₄, and to a lesser extent N₂) of coal seam gas in the basin, we evaluated the relative wettability of coal by CH₄, CO₂ and N₂ gases in the presence of water. Measurements were taken at various pressures of up to 15 MPa for CH₄ and N₂, and up to 6 MPa for CO₂ at a constant temperature of 22°C. Overall, our results show that CO₂ wets coal more extensively than CH₄, which in turn wets coal slightly more than N₂. Moreover, the contact angle reduces as the pressure increases, and becomes < 90° at various pressures depending on the gas type. In other words, all three gases wet coal better than water under sufficiently high pressure.     

Diagenesis and elemental geochemistry under varying reservoir oil saturation in the Junggar Basin of NW China: implication for differentiating hydrocarbon‐bearing horizons

In this paper, we attempt to differentiate hydrocarbon‐bearing reservoir horizons of the Junggar Basin of NW China based on the characteristics of diagenesis and associated elemental geochemistry. Reservoirs at this site have varying levels of oil saturation that correlate with the degree of dissolution in minerals (e.g., calcite and feldspar). Four different horizons with varying diagenetic mineral assemblages were observed, including (i) kaolinite‐rich, oil‐dominated horizons, (ii) kaolinite–pyrite–hematite‐rich, oil–water‐dominated horizons, (iii) siderite–chlorite‐rich, water‐dominated horizons, and (iv) chlorite‐rich horizons with negligible hydrocarbon production. The mean MnO content of the representative diagenetic mineral (e.g., calcite) in each of the above horizons is >2.5, 2.0–2.5, 1.5–2.0, and <1.0 wt%, respectively. We propose that the above methodology can be used for the identification of reservoir hydrocarbon‐bearing horizons. We argue that the indicators presented here can be applied in oil exploration across the Junggar Basin.     

Constraining the rate and extent of mantle serpentinization from seismic and petrological data: implications for chemosynthesis and tectonic processes

We used seismic velocity as a proxy for serpentinization of the mantle, which occurred beneath thinned but laterally continuous continental crust during continental break up, prior to opening of the Atlantic Ocean. The serpentinized sub‐continental mantle is now exhumed, beneath the Iberia Abyssal Plain and was accessed by scientific drilling on Ocean Drilling Program legs 149 and 173. Chromatographic modelling of kinetically limited transport of the serpentinization front yields a front displacement of 2197 ± 89 m, a time‐integrated fluid flux of 1098 ± 45 m³ m^?2 and a Damköhler number of 6.0 ± 0.2. Whether either surface reaction or chemical transport limit the rate of reaction, we calculate timescales for serpentinization of approximately 10⁵–10⁶ years. This yields time‐average fluid flux rates for H₂O, entering and reacting with the mantle, of 60–600 mol m^?2 a^?1 and for CH₄, produced as a by‐product of oxidation of Fe⁺⁺ to magnetite and exiting the mantle, of 0.55–5.5 mol m^?2 a^?1. This equates to a CH₄‐flux of 0.18–1.8 Tg a^?1 for coeval serpentinization of the mantle that was exhumed west of Iberia. This represents 0.03–0.3% of the present‐day annual CH₄‐flux from all sources and a higher fraction of pre‐anthropogenic (lower) CH₄ levels. CH₄ released by serpentinization at or beneath the seafloor could provide substrate for biological chemosynthesis and/or promote gas‐hydrate formation. Finally, noting its volumetric extent and rapidity (<10⁶ years), we interpret serpentinization to be a reckonable component of tectonic processes, contributing both diapiric and expansional forces and helping to ‘lubricate’ extensional processes. Given its anisotropic permeability, actively deforming serpentinite might impede melt migration which may be of interest, given the apparent lack of melt in some rifted margins.     

Hydrothermal palaeofluid circulation in the fracture network of the Baksa Gneiss Complex of SW Pannonian Basin,Hungary

A well‐developed fracture‐filling network is filled by dominantly Ca‐Al‐silicate minerals that can be found in the polymetamorphic rock body of the Baksa Gneiss Complex (SW Hungary). Detailed investigation of this vein network revealed a characteristic diopside→epidote→sphalerite→albite ± kfeldspar→chlorite1 ± prehnite ± adularia→chlorite2→chlorite3→pyrite→calcite1→calcite2→calcite3 fracture‐filling mineral succession. Thermobarometric calculations (two feldspar: 230–336°C; chlorites: approximately 130–300°C) indicate low‐temperature vein formation conditions. The relative succession of chlorites in the mineral sequence combined with the calculated formation temperatures reveals a cooling trend during precipitation of the different chlorite phases (T_chlorite1: 260 ± 32°C →T_chlorite2: 222 ± 20°C →T_chlorite3: 154 ± 13°C). This cooling trend can be supported by the microthermometry data of primary fluid inclusions in diopside (T_h: 276–362°C) and epidote (T_h: 181–359°C) phases. The identical chemical character (0.2–1.5 eq. wt% NaCl) of these inclusions mean that vein mineralization occurred in a same fluid environment. The high trace element content (e.g. As, Cu, Zn, Mn) and Co/Ni ratio approximately 1–5 of pyrite grains support the postmagmatic hydrothermal origin of the veins. The vein microstructure and identical fluid composition indicate that vein mineralization occurred in an interconnected fracture system where crystals grew in fluid filled cracks. Vein system formed at approximately <200 MPa pressure conditions during cooling from approximately 480°C to around 150°C. The rather different fluid characteristics (T_h: 75–124°C; 17.5–22.6 eq. wt% CaCl₂) of primary inclusions of calcite1 combining with the special δ¹⁸O signature of fluid from which this mineral phase precipitated refer to hydrological connection between the crystalline basement and the sedimentary cover.     

Low‐temperature catalytic CO2 hydrogenation with geological quantities of ruthenium: a possible abiotic CH4 source in chromitite‐rich serpentinized rocks

Metal‐catalysed CO₂ hydrogenation is considered a source of methane in serpentinized (hydrated) igneous rocks and a fundamental abiotic process germane to the origin of life. Iron, nickel, chromium and cobalt are the catalysts typically employed in hydrothermal simulation experiments to obtain methane at temperatures >200°C. However, land‐based present‐day serpentinization and abiotic gas apparently develop below 100°C, down to approximately 40–50°C. Here, we document considerable methane production in thirteen CO₂ hydrogenation experiments performed in a closed dry system, from 20 to 90°C and atmospheric pressure, over 0.9–122 days, using concentrations of non‐pretreated ruthenium equivalent to those occurring in chromitites in ophiolites or igneous complexes (from 0.4 to 76 mg of Ru, equivalent to the amount occurring approximately in 0.4–760 kg of chromitite). Methane production increased with time and temperature, reaching approximately 87 mg CH₄ per gram of Ru after 30 days (2.9 mgCH₄/g_ru/day) at 90°C. At room temperature, CH₄ production rate was approximately three orders of magnitude lower (0.003 mgCH₄/g_ru/day). We report the first stable carbon and hydrogen isotope ratios of abiotic CH₄ generated below 100°C. Using initial δ¹³C_CO2 of ‐40‰, we obtained room temperature δ¹³C_CH4 values as ¹³C depleted as ?142‰. With time and temperature, the C‐isotope separation between CO₂ and CH₄ decreased significantly and the final δ¹³C_CH4 values approached that of initial δ¹³C_CO2. The presence of minor amounts of C₂‐C₆ hydrocarbons is consistent with observations in natural settings. Comparative experiments at the same temperatures with iron and nichel catalysts did not generate CH₄. Ru‐enriched chromitites could potentially generate methane at low temperatures on Earth and on other planets.     

On the geochemistry of gases and noble gas isotopes (including 222Rn) in deep crustal fluids: the 4000 m KTB-pilot hole fluid production test 2002–03

The concentrations of H₂, O₂, CO₂, and concentrations and isotopic composition of the noble gases (including ²²²Rn), N₂, CH₄, and higher hydrocarbons dissolved in 4000 m deep‐seated fluids from a 12‐month fluid production test in the KTB pilot hole were analyzed. This determination of the gas geochemistry during the test in combination with the knowledge of the hydraulic data provides relevant information about the fluid hydraulics of the deep system. All gas concentrations and isotopic signatures, except for ²²²Rn, showed constancy during the course of the test. This, in combination with large fluid flow rates at a moderate water table drawdown, imply an almost infinite fluid reservoir in 4000 m depth. From the change in ²²²Rn‐activity as a function of pump rate, the contribution of smaller and wider pores to the overall fluid flow in an aquifer can be deduced. This ²²²Rn‐activity monitoring proved therefore to be a valuable instrument for the qualitative observation of the scavenging of pore and fracture surfaces, a hydraulic feature invisible to standard hydraulic testing tools. The observance of this scavenging effect is due to (i) the continuous on‐line geochemical monitoring, (ii) the durability of the test, (iii) a change in pump rate during the course of the test, and (iv) due to the short half‐life of ²²²Rn. The fluids have a 5.9% mantle He component, and a δ²¹Ne excess of 14%, and a noble gas model age of about (5.5–6.2) ± 2.0 Myr. The mean N₂/Ar‐ratio of 516 and δ¹⁵N‐data of about +1.5‰ indicates sedimentary or metamorphic origin of N₂. The hydrocarbons, amounting to 33 vol.% in the gas phase, are derived from thermal decomposition of marine organic matter of low maturity. But a key question, the identification of the potential source region of the fluids and the migration pathway, is still unidentified.