Supercritical Carbon Dioxide Extraction of Organic Matter from Petroleum Source Rocks and Its Implications

Organic matter was experimentally extracted by supercritical fluids(CO2 1% isopropanol)from petroleum source rocks of different thermo-maturities at different buried depths in the same stratigraphic unit in the Dongying Basin.The results show that supercritical fluid extraction(SFE)is more effective than Soxhlet extraction(SE),with higher amounts and greater varieties of hydrocarbons and soluble organic matter becoming extractive.The supercritical CO2 extraction is therefore considered more valuable in evaluation of petroleum source rocks and oil resources,particularly those of immature types.     

长岭凹陷深层天然气藏中CO_2及CH_4充注次序的流体包裹体证据

对长岭凹陷深层天然气藏储层——营城组火山岩中发育的流体包裹体进行了详细研究,结果表明在火山岩发育的石英、方解石细网脉中均存在较多的碳质流体包裹体,单个包裹体激光拉曼光谱分析结果表明其主要为CO2及CH4两种类型的碳质包裹体。其中方解石细网脉体中发育有原生及次生CH4包裹体,而含CO2包裹体多以原生包裹体产于石英细网脉中。很多含CO2包裹体的石英细脉中发现了含CH4包裹体的方解石脉体的角砾,这就表明石英细脉形成晚于方解石细脉。营城组火山岩储层中CO2及CH4包裹体的产状特征研究表明,松辽盆地深层天然气藏的形成系火山岩成岩后CO2及CH4等气体不同期次充注的结果,CH4气的充注时间早于CO2气,火山岩中发育的原生孔隙及次生裂隙为上述气体的充注和聚集提供了重要通道。     

Oxygen isotope exchange between H2O and CO2 at elevated CO2 pressures: Implications for monitoring of geological CO2 storage

Traditionally, the application of stable isotopes in Carbon Capture and Storage (CCS) projects has focused on δ¹³C values of CO₂ to trace the migration of injected CO₂ in the subsurface. More recently the use of δ¹⁸O values of both CO₂ and reservoir fluids has been proposed as a method for quantifying in situ CO₂ reservoir saturations due to O isotope exchange between CO₂ and H₂O and subsequent changes in δ¹⁸O_H2O values in the presence of high concentrations of CO₂. To verify that O isotope exchange between CO₂ and H₂O reaches equilibrium within days, and that δ¹⁸O_H2O values indeed change predictably due to the presence of CO₂, a laboratory study was conducted during which the isotope composition of H₂O, CO₂, and dissolved inorganic C (DIC) was determined at representative reservoir conditions (50 °C and up to 19 MPa) and varying CO₂ pressures. Conditions typical for the Pembina Cardium CO₂ Monitoring Pilot in Alberta (Canada) were chosen for the experiments. Results obtained showed that δ¹⁸O values of CO₂ were on average 36.4 ± 2.2‰ (1σ, n = 15) higher than those of water at all pressures up to and including reservoir pressure (19 MPa), in excellent agreement with the theoretically predicted isotope enrichment factor of 35.5‰ for the experimental temperatures of 50 °C. By using ¹⁸O enriched water for the experiments it was demonstrated that changes in the δ¹⁸O values of water were predictably related to the fraction of O in the system sourced from CO₂ in excellent agreement with theoretical predictions. Since the fraction of O sourced from CO₂ is related to the total volumetric saturation of CO₂ and water as a fraction of the total volume of the system, it is concluded that changes in δ¹⁸O values of reservoir fluids can be used to calculate reservoir saturations of CO₂ in CCS settings given that the δ¹⁸O values of CO₂ and water are sufficiently distinct.     

松辽盆地含CO_2火山岩气藏的形成和分布

松辽盆地特有的深部构造背景和裂谷演化特征,造成盆地内含CO_2火山岩气藏的形成和富集。松辽裂谷盆地中新生代火山岩浆活动发育,总体上具有多期喷发、分布广泛和储集条件良好的特点。火山活动以中心式喷发为主,主要发育中基性-酸性火山岩,发育流纹岩、凝灰岩等多种岩石类型,爆发相和溢流相2种火山岩相。中生代火山岩在盆地内分布广泛,营域组构成深层有利储层,新生代火山岩在盆地外围出露较多,而在盆内出露较少。盆地高含量的二氧化碳为无机幔源成因,由青山口期和新生代幔源岩浆脱气形成。含CO_2火山岩气藏的形成主要受深部构造背景、深大断裂和中新生代火山岩控制。已发现含CO_2火山岩气藏主要分布于古中央隆起带及其两侧断陷的营城组火山岩中,具有点状、带状分布,局部富集的特点。根据主控因素分析,预测了5个CO_2富集区带。     

Geochemical effects of CO2 sequestration in sandstones under simulated in situ conditions of deep saline aquifers

The geochemical effects of brine and supercritical CO₂ (SCCO₂) on reservoir rocks from deep (1500–2000 m) saline aquifers were examined via experimental simulation at in situ conditions. Dry sandstone samples were mounted in a triaxial cell and autoclave system, evacuated, and saturated with 1 M NaCl solution. The brine-rock system was allowed to react at 30 MPa confining pressure, 15 MPa pore fluid pressure, and 60 °C while SCCO₂ was injected at a pressure gradient of 1–2 MPa. The experiment was conducted for a period of 1496 h, during which fluids were periodically sampled and analyzed. The pH measured in partially degassed fluid samples at 25 °C decreased from a starting value of 7.0–4.3 (9 days) and finally 5.1 after saturation with SCCO₂.     

接触变质条件下变碳酸岩CO2释放与定量计算——以郯庐断裂南段肥东县双山为例

为了探讨接触变质带内变碳酸盐岩变质过程CO₂释放的数量和排放CO₂的物理、化学及地质条件,根据递进变质反应和时间积分流体通量模型,定量分析和定量计算了双山地区变碳酸盐岩在接触变质作用中释放CO₂的通量。计算结果得到CO₂的通量值为0.729×104~2.446×104 mol/cm2,CO₂的来源以接触变质反应释放为主;CO₂的生成释放与变质程度呈正相关关系。自白云石带至方解石带变质流体中X_CO2不断升高,但钙铝榴石带由于岩浆水影响,流体通量最高而X_CO2急剧下降。      

Caprock interaction with CO2: A laboratory study of reactivity of shale with supercritical CO2 and brine

Crushed rock from two caprock samples, a carbonate-rich shale and a clay-rich shale, were reacted with a mixture of brine and supercritical CO₂ (CO₂–brine) in a laboratory batch reactor, at different temperature and pressure conditions. The samples were cored from a proposed underground CO₂ storage site near the town of Longyearbyen in Svalbard. The reacting fluid was a mixture of 1 M NaCl solution and CO₂ (110 bar) and the water/rock ratio was 20:1. Carbon dioxide was injected into the reactors after the solution had been bubbled with N₂, in order to mimic O₂-depleted natural storage conditions. A control reaction was also run on the clay-rich shale sample, where the crushed rock was reacted with brine (CO₂-free brine) at the same experimental conditions. A total of 8 batch reaction experiments were run at temperatures ranging from 80 to 250 °C and total pressures of 110 bar (∼40 bar for the control experiment). The experiments lasted 1–5 weeks.Fluid analysis showed that the aqueous concentration of major elements (i.e. Ca, Mg, Fe, K, Al) and SiO₂ increased in all experiments. Release rates of Fe and SiO₂ were more pronounced in solutions reacted with CO₂–brine as compared to those reacted with CO₂-free brine. For samples reacted with the CO₂–brine, lower temperature reactions (80 °C) released much more Fe and SiO₂ than higher temperature reactions (150–250 °C). Analysis by SEM and XRD of reacted solids also revealed changes in mineralogical compositions. The carbonate-rich shale was more reactive at 250 °C, as revealed by the dissolution of plagioclase and clay minerals (illite and chlorite), dissolution and re-precipitation of carbonates, and the formation of smectite. Carbon dioxide was also permanently sequestered as calcite in the same sample. The clay-rich shale reacted with CO₂–brine did not show major mineralogical alteration. However, a significant amount of analcime was formed in the clay-rich shale reacted with CO₂-free brine; while no trace of analcime was observed in either of the samples reacted with CO₂–brine.     

二氧化碳羽流地热系统的碳封存经济分析

【研究目的】 二氧化碳羽流地热系统（CPGS）在取热的同时可实现CO₂地质封存，在碳达峰与碳中和背景下，CPGS碳封存的经济性是众多学者关注的要点。【研究方法】 以松辽盆地泉头组为例，采用数值模拟方法对比分析了注入压力、井间距与回注温度对热提取率的影响，在供暖情景下，计算了CPGS供暖效益与碳封存成本，并与常规水热型地热系统供暖效益进行了对比。【研究结果】 受携热介质转变与热突破影响，CPGS开采井温度呈现“降低-稳定-降低”的趋势，其中井间距对开采井温降影响显著，井间距越小开采井温降越明显；热提取率与回注压力呈现正相关性，与回注温度呈现负相关性，井间距对热提取率影响不显著；CPGS与常规水热型地热系统相比，采热量呈现“高-低-高”三个阶段，其中回注压力越小、回注温度与储层温度越接近，实现CPGS较水介质多采热能所需的时间越短。【结论】 仅考虑CO₂价格与取热效益，供暖收益抵消部分碳封存成本后，井间距对CO₂封存单位成本影响最为显著，井间距越小，CO₂封存单位成本降低越迅速，在注采井间距300 m条件下，持续开采30 a后CO₂封存单位成本可降至160元/t。     

Carbon-13 exchange between CO2 and CH4 under geothermal conditions

On the basis of recently reported data on the kinetics of carbon-13 exchange between CO₂ and CH₄ at temperatures above 500°C, first order rate constants $\text{log k = 11.16?10,190/T}$ were derived allowing variations in Δ, the difference in the isotopic composition of coexisting CO₂ and CH₄, to be evaluated as a function of initial composition and cooling rate of the rising geothermal fluid. Observed Δ-values in geothermal discharges are likely to represent frozen in compositions attained after minimum residence times of 20 ka at 400°C or 10 Ma at 300°C. The carbon-13 contents of any biogenic gases are unlikely to have been affected by thermal re-equilibration at temperatures below 200°C. The chemical equilibrium involving CO₂ and CH₄ can be expected to proceed about a hundred times faster than isotopic equilibration.     

Geologic factors controlling CO2 storage capacity and permanence: case studies based on experience with heterogeneity in oil and gas reservoirs applied to CO2 storage

A variety of structural and stratigraphic factors control geological heterogeneity, inferred to influence both sequestration capacity and effectiveness, as well as seal capacity. Structural heterogeneity factors include faults, folds, and fracture intensity. Stratigraphic heterogeneity is primarily controlled by the geometry of depositional facies and sandbody continuity, which controls permeability structure. The permeability structure, in turn, has implications for CO₂ injectivity and near-term migration pathways, whereas the long-term sequestration capacity can be inferred from the production history. Examples of Gulf Coast oil and gas reservoirs with differing styles of stratigraphic heterogeneity demonstrate the impact of facies variability on fluid flow and CO₂ sequestration potential. Beach and barrier-island deposits in West Ranch field in southeast Texas are homogeneous and continuous. In contrast, Seeligson and Stratton fields in south Texas, examples of major heterogeneity in fluvial systems, are composed of discontinuous, channel-fill sandstones confined to narrow, sinuous belts. These heterogeneous deposits contain limited compartments for potential CO₂ storage, although CO₂ sequestration effectiveness may be enhanced by the high number of intraformational shale beds. These field examples demonstrate that areas for CO₂ storage can be optimized by assessing sites for enhanced oil and gas recovery in mature hydrocarbon provinces.     

Brucite [Mg(OH2)] carbonation in wet supercritical CO2: An in situ high pressure X-ray diffraction study

Understanding mechanisms and kinetics of mineral carbonation reactions relevant to sequestering carbon dioxide as a supercritical fluid (scCO₂) in geologic formations is crucial to accurately predicting long-term storage risks. Most attention so far has been focused on reactions occurring between silicate minerals and rocks in the aqueous dominated CO₂-bearing fluid. However, water-bearing scCO₂ also comprises a reactive fluid, and in this situation mineral carbonation mechanisms are poorly understood. Using in situ high-pressure X-ray diffraction, the carbonation of brucite [Mg(OH)₂] in wet scCO₂ was examined at pressure (82 bar) as a function of water concentration and temperature (50 and 75 °C). Exposing brucite to anhydrous scCO₂ at either temperature resulted in little or no detectable reaction over three days. However, addition of trace amounts of water resulted in partial carbonation of brucite into nesquehonite [MgCO₃·3H₂O] within a few hours at 50 °C. By increasing water content to well above the saturation level of the scCO₂, complete conversion of brucite into nesquehonite was observed. Tests conducted at 75 °C resulted in the conversion of brucite into magnesite [MgCO₃] instead, apparently through an intermediate nesquehonite step. Raman spectroscopy applied to brucite reacted with ¹⁸O-labeled water in scCO₂ show it was incorporated into carbonate at a relatively high concentration. This supports a carbonation mechanism with at least one step involving a direct reaction between the mineral and water molecules without mediation by a condensed aqueous layer.     

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.     

GEOCARBSULF: A combined model for Phanerozoic atmospheric O2 and CO2

A model for the combined long-term cycles of carbon and sulfur has been constructed which combines all the factors modifying weathering and degassing of the GEOCARB III model [Berner R.A., Kothavala Z., 2001. GEOCARB III: a revised model of atmospheric CO₂ over Phanerozoic time. Am. J. Sci. 301, 182-204] for CO₂ with rapid recycling and oxygen dependent carbon and sulfur isotope fractionation of an isotope mass balance model for O₂ [Berner R.A., 2001. Modeling atmospheric O₂ over Phanerozoic time. Geochim. Cosmochim. Acta65, 685-694]. New isotopic data for both carbon and sulfur are used and new feedbacks are created by combining the models. Sensitivity analysis is done by determining (1) the effect on weathering rates of using rapid recycling (rapid recycling treats carbon and sulfur weathering in terms of young rapidly weathering rocks and older more slowly weathering rocks); (2) the effect on O₂ of using different initial starting conditions; (3) the effect on O₂ of using different data for carbon isotope fractionation during photosynthesis and alternative values of oceanic δ¹³C for the past 200 million years; (4) the effect on sulfur isotope fractionation and on O₂ of varying the size of O₂ feedback during sedimentary pyrite formation; (5) the effect on O₂ of varying the dependence of organic matter and pyrite weathering on tectonic uplift plus erosion, and the degree of exposure of coastal lands by sea level change; (6) the effect on CO₂ of adding the variability of volcanic rock weathering over time [Berner, R.A., 2006. Inclusion of the weathering of volcanic rocks in the GEOCARBSULF model. Am. J. Sci.306 (in press)]. Results show a similar trend of atmospheric CO₂ over the Phanerozoic to the results of GEOCARB III, but with some differences during the early Paleozoic and, for variable volcanic rock weathering, lower CO₂ values during the Mesozoic. Atmospheric oxygen shows a major broad late Paleozoic peak with a maximum value of about 30% O₂ in the Permian, a secondary less-broad peak centered near the Silurian/Devonian boundary, variation between 15% and 20% O₂ during the Cambrian and Ordovician, a very sharp drop from 30% to 15% O₂ at the Permo-Triassic boundary, and a more-or less continuous rise in O₂ from the late Triassic to the present.     

The problem of CO2 recycling in subduction zones

In connection with the imbalance between the carbon dioxide absorbed in the carbonate minerals in subduction zones and that emitted during island arc volcanism, the problem of redistribution the rest of the CO₂ from the plate to the mantle arises. Experimental modeling of the interaction between model analogs of the oceanic crust and the mantle wedge was performed for two systems: glaucophane schist-olivine and glaucophane schist-silicate marble-olivine under high pressure and varying temperature conditions that correspond to the oceanic crust-mantle transition zone in the subduction zone beneath the Cascade Mountains. The experiments carried out showed that there is a possibility that intensive CO₂ degassing occurs from the plate in the forearc area, which is controlled by carbonate dissolution in an aqueous fluid. As a result of this process, carbonates can redeposit in the form of magnesite in the overlying mantle rocks according to the vertical temperature gradient. It is assumed that part of the carbon dioxide bonded in mantle rocks can be transported by viscous flow from the forearc area to the deep mantle horizons within the field of the thermodynamic stability of magnesite. In addition, the experiments we carried out showed that between marble and olivine in the ultrahigh pressure a metasomatic column consisting of four zones develops: Fe-Mg-Ca carbonate|dolomite|diopside|magnesite.     

CO2 solubility in dacitic melts equilibrated with H2O-CO2 fluids: Implications for modeling the solubility of CO2 in silicic melts

The solubility of CO₂ in dacitic melts equilibrated with H₂O-CO₂ fluids was experimentally investigated at 1250°C and 100 to 500 MPa. CO₂ is dissolved in dacitic glasses as molecular CO₂ and carbonate. The quantification of total CO₂ in the glasses by mid-infrared (MIR) spectroscopy is difficult because the weak carbonate bands at 1430 and 1530 cm⁻¹ can not be reliably separated from background features in the spectra. Furthermore, the ratio of CO_2,mol/carbonate in the quenched glasses strongly decreases with increasing water content. Due to the difficulties in quantifying CO₂ species concentrations from the MIR spectra we have measured total CO₂ contents of dacitic glasses by secondary ion mass spectrometry (SIMS).At all pressures, the dependence of CO₂ solubility in dacitic melts on x^fluid_CO2,total shows a strong positive deviation from linearity with almost constant CO₂ solubility at x_CO2fluid > 0.8 (maximum CO₂ solubility of 795 ± 41, 1376 ± 73 and 2949 ± 166 ppm at 100, 200 and 500 MPa, respectively), indicating that dissolved water strongly enhances the solubility of CO₂. A similar nonlinear variation of CO₂ solubility with x_CO2fluid has been observed for rhyolitic melts in which carbon dioxide is incorporated exclusively as molecular CO₂ (Tamic et al., 2001). We infer that water species in the melt do not only stabilize carbonate groups as has been suggested earlier but also CO₂ molecules.A thermodynamic model describing the dependence of the CO₂ solubility in hydrous rhyolitic and dacitic melts on T, P, f_CO2 and the mol fraction of water in the melt (x_water) has been developed. An exponential variation of the equilibrium constant K₁ with x_water is proposed to account for the nonlinear dependence of x_CO2,totalmelt on x_CO2fluid. The model reproduces the CO₂ solubility data for dacitic melts within ±14% relative and the data for rhyolitic melts within 10% relative in the pressure range 100-500 MPa (except for six outliers at low x_CO2fluid). Data obtained for rhyolitic melts at 75 MPa and 850°C show a stronger deviation from the model, suggesting a change in the solubility behavior of CO₂ at low pressures (a Henrian behavior of the CO₂ solubility is observed at low pressure and low H₂O concentrations in the melt). We recommend to use our model only in the pressure range 100-500 MPa and in the x_CO2fluid range 0.1-0.95. The thermodynamic modeling indicates that the partial molar volume of total CO₂ is much lower in rhyolitic melts (31.7 cm³/mol) than in dacitic melts (46.6 cm³/mol). The dissolution enthalpy for CO₂ in hydrous rhyolitic melts was found to be negligible. This result suggests that temperature is of minor importance for CO₂ solubility in silicic melts.     

The role of CO2 in the chemical modification of deep continental crust

Compositional differences between granulite facies rocks and equivalent amphibolite facies rocks and the observation of CO₂-rich fluid inclusions in granulites, have led to the suggestion that CO₂ must play a role in modifying the composition of deep continental crust. How CO₂ effects this change has remained unclear. Using the thermodynamic properties of aqueous ions in a fluid of evolving $\text{CO}{}_2\text{H}{}_2\text{O}$ ratio, it is possible to model the incongruent dissolution of feldspars under conditions appropriate for granulite facies metamorphism. The results demonstrate that dissolution will be strongly enhanced at high $\text{CO}{}_2\text{H}{}_2\text{O}$ ratios, with ion solubilities being Na⁺ >K⁺ ? Ca⁺⁺. This enhancement is compatible with the reported compositional contrasts between granulite and amphibolite facies rock, but requires large fluid volumes.To test the dissolution model, a detailed field and petrologic study was conducted in a well exposed granulite facies terrane in West Greenland. Strong correlation between fluid composition and bulk rock chemistry can be documented; CO₂-rich regions contain rocks which consistently have low ratios, while H₂O-rich regions consistently have high ratios. Magnetite rims on sulfide grains are ubiquitous in high regions and are absent in high regions, and they provide evidence that CO₂ was introduced into the region. These correlations and observations are predictable from the properties of the dissolution process. These considerations, along with observations regarding graphite petrogenesis, provide strong arguments that the total fluid volume interacting with the rock during metamorphism was very large, in some cases equaling or exceeding total rock volume. Such large fluid volumes can lead to significant compositional modification of the crust, and will mask the original protolith chemistry. Such processes should lead to Ca- and Al-enriched, Na-, K-, S- and Si-depleted residues in the deep crust.     

蔡家营铅锌银矿区CO2异常分布特征及其成因的讨论

本文介绍了蔡家营矿区壤中气CO₂和岩矿石中热释CO₂异常的分布特征。通过CO₂异常分布与矿体赋存关系的研究,对异常形成机理做了初步探讨,阐明了厚覆盖区CO₂异常的分布规律,以及在寻找隐伏矿、查明区域控矿构造中的作用。     

Interactions between basalts and oil source rocks in rift basins： CO2 generation

Basalts interbedded with oil source rocks are discovered frequently in rift basins of eastern China, where CO2 is found in reservoirs around or within basalts, for example in the Binnan reservoir of the Dongying Depression. In the reservoirs, CO2 with heavy carbon isotopic composition (δ13C>-10‰ PDB) is in most cases accounts for 40% of the total gas reserve, and is believed to have resulted from degassing of basaltic magma from the mantle. In their investigations of the Binnan reservoir, the authors suggested that the CO2 would result from interactions between the source rocks and basalts. As the source rocks around basalts are rich in carbonate minerals, volcanic minerals, transition metals and organic matter, during their burial history some of the transition metals were catalyzed on the thermal degradation of organic matter into hydrocarbons and on the decomposition of carbonate minerals into CO2, which was reproduced in thermal simulations of the source rocks with the transition metals (Ni and Co). This kind of CO2 accounts for 55%-85% of the total gas reserve generated in the process of thermal simulation, and its δ13C values range from -11‰- -7.2‰ PDB, which are very similar to those of CO2 found in the Binnan reservoir. The co-generation of CO2 and hydrocarbon gases makes it possible their accumulation together in one trap. In other words, if the CO2 resulted directly from degassing of basaltic magma or was derived from the mantle, it could not be accumulated with hydrocarbon gases because it came into the basin much earlier than hydrocarbon generation and much earlier than trap formation. Therefore, the source rocks around basalts generated hydrocarbons and CO2 simultaneously through catalysis of Co and Ni transition metals, which is useful for the explanation of co-accumulation of hydrocarbon gases and CO2 in rift basins in eastern China.     

Atmospheric CO2 consumption by chemical weathering in North America

CO₂ consumption by chemical weathering is an integral part of the boundless carbon cycle, whose spatial patterns and controlling factors on continental scale are still not fully understood. A dataset of 338 river catchments throughout North America was used to empirically identify predictors of bicarbonate fluxes by chemical weathering and interpret the underlying controlling factors. Detailed analysis of major ion ratios enables distinction of the contributions of silicate and carbonate weathering and thus quantifying CO₂ consumption. Extrapolation of the identified empirical model equations to North America allows the analysis of the spatial patterns of the CO₂ consumption by chemical weathering.Runoff, lithology and land cover were identified as the major predictors of the riverine bicarbonate fluxes and the associated CO₂ consumption. Other influence factors, e.g. temperature, could not be established in the models. Of the distinguished land cover classes, artificial surfaces, dominated by urban areas, increase bicarbonate fluxes most, followed by shrubs, grasslands, managed lands, and forests. The extrapolation results in an average specific bicarbonate flux of 0.3 Mmol km⁻² a⁻¹ by chemical weathering in North America, of which 64% originates from atmospheric CO₂, and 36% from carbonate mineral dissolution. Chemical weathering in North America thus consumes 50 Mt atmospheric CO₂-C per year. About half of that originates from 10% of the area of North America.The estimated strength of individual predictors differs from previous studies. This highlights the need for a globally representative set of regionally calibrated models of CO₂ consumption by chemical weathering, which apply very detailed spatial data to resolve the heterogeneity of earth surface processes.     

Stable carbon isotopes of HCO3− in oil-field waters—implications for the origin of CO2

The δ¹³C values of dissolved HCO₃^? in 75 water samples from 15 oil and gas fields (San Joaquin Valley, Calif., and the Houston-Galveston and Corpus Christi areas of Texas) were determined to study the sources of CO₂ of the dissolved species and carbonate cements that modify the porosity and permeability of many petroleum reservoir rocks. The reservoir rocks are sandstones which range in age from Eocene through Miocene. The δ¹³C values of total HCO₃^? indicate that the carbon in the dissolved carbonate species and carbonate cements is mainly of organic origin.The range of δ¹³C values for the HCO₃^? of these waters is ?20–28 per mil relative to PDB. This wide range of δ¹³C values is explained by three mechanisms. Microbiological degradation of organic matter appears to be the dominant process controlling the extremely low and high δ¹³C values of HCO₃^? in the shallow production zones where the subsurface temperatures are less than 80°C. The extremely low δ¹³C values (< ?10 per mil) are obtained in waters where concentrations of SO₄^2? are more than 25 mg/l and probably result from the degradation of organic acid anions by sulfate-reducing bacteria (SO₄^2? + CH₃COO^? → 2HCO₃^? + HS^?). The high δ¹³C values probably result from the degradation of these anions by methanogenic bacteria (CH₃COO^? + H₂OaiHCO₃^? + CH₄).Thermal decarboxylation of short-chain aliphatic acid anions (principally acetate) to produce CO₂ and CH₄ is probably the major source of CO₂ for production zones with subsurface temperatures greater than 80°C. The δ¹³C values of HCO₃^? for waters from zones with temperatures greater than 100°C result from isotopic equilibration between CO₂ and CH₄. At these high temperatures, δ¹³C values of HCO₃^? decrease with increasing temperatures and decreasing concentrations of these acid anions.