CO2 solubility and speciation in intermediate (andesitic) melts: the role of H2O and composition

We determined total CO₂ solubilities in andesite melts with a range of compositions. Melts were equilibrated with excess C-O(-H) fluid at 1 GPa and 1300°C then quenched to glasses. Samples were analyzed using an electron microprobe for major elements, ion microprobe for C-O-H volatiles, and Fourier transform infrared spectroscopy for molecular H₂O, OH⁻, molecular CO₂, and CO₃²⁻. CO₂ solubility was determined in hydrous andesite glasses and we found that H₂O content has a strong influence on C-O speciation and total CO₂ solubility. In anhydrous andesite melts with ∼60 wt.% SiO₂, total CO₂ solubility is ∼0.3 wt.% at 1300°C and 1 GPa and total CO₂ solubility increases by about 0.06 wt.% per wt.% of total H₂O. As total H₂O increases from ∼0 to ∼3.4 wt.%, molecular CO₂ decreases (from 0.07 ± 0.01 wt.% to ∼0.01 wt.%) and CO₃²⁻ increases (from 0.24 ± 0.04 wt.% to 0.57 ± 0.09 wt.%). Molecular CO₂ increases as the calculated mole fraction of CO₂ in the fluid increases, showing Henrian behavior. In contrast, CO₃²⁻ decreases as the calculated mole fraction of CO₂ in the fluid increases, indicating that CO₃²⁻ solubility is strongly dependent on the availability of reactive oxygens in the melt. These findings have implications for CO₂ degassing. If substantial H₂O is present, total CO₂ solubility is higher and CO₂ will degas at relatively shallow levels compared to a drier melt. Total CO₂ solubility was also examined in andesitic glasses with additional Ca, K, or Mg and low H₂O contents (<1 wt.%). We found that total CO₂ solubility is negatively correlated with (Si + Al) cation mole fraction and positively correlated with cations with large Gibbs free energy of decarbonation or high charge-to-radius ratios (e.g., Ca). Combining our andesite data with data from the literature, we find that molecular CO₂ is more abundant in highly polymerized melts with high ionic porosities (>∼48.3%), and low nonbridging oxygen/tetrahedral oxygen (<∼0.3). Carbonate dominates most silicate melts and is most abundant in depolymerized melts with low ionic porosities, high nonbridging oxygen/tetrahedral oxygen (>∼0.3), and abundant cations with large Gibbs free energy of decarbonation or high charge-to-radius ratio. In natural silicate melt, the oxygens in the carbonate are likely associated with tetrahedral and network-modifying cations (including Ca, H, or H-bonds) or a combinations of those cations.     

Impact of nitrogenous fertiliser-induced proton release on cultivated soils with contrasting carbonate contents: A column experiment

An experimental study was carried out in order to evaluate the impact of nitrogen fertiliser-induced acidification in carbonated soils. Undisturbed soil columns containing different carbonate content were sampled in the field. Fertiliser spreading was simulated by NH₄Cl addition on top of the soil column. Soil solution composition (mainly nitrate and base cations) was studied at the soil column’s base. Nitrification occurred to a different extent depending on soil type. Higher nitrification rates were observed in calcareous soils. In all the soil types, strong correlations between leached base cation and nitrate concentrations were observed. Regression coefficients between base cations, nitrate and chloride were used to determine the dominant processes occurring following NH₄Cl spreading. In non-carbonated soils, nitrogen nitrification induced base cation leaching and soil acidification. In carbonated soils, no change of soil pH was observed. However, fertilisers induced a huge cation leaching. Carbonate mineral weathering led to the release of base cations, which replenished the soil exchangeable complex. Carbonated mineral weathering buffered acidification. Since direct weathering might have occurred without atmospheric CO₂ consumption, the use of nitrogen fertiliser on carbonated soil induces a change in the cation and carbon budgets. When the results of these experiments are extrapolated on a global scale to the surface of fertilised areas lying on carbonate, carbonated reactions with N fertilisers would imply an additional flux of 5.7 × 10¹² mol yr⁻¹ of Ca + Mg. The modifications of weathering reactions in cultivated catchments and the ability of nitrogen fertilisers to significantly modify the CO₂ budget should be included in carbon global cycle assessment.     

Calculating field weathering rates using a mechanistic geochemical model PROFILE

A new model for base cation release due to chemical weathering of soil minerals has been developed based on transition state theory, and included in the integrated soil chemistry model PROFILE. The data required for model application can be operationally determined on soil samples, making the model generally applicable and independent of any type of calibration. The model considers the contribution to the weathering rate from 12 groups of the most common primary and secondary minerals of soils, reacting in separate reactions with H⁺-ion, H₂O, CO₂ and organic acids expressed as dissolved organic carbon (DOC). The weathering rate sub-model couples the effects of dissolved Al and base cations on the reaction mechanisms. The model takes into account changes in soil temperature, different chemical conditions, the effect of vegetation interactions with the soil and N transformations. The kinetic coefficients and reaction orders are based on a complete re-evaluation of weathering data available in the literature, and additional kinetic data determined by the authors.Data from 23 different independent determinations of the field weathering rate from 15 sites in Scandinavia, Central Europe and North America were compiled and used to verify the model. The model is capable of estimating the release rate of base cations due to chemical weathering from information on soil mineralogy, texture and geochemical properties of the order of ±20% of the rate determined by independent methods. The results indicate that small amounts of dark minerals like epidote and hornblende, and the plagioclase content, largely determine the field weathering rate.     

Adsorption of H<Subscript>2</Subscript>O,NH<Subscript>3</Subscript> and C<Subscript>6</Subscript>H<Subscript>6</Subscript> on alkali metal cations in internal surface of mordenite and in external surface of smectite: a DFT study

Adsorption of H₂O, NH₃ and C₆H₆ on H- and alkali metal-exchanged structures of mordenite and on corresponding cations on the smectite layer is investigated by ab initio density-functional calculations. Proton or an alkali metal cation compensates one Al/Si framework substitution and resides in the extra-framework position of zeolite or above flat smectite layer close to the Al/Si substitution. Pronounced similarities between zeolite and smectite are observed in changes of the adsorption energies and location of the external cation with changing character of the external cation. Calculated adsorption energies exhibit the following trend: E(NH₃) > E(H₂O) > E(C₆H₆). Because of looser contact with the framework, zeolitic cations are stronger adsorption centers and calculated adsorption energies of zeolites are by ~20–30% larger than cations of smectites. The highest adsorption energy is calculated for H-exchanged structures and down the group of alkali metal cations a decrease of the adsorption energy is observed. Deviations from the smooth variation of the adsorption energy are caused by: (1) formation of strong hydrogen bonds in H-exchanged structures, (2) adsorption induced migration of the external Li⁺ cation, and (3) steric hindrances of the flat C₆H₆ molecule adsorbed on the cation in the cage of zeolite.     

The effect of CO<Subscript>2</Subscript> on the solubility of aqueous chloride fluid in dacite,phonolite, and rhyolite melts

The solubility of H₂O–CO₂–Cl-containing fluids of various concentrations (0, 3, 10, and 23 wt % of HCl and from 0 to ~8–15 wt % of CO₂) in dacite, phonolite, and rhyolite melts at 1000°C and 200 MPa was studied in experiments. It was shown that the Cl concentration in the melt increased substantially from rhyolite to phonolite and dacite (up to 0.25, 0.85, and 1.2 wt %, respectively). The introduction of CO₂ into the system resulted in an increase in the Cl content in the melt composition by 20–25%. One may suppose that Cl reactivity in a fluid increases in the presence of CO₂ to cause growth of the Cl content in the melt. The introduction of CO₂ into the system considerably affects the content of H₂O in aluminosilicate melts as well. Thus, the addition of CO₂ decreases the H₂O content in the melt by ~0.5–1.0 wt %. The decrease in the H₂O content in an aluminosilicate melt is probably caused by fluid dilution with CO₂ resulting in a decrease in the H₂O mole fraction and fugacity in the fluid.     

Thermodynamic Analysis of Secondary Minerals Stability in Altered Carbonatites of the Oldoinyo Lengai Volcano,Northern Tanzania

Carbonatites from the Oldoinyo Lengai volcano, northern Tanzania, are unstable under normal atmospheric conditions. Owing to carbonatite interaction with water, the major minerals—gregoryite Na₂(CO₃), nyerereite Na₂Ca(CO₃)₂, and sylvite KCl—are dissolved and replaced with secondary low-temperature minerals: thermonatrite Na₂(CO₃) · H₂O, trona Na₃(CO₃)(HCO₃) · 2H₂O, nahcolite Na(HCO₃), pirssonite Na₂Ca(CO₃)₂ · 2H₂O, calcite Ca(CO₃), and shortite Na₂Ca₂(CO₃)₃. Thermodynamic calculations show that the formation of secondary minerals in Oldoinyo Lengai carbonatites are controlled by the pH of the pore solution, H₂O and CO₂ fugacity, and the ratio of Ca and Na activity in the Na₂O–CaO–CO₂–H₂O system.     

The effect of alkalis and polymerization on the solubility of H<Subscript>2</Subscript>O and CO<Subscript>2</Subscript> in alkali-rich silicate melts

The effect of alkalis on the solubility of H₂O and CO₂ in alkali-rich silicate melts was investigated at 500 MPa and 1,250 °C in the systems with H₂O/(H₂O + CO₂) ratio varying from 0 to 1. Using a synthetic analog of phonotephritic magma from Alban Hills (AH1) as a base composition, the Na/(Na + K) ratio was varied from 0.28 (AH1) to 0.60 (AH2) and 0.85 (AH3) at roughly constant total alkali content. The obtained results were compared with the data for shoshonitic and latitic melts having similar total alkali content but different structural characteristics, e.g., NBO/T parameter (the ratio of non-bridging oxygens over tetrahedrally coordinated cations), as those of the AH compositions. Little variation was observed in H₂O solubility (melt equilibrated with pure H₂O fluid) for the whole compositional range in this study with values ranging between 9.7 and 10.2 wt. As previously shown, the maximum CO₂ content in melts equilibrated with CO₂-rich fluids increases strongly with the NBO/T from 0.29 wt % for latite (NBO/T = 0.17) to 0.45 wt % for shoshonite (NBO/T = 0.38) to 0.90 wt % for AH2 (NBO/T = 0.55). The highest CO₂ contents determined for AH3 and AH1 are 1.18 ± 0.05 wt % and 0.86 ± 0.12 wt %, respectively, indicating that Na is promoting carbonate incorporation stronger than potassium. At near constant NBO/T, CO₂ solubility increases from 0.86 ± 0.12 wt % in AH1 [Na/(Na + K)] = 0.28, to 1.18 ± 0.05 wt % in AH3 [Na/(Na + K)] = 0.85, suggesting that Na favors CO₂ solubility on an equimolar basis. An empirical equation is proposed to predict the maximum CO₂ solubility at 500 MPa and 1,100–1,300 °C in various silicate melts as a function of the NBO/T, (Na + K)/∑cations and Na/(Na + K) parameters: \({\text{wt}}\% \;{\text{CO}}_{2} = - 0.246 + 0.014\exp \left( {6.995 \cdot \frac{\text{NBO}}{T}} \right) + 3.150 \cdot \frac{{{\text{Na}} + {\text{K}}}}{{\varSigma {\text{cations}}}} + 0.222 \cdot \frac{\text{Na}}{{{\text{Na}} + {\text{K}}}}.\) This model is valid for melt compositions with NBO/T between 0.0 and 0.6, (Na + K)/∑cation between 0.08 and 0.36 and Na/(Na + K) ratio from 0.25 to 0.95 at oxygen fugacities around the quartz–fayalite–magnetite buffer and above.     

Fluid inclusions in quartz from deep-seated granitic intrusions,south Norway

H₂O, CO₂, and H₂OCO₂ inclusions were observed in quatz from deep-seated granitic intrusions belonging to the Precambrian Farsund plutonic complex, south Norway. These inclusions represent solidus and/or sub-solidus fluids that were present in these rocks at some period between the initial melt and the present. Early CO₂ and H₂OCO₂ inclusions with about 20 mole% CO₂ contain up to 10 mole% CH₄ in the CO₂ phase and have densities from 0.96 to 0.85 g/cc. These inclusions are considered to most nearly approximate solidus vapour phases and suggest conditions of final solidification of the magma at 5 to 6 Kb and 700°C to 800°C. The H₂O inclusions have salinities between 2 and 60 wt%; the majority contain 5 to 20 equivalent wt.% NaCl and have densities from 1.05 to 0.85 g/cc. Microthermometry indicates that other cations such as K⁺, Ca²⁺ and / or Mg²⁺ are present in these aqueous fluids. The H₂O inclusions primarily represent fluids present at a post-magmatic stage of fracturing and healing of these rocks during uplift.     

车载小型气体质谱仪现场地气分析应用

OmniStar小型气体质谱仪用于车载实验室,可根据野外情况采取灵活的采样方式,实现对H2、He、CH4、N2、O2、Ar、CO2以及C3H8、C4H10的现场分析。对浓度为100×10-6的H2、He、CH4、N2、O2、Ar、CO2混合标气进行100次连续测定,得到的各组分的精密度(RSD)均优于1%,H2、He、Ar、CO2准确度(RE)分别为3.74、0.94、1.83、10.5;对室内空气进行连续3 500次测定,得到的H2、He、CO2的精密度分别为2.25%、5.55%、4.06%,N2、O2、Ar的精密度优于1%;对CH4、C2H6、C3H8、C4H10混合标准气体进行连续13次测量,得到的C3H8、C4H10的精密度(RSD)优于1%,测量的平均值与标准值完全吻合,能够满足野外现场分析需求。在内蒙古西乌旗及新疆金窝子地区应用该仪器,采用采样袋取气、螺旋钻及井孔原位在线测定等方式得到样品数据,并发现两区域内部分采样点的CO2、H2及He异常。     

On the interaction of pure and impure supercritical CO2 with rock forming minerals in saline aquifers: An experimental geochemical approach

The aim of this experimental study was to evaluate and compare the geochemical impact of pure and impure CO₂ on rock forming minerals of possible CO₂ storage reservoirs. This geochemical approach takes into account the incomplete purification of industrial captured CO₂ and the related effects during injection, and provides relevant data for long-term storage simulations of this specific greenhouse gas. Batch experiments were conducted to investigate the interactions of supercritical CO₂, brine and rock-forming mineral concentrates (albite, microcline, kaolinite, biotite, muscovite, calcite, dolomite and anhydrite) using a newly developed experimental setup. After up to 42 day (1000 h) experiments using pure and impure supercritical CO₂ the dissolution and solution characteristics were examined by XRD, XRF, SEM and EDS for the solid, and ICP–MS and IC for the fluid reactants, respectively. Experiments with mixtures of supercritical CO₂ (99.5 vol.%) and SO₂ or NO₂ impurities (0.5 vol.%) suggest the formation of H₂SO₄ and HNO₃, reflected in pH values between 1 and 4 for experiments with silicates and anhydrite and between 5 and 6 for experiments with carbonates. These acids should be responsible for the general larger amount of cations dissolved from the mineral phases compared to experiments using pure CO₂. For pure CO₂ a pH of around 4 was obtained using silicates and anhydrite, and 7–8 for carbonates. Dissolution of carbonates was observed after both pure and impure CO₂ experiments. Anhydrite was corroded by approximately 50 wt.% and gypsum precipitated during experiments with supercritical CO₂ + NO₂. Silicates do not exhibit visible alterations during all experiments but released an increasing amount of cations in the reaction fluid during experiments with impure CO₂. Nonetheless, precipitated secondary carbonates could not be identified.     

Influence of a CO2 long term exposure on the mobilisation and speciation of metals in soils

This study investigates the potential risks associated with high levels and long term exposure of carbon dioxide (CO₂) on the mobility and speciation of exchangeable metals in soils. CO₂ incubation batch experiments at high pressure and temperature coupled with geochemical modelling were carried out to elucidate the behaviour and mobilisation of metals and the response of soil chemical parameters as a result of long term CO₂ exposure. A t-Student analysis was performed to ascertain whether differences in the mean concentration of exchangeable metals in soils before and after CO₂-incubations are attributable to increase of metal molibilisation because of the long term CO₂ exposure. The t-Student revealed the CO₂ long term incubation was statistically significant (p < 0.05) for the exchangeable concentration of Ni, Zn, and Pb. The CO₂-soil incubation induces the acidification of the pore water of soils via CO₂ hydrolysis and as a consequence, it increases the exchangeable concentration of Ni, Zn, and Pb in the soils. As, Al, Cr, Cu, and Fe show a different mobilisation pattern depending on the moisture content in soils. Al³⁺, Fe²⁺, Cr³⁺, and Cu²⁺ as free cations, As as HAsO₂, Pb²⁺and PbHCO₃⁻, Zn²⁺ and ZnHCO₃⁻, are predicted to be the predominant aqueous complexes in the pore water of the incubated soils.     

Composition and origin of coalbed gases in the Lower Silesian basin,southwest Poland

Coalbed gases in the Lower Silesian Coal Basin (LSCB) of Poland are highly variable in both their molecular and stable isotope compositions. Geochemical indices and stable isotope ratios vary within the following ranges: hydrocarbon (C_HC) index C_HC=CH₄/(C₂H₆₊ C₃H₈) from 1.1 to 5825, wet gas (C₂₊) index C₂₊=(C₂H₆₊ C₃H₈₊ C₄H₁₀₊ C₅H₁₂) / (CH₄₊ C₂H₆₊ C₃H₈₊ C₄H₁₀₊ C₅H₁₂) 100 (%) from 0.0 to 48.3%, CO₂–CH₄ (CDMI) index CDMI=CO₂/(CO₂₊ CH₄) 100 (%) from 0.1 to 99.9%, δ¹³C(CH₄) from −66.1 to −24.6‰, δD(CH₄) from −266 to −117‰, δ¹³C(C₂H₆) from −27.8 to −22.8‰, and δ¹³C(CO₂) from −26.6 to 16.8‰. Isotopic studies reveal the presence of 3 genetic types of natural gases: thermogenic (CH₄, higher gaseous hydrocarbons, and CO₂), endogenic CO₂, and microbial CH₄ and CO₂. Thermogenic gases resulted from coalification processes, which were probably completed by Late Carboniferous and Early Permian time. Endogenic CO₂ migrated along the deep-seated faults from upper mantle and/or magma chambers. Minor volumes of microbial CH₄ and CO₂ occur at shallow depths close to the abandoned mine workings. “Late-stage” microbial processes have commenced in the Upper Cretaceous and are probably active at present. However, depth-related isotopic fractionation which has resulted from physical and physicochemical (e.g. diffusion and adsorption/desorption) processes during gas migration cannot be neglected. The strongest rock and gas outbursts occur only in those parts of coal deposits of the LSCB which are dominated by large amounts of endogenic CO₂.     

A new solid state diffusion model applied to inverse zoning and diffusion rims in minerals

Any oxide and silicate mineral which is nominally anhydrous but crystallized in the presence of H₂O incorporates traces of H₂O in solid solution. In the case of MgO it can be shown that OH^? pairs convert into H₂+O ₂ ^2? . If the H₂ molecules are lost, the O ₂ ^2? remain in the lattice as excess oxygen stabilized by excess cation vacancies. When the O ₂ ^2? anions decay either thermally or by decompression unbound O^? states (positive holes) are generated which lead to surface charges and subsurface space charge layers. Calculated space charge profiles are presented. O^? concentrations as small as 10–20 ppm suffice to create electric surface fields of the order of 4·10⁷ V·m^?1. The diffusion mechanism which derives from these premises incorporates novel features: the cation diffusion is coupled to the counterdiffusion of unbound and vacancy-bound O^? states. The cation diffusion is predicted to be very fast because first, it is field-enhanced (electrochemically driven) and second, it is not rate-limited by the intrinsic cation vacancy concentration nor by the counter-diffusion of other cations. The model may apply to cases of inverse zoning and diffusion rim formation in minerals under certain P-T conditions.     

A Revised Analytical Method for HCO3- and CO32-Determinations in Geothermal Waters: An Assessment of IAGC and IAEA Interlaboratory Comparisons

A statistical evaluation of the results of HCO₃^‐ determinations in geothermal waters during the interlaboratory comparison programmes of the International Association of Geochemistry and Cosmochemistry (IAGC) and International Atomic Energy Agency (IAEA) indicated that the analytical uncertainty increases with decreasing concentration of HCO_3‐ and was ? 25% for 50 μg ml^‐1 and ? 60% for 25 μg ml^‐1 of HCO₃^‐. The analytical method (Method 1) used by chemists and hydrologists works well for waters containing carbonic alkalinity, whereas Method 2 used by geochemists is conceptually incorrect. A stepwise comparison between the theoretical and experimental titration results for a given concentration Na₂CO₃ (0.0988 mol l^‐1) solution was performed to understand the limitations of the titration method for geothermal water analysis. Backward titration from the carbonic acid equivalence point (H₂CO₃EP) to the original pH after CO₂ removal, as had been practised earlier in the geothermal industry, in order to estimate the contribution of silicic and boric alkalinities to the total alkalinity, is incorrect because the amount of standard base (NaOH) added is equivalent to silicic and boric alkalinities plus some OH^‐ alkalinity. In a Na₂CO₃ solution, the added NaOH is equivalent to OH^‐ alkalinity only. Backward titration is only needed from the forward titration end point to the H₂CO₃EP in order to correct the total alkalinity for the excess of standard acid (HCl) added during the forward titration. In the case of a Na₂CO₃ solution, the H₂CO₃EP, after removal of CO₂ during the forward titration, is at pH = 7, not at pH = 4.5 (3.8) as has been considered in literature. Similarly, the liberation of CO₂ during titration occurs well before the point expected theoretically and it is less for shorter titration time. The revised procedure for the determination of carbonic species concentration is presented and illustrated for a water sample from Alchichica Lake, Puebla, Mexico.     

The microdetermination of H2O,CO2, and SO2 in glass using a 1280°C microscope vacuum heating stage,cryopumping, and vapor pressure measurements from 77 to 273 K

A new microscope vacuum heating stage and gas analyzer has been developed for measurement of H₂O, CO₂, SO₂, and noncondensable gas (H₂, CO, N₂, Ar, CH₄, etc.) evolved from samples, particularly natural glass, at temperatures up to 1280°C. The gas evolved upon heating to 1280δC is collected in a liquid nitrogen cold trap. Gas components are identified by the characteristic vapor pressure and temperature ranges over which solid and vapor are in equilibrium during sublimation of individual components. The masses of CO₂, SO₂, and H₂O derived from samples and blanks are calculated using the ideal gas law, the molecular weights of the components, and the gauge constant (i.e. the ratio of the number of moles of a gas to its partial pressure in the constant volume). Results obtained by repeated determinations of H₂O, CO₂, and SO₂ evolved from a submarine basaltic glass from Kilauea volcano, Hawaii, (average sample mass = 3 × 10^?3 g) gave probable errors for the determinations of H₂O (0.23%), CO₂ (0.025%), and S (0.071%) equal to 4, 10, and 8% respectively, of the concentrations. Determinations of H₂O in smaller samples of H₂O-poor basaltic pumice show a linear proportionality (0.063%) between the measured H₂O and the sample mass over the range 0.1 × 10^?6 to 1.7 × 10^?6 g H₂O. Comparisons of H₂O determinations by this technique with those obtained by Penfield, gas chromatic, microcoulometric, and vacuum fusion techniques used elsewhere show reasonably good agreement. Determinations of SO₂ by this technique agree reasonably well X-ray fluorescence and electron microprobe determinations of sulfur. Determinations of CO₂ by the present technique are reproducible but cannot be compared directly to measurements made in other labs because of differences in samples analyzed. The principle advantages of this analytical technique are the very small sample required, the simultaneous determination of H₂O, CO₂, SO₂ and noncondensable gas, the avoidance of calibration procedures dependent on chemical standards, and the visual observations that can be made during sample outgassing.     

Fluid inclusion geochemistry of the early Proterozoic Pirilä gold deposit in Rantasalmi,Southeastern Finland

The small Pirilä gold deposit, which is located in the southeastern part of the Svecofennian complex near the Archean/Proterozoic boundary, is hosted by quartz veins and lenses occurring in mica schist. The rocks of the area were metamorphosed under conditions of amphibolite facies. Gold is invariably associated with sulphides. Microthermometry of fluid inclusions in quartz indicates four types of inclusions: (1) weakly saline H₂O-CO₂ (< 4.0 eq.wt% NaCl) with small amounts of CH₄ (< 10 mole% CH₄); (2) CO₂ (< 10 mole% CH₄); (3) CH₄; and (4) H₂O (< 25 eq.wt% NaCl) with less than 0.85 mole% CO₂ in the vapour phase. Texturally these inclusion types are classified as primary (H₂O-CO₂) and secondary (H₂O, CO₂ and CH₄). Leachate analysis shows that, in addition to Na, the aqueous fluids contain Ca and Fe with minor amounts of K and Mg. The primary H₂O-CO₂ and the secondary H₂O inclusions contain sulphide and unidentified opaque grains, respectively. The secondary CH₄ inclusions are often associated with short trails of arsenopyrite grains. Fluid inclusion and geological data suggest ore mineral mobilization, crystallization of host quartz, and deposition of sulphides controlled by the D₂ and D₃ structures in the presence of a H₂O-CO₂ fluid mainly during the plastic D₃ deformation and during the amphibolite facies metamorphism (i.e. 3.4 kbars/540–670°C). During ductile-brittle deformation (probably D₄), precipitation of tectonic remobilized gold from sulphides in fractures occurred in the presence of CH₄ and H₂O fluids at lowered temperature (< 440°C) and pressure (< 2 kbars).     

CO<Subscript>2</Subscript> Air–Sea Exchange due to Calcium Carbonate and Organic Matter Storage,and its Implications for the Global Carbon Cycle

Release of CO₂ from surface ocean water owing to precipitation of CaCO₃ and the imbalance between biological production of organic matter and its respiration, and their net removal from surface water to sedimentary storage was studied by means of a quotient θ = (CO₂ flux to the atmosphere)/(CaCO₃ precipitated). θ depends not only on water temperature and atmospheric CO₂ concentration but also on the CaCO₃ and organic carbon masses formed. In CO₂ generation by CaCO₃ precipitation, θ varies from a fraction of 0.44 to 0.79, increasing with decreasing temperature (25 to 5°C), increasing atmospheric CO₂ concentration (195–375 ppmv), and increasing CaCO₃ precipitated mass (up to 45% of the initial DIC concentration in surface water). Primary production and net storage of organic carbon counteracts the CO₂ production by carbonate precipitation and it results in lower CO₂ emissions from the surface layer. When atmospheric CO₂ increases due to the ocean-to-atmosphere flux rather than remaining constant, the amount of CO₂ transferred is a non-linear function of the surface layer thickness because of the back-pressure of the rising atmospheric CO₂. For a surface ocean layer approximated by a 50-m-thick euphotic zone that receives input of inorganic and organic carbon from land, the calculated CO₂ flux to the atmosphere is a function of the CaCO₃ and C_org net storage rates. In general, the carbonate storage rate has been greater than that of organic carbon. The CO₂ flux near the Last Glacial Maximum is 17 to 7×10¹² mol/yr (0.2–0.08 Gt C/yr), reflecting the range of organic carbon storage rates in sediments, and for pre-industrial time it is 38–42×10¹² mol/yr (0.46–0.50 Gt C/yr). Within the imbalanced global carbon cycle, our estimates indicate that prior to anthropogenic emissions of CO₂ to the atmosphere the land organic reservoir was gaining carbon and the surface ocean was losing carbon, calcium, and total alkalinity owing to the CaCO₃ storage and consequent emission of CO₂. These results are in agreement with the conclusions of a number of other investigators. As the CO₂ uptake in mineral weathering is a major flux in the global carbon cycle, the CO₂ weathering pathway that originates in the CO₂ produced by remineralization of soil humus rather than by direct uptake from the atmosphere may reduce the relatively large imbalances of the atmosphere and land organic reservoir at 10²–10⁴-year time scales.     

Detailed compositional analysis of gas seepage at the National Carbon Storage Test Site,Teapot Dome,Wyoming, USA

A baseline determination of CO₂ and CH₄ fluxes and soil gas concentrations of CO₂ and CH₄ was made over the Teapot Dome oil field in the Naval Petroleum Reserve No. 3 (NPR-3) in Wyoming, USA. This was done in anticipation of experimentation with CO₂ sequestration in the Pennsylvanian Tensleep Sandstone underlying the field at a depth of 1680 m.The baseline data were collected during the winter, 2004 in order to minimize near-surface biological activity in the soil profile. The baseline data were used to select anomalous locations that may be the result of seeping thermogenic gas, along with background locations. Five 10-m holes were drilled, 3 of which had anomalous gas microseepage, and 2 were characterized as “background.” These were equipped for nested gas sampling at depths of 10-, 5-, 3-, 2-, and 1-m depths. Methane concentrations as high as 170,000 ppmv (17%) were found, along with high concentrations of C₂H₆, C₃H₈, n-C₄H₁₀, and i-C₄H₁₀. Much smaller concentrations of C₂H₄ and C₃H₆ were observed indicating the beginning of hydrocarbon oxidation in the anomalous holes. The anomalous 10-m holes also had high concentrations of isotopically enriched CO₂, indicating the oxidation of hydrocarbons. Concentrations of the gases decreased upward, as expected, indicating oxidation and transport into the atmosphere. The ancient source of the gases was confirmed by ¹⁴C determinations on CO₂, with radiocarbon ages approaching 38 ka within 5 m of the surface.Modeling was used to analyze the distribution of hydrocarbons in the anomalous and background 10-m holes. Diffusion alone was not sufficient to account for the hydrocarbon concentration distributions, however the data could be fit with the addition of a consumptive reaction. First-order rate constants for methanotrophic oxidation were obtained by inverse modeling. High rates of oxidation were found, particularly near the surface in the anomalous 10-m holes, demonstrating the effectiveness of the process in the attenuation of CH₄ microseepage. The results also demonstrate the importance of CH₄ measurements in the planning of a monitoring and verification program for geological CO₂ sequestration in sites with significant remaining hydrocarbons (i.e. spent oil reservoirs).     

Crystallization conditions and evolution of magmatic fluids in the Harney Peak Granite and associated pegmatites, Black Hills, South Dakota—Evidence from fluid inclusions

A microthermometric study of inclusions in granites and pegmatites in the Proterozoic Harney Peak Granite system identified four types of inclusions. Type 1 inclusions are mixtures of CO₂ and H₂O and have low salinities, on average 3.5 wt.% NaCl_eq; type 2 inclusions are aqueous solutions of variable salinities, from 0 to 40% wt.% NaCl_eq; type 3 inclusions are carbonic, dominated by CO₂, with no detectable water; and type 4 inclusions consist of 20 to 100% solids, with the remaining volume occupied by a CO₂-H₂O fluid. Many inclusions have a secondary character; however, a primary character can be unambiguously established in several occurrences of the type 1 inclusions. These inclusions were trapped above the solidus and represent the exsolved magmatic fluid. The secondary populations of types 1, 2, and 3 probably formed as a result of reequilibration and unmixing of the type 1 fluid that progressively changed composition and density with decreasing temperature and pressure and was finally trapped along healed microfractures under subsolidus conditions. Type 4 inclusions are primary and are interpreted to be trapped, fluid-bearing, complex silicate melts that subsequently solidified or underwent other posttrapping changes.It is demonstrated that primary type 1 fluid inclusions that coexist with crystallized melt inclusions in the complex, Li-bearing Tin Mountain pegmatite were trapped along the two-fluid phase boundary in the system CO₂-H₂O-NaCl_eq. Consequently, the temperature and pressure conditions of trapping are identical to the bulk homogenization conditions—on average 340°C and 2.7 kbar. These conditions indicate that this Li-, Cs-, Rb-, P-, and B-rich pegmatite crystallized at some of the lowest known temperatures for a silicate melt in the crust. An internally consistent, empirical solvus surface in P-T-X_CO2 coordinates was generated for the pseudobinary CO₂-(H₂O-4.3 wt.% NaCl_eq) pegmatite fluid system. Distribution coefficients for the major species CO₂, H₂O, NaCl, and CH₄ between the immiscible CO₂-rich and H₂O-rich fluid phases as a function of pressure and temperature were extracted from data for the two cogenetic fluid inclusions types.     

Fluid inclusions in high-grade gneisses of the Kapuskasing structural zone,Ontario: metamorphic fluids and uplift/erosion path

Fluid inclusions in quartz grains from five samples of high-grade rocks (two paragneisses, an amphibolite, a mafic gneiss and a tonalite dike) from the 2.7 Ga Kapuskasing structural zone (KSZ), Ontario, were examined with petrographic, microthermometric and laser Raman techniques. Three types of fluid inclusions were observed: CO₂-rich, H₂O-rich and mixed CO₂-H₂O. CO₂-rich fluid inclusions are pseudosecondary or secondary in nature and are generally pure CO₂; a few contain varying amounts of CH₄·H₂O-rich fluid inclusions are secondary in nature, contain variable amounts of dissolved salts, and generally contain daughter crystals. Mixed CO₂-H₂O fluid inclusions occur where trails of H₂O-rich inclusions intersect trails of CO₂-rich inclusions. Isochores for high density (p=1.03 g/cm³) pseudosecondary, pure CO₂ inclusions intersect the lower pressure portion of the estimated P-T field for high-grade metamorphism, implying that pure CO₂ was the peak metamorphic fluid. The variable CH₄ content of CO₂ inclusions within graphite-bearing samples suggests that CH₄ was introduced locally after the formation of the CO₂ inclusions; however the origin of the CH₄ remains problematic. An aqueous fluid clearly penetrated the gneisses after the peak metamorphism (during uplift/erosion), forming secondary inclusions and contributing to the minor retrogressive hydration observed in these rocks. The presence of the pseudosecondary, high-density CO₂ inclusions in quartz crystals in the KSZ rocks constrains the uplift/ erosion path for the KSZ to one of simultaneous decrease in pressure and temperature.