Comparative study on CO2 sources in soil developed on carbonate rock and non-carbonate rock in Central Guizhou

In this paper, by using concentration and carbon stable isotope the CO2 sources of soil profiles developed on limestone, dolostone and claystone basements in Central Guizhou, China are comparatively studied. The results show that CO2 concentration of soil profiles developed on different basements is different, having the following sequence: limestone>dolostone>claystone. Below the soil depth of 20 cm from the surface the ? 13C value of CO2 in soil profile developed on limestone ranges from -12.811‰ - -13.492‰(PDB), that in soil profile developed on dolostone varys from -13.212‰ - -14.271‰(PDB) and that in soil profile developed on claystone is about -20.234‰ - -21.485‰(PDB). Taking the carbon isotope of soil organic matter and carbonate rock as two isotopic endmembers, the proportion of soil CO2 generated by dissolution of carbonate rock is calculated, about 21%-25% for soil profile developed on limestone basement, 19%-21% for soil profile developed on dolostone basement. There is almost no influx of CO2 generated by the dissolution of carbonate rock in soil profile developed on claystone basement.     

Geochemical features of the geothermal CO2-watercarbonate rock system and analysis on its CO2 sources

Taking Huanglong Ravine and Kangding, Sichuan, and Xiage, Zhongdian, Yunnan, as examples, the authors summarize the hydrogeochemical and carbon stable isotopic features of the geothermal CO₂-water-carbonate rock system and analyze the CO₂ sources of the system. It was found that the hydrogeochemical and carbon stable isotopic features of such a system are different from those of shallow CO₂-water-carbonate rock system, which is strongly influenced by biosphere. The former has higher CO₂ partial pressure, and is rich in heavy carbon stable isotope. In addition, such a geothermal system is also different from that developed in igneous rock. The water in the latter system lacks Ca²⁺, and thus, there are few tufa deposits on ground surface, but it is rich in light carbon stable isotope. Further analysis shows that CO₂ of the geothermal CO₂-water-carbonate rock system is a mixture of metamorphic CO₂ and magmatic CO₂.     

CO2-induced dissolution of low permeability carbonates. Part II: Numerical modeling of experiments

We used the 3D continuum-scale reactive transport models to simulate eight core flood experiments for two different carbonate rocks. In these experiments the core samples were reacted with brines equilibrated with pCO₂ = 3, 2, 1, 0.5 MPa (Smith et al., 2013 [27]). The carbonate rocks were from specific Marly dolostone and Vuggy limestone flow units at the IEAGHG Weyburn-Midale CO₂ Monitoring and Storage Project in south-eastern Saskatchewan, Canada. Initial model porosity, permeability, mineral, and surface area distributions were constructed from micro tomography and microscopy characterization data. We constrained model reaction kinetics and porosity–permeability equations with the experimental data. The experimental data included time-dependent solution chemistry and differential pressure measured across the core, and the initial and final pore space and mineral distribution. Calibration of the model with the experimental data allowed investigation of effects of carbonate reactivity, flow velocity, effective permeability, and time on the development and consequences of stable and unstable dissolution fronts.The continuum scale model captured the evolution of distinct dissolution fronts that developed as a consequence of carbonate mineral dissolution and pore scale transport properties. The results show that initial heterogeneity and porosity contrast control the development of the dissolution fronts in these highly reactive systems. This finding is consistent with linear stability analysis and the known positive feedback between mineral dissolution and fluid flow in carbonate formations. Differences in the carbonate kinetic drivers resulting from the range of pCO₂ used in the experiments and the different proportions of more reactive calcite and less reactive dolomite contributed to the development of new pore space, but not to the type of dissolution fronts observed for the two different rock types. The development of the dissolution front was much more dependent on the physical heterogeneity of the carbonate rock. The observed stable dissolution fronts with small but visible dissolution fingers were a consequence of the clustering of a small percentage of larger pores in an otherwise homogeneous Marly dolostone. The observed wormholes in the heterogeneous Vuggy limestone initiated and developed in areas of greater porosity and permeability contrast, following pre-existing preferential flow paths.Model calibration of core flood experiments is one way to specifically constrain parameter input used for specific sites for larger scale simulations. Calibration of the governing rate equations and constants for Vuggy limestones showed that dissolution rate constants reasonably agree with published values. However the calcite dissolution rate constants fitted to the Marly dolostone experiments are much lower than those suggested by literature. The differences in fitted calcite rate constants between the two rock types reflect uncertainty associated with measured reactive surface area and appropriately scaling heterogeneous distribution of less abundant reactive minerals. Calibration of the power-law based porosity–permeability equations was sensitive to the overall heterogeneity of the cores. Stable dissolution fronts of the more homogeneous Marly dolostone could be fit with the exponent n = 3 consistent with the traditional Kozeny–Carman equation developed for porous sandstones. More impermeable and heterogeneous cores required larger n values (n = 6–8).     

Preliminary study on weathering and pedogenesis of carbonate rock

South China is the largest continuous distribution area of carbonate rock in the world. The origin of the soils over the bedrock carbonate rock has long been a controversial topic. Here further exploration is made by taking five soil profiles as examples, which are developed over the bedrock dolomitite and limestone and morphologically located in upland in karst terrain in the central, west and north Guizhou as well as west Hunan, and proved to be the weathering profiles of carbonate rock by the research results of acid-dissolved extraction experiment of bedrock, mineralogy and trace element geochemistry. Field, mineralogical and trace element geochemical characteristics of weathering and pedogenesis for carbonate rock are discussed in detail. It is pointed out that weathering and pedogenesis of carbonate rock are important pedogenetic mechanisms for soil resources in karst area, providing a basis for further researches on the origin of soils widely overlying bedrock carbonate rocks in South China. Project supported by the National Natural Science Foundation of China (Grant No. 498330003) and National Key Basic Research Project (Grant No. 95pre-39).     

Strongly magnetic soil developed on a non-magnetic rock basement: A case study from NW Bulgaria

The enhanced magnetic susceptibility of modern soils is assumed to have several reasons including, e.g., weathering of an iron-rich geological basement, natural fires, bacterial processes and atmospheric deposition of anthropogenic particles. We report on a case where none of the above sources of magnetic enhancement is evident: a modern soil with high magnetic susceptibility over the whole soil profile, developed on nonmagnetic limestones, in an area with no industrial activities. The surface magnetic susceptibility varies from 60 to 110×10⁻⁵ SI, while that of the rock basement is nearly zero. Moreover, significant frequency-dependent magnetic susceptibility (> 12%) suggests that superparamagnetic secondary magnetite/maghemite plays an important role. Possible mechanisms, responsible for this magnetic enhancement, are discussed.     

Limestone assimilation and the origin of CO2 emissions at the Alban Hills (Central Italy): Constraints from experimental petrology

The Alban Hills volcanic region (20 km south of Rome, in the Roman Province) emitted a large volume of potassic magmas (> 280 km³) during the Quaternary. Chemical interactions between ascending magmas and the ∼ 7000–8000-m-thick sedimentary carbonate basement are documented by abundant high temperature skarn xenoliths in the eruptive products and have been frequently corroborated by geochemical surveys. In this paper we characterize the effect of carbonate assimilation on phase relationships at 200 MPa and 1150–1050 °C by experimental petrology. Calcite and dolomite addition promotes the crystallization of Ca-rich pyroxene and Mg-rich olivine respectively, and addition of both carbonates results in the desilication of the melt. Furthermore, carbonate assimilation liberates a large quantity of CO₂-rich fluid. A comparison of experimental versus natural mineral, glass and bulk rock compositions suggests large variations in the degree of carbonate assimilation for the different Alban Hills eruptions. A maximum of 15 wt.% assimilation is suggested by some melt inclusion and clinopyroxene compositions; however, most of the natural data indicate assimilation of between 3 and 12 wt.% carbonate. Current high CO₂ emissions in this area most likely indicate that such an assimilation process still occurs at depth. We calculate that a magma intruding into the carbonate basement with a rate of ∼ 1 – 2 · 10⁶ m³/year, estimated by geophysical studies, and assimilating 3–12 wt.% of host rocks would release an amount of CO₂ matching the current yearly emissions at the Alban Hills. Our results strongly suggest that current CO₂ emissions in this region are the shallow manifestation of hot mafic magma intrusion in the carbonate-hosted reservoir at 5–6 km depth, with important consequences for the present-day volcanic hazard evaluation in this densely populated and historical area.     

Carbon stable isotopic composition of karst soil CO2 in central Guizhou, China

The δ¹³c values of soil CO₂ are less than that of atmosphere CO₂ in the karst area. On the soil-air interface, the δ¹³c vlaues of soil CO₂ decrease with the increase in soil depth; below the soil-air interface, the δ¹³c values of soil CO₂ are invariable. The type of vegetation on the land surface has an influence on the δ¹³C values of soil CO₂. Due to the activity of soil microbes, the δ¹³C values of soil CO₂ are variable with seasonal change in ps. Isotopic tracer indicates that atmosphere CO₂ has a great deal of contribution to soil CO₂ at the lower parts of soil proflie. Project supported by the National Natural Science Foundation of China (Grant Nos. 49703048 and 49833002)     

Uncertainty analysis of CO<Subscript>2</Subscript> flux components in subtropical evergreen coniferous plantation

We present an uncertainty analysis of ecological process parameters and CO₂ flux components (R _eco, NEE and gross ecosystem exchange (GEE)) derived from 3 years’ continuous eddy covariance measurements of CO₂ fluxes at subtropical evergreen coniferous plantation, Qianyanzhou of ChinaFlux. Daily-differencing approach was used to analyze the random error of CO₂ fluxes measurements and bootstrapping method was used to quantify the uncertainties of three CO₂ flux components. In addition, we evaluated different models and optimization methods in influencing estimation of key parameters and CO₂ flux components. The results show that: (1) Random flux error more closely follows a double-exponential (Laplace), rather than a normal (Gaussian) distribution. (2) Different optimization methods result in different estimates of model parameters. Uncertainties of parameters estimated by the maximum likelihood estimation (MLE) are lower than those derived from ordinary least square method (OLS). (3) The differences between simulated R_eco, NEE and GEE derived from MLE and those derived from OLS are 12.18% (176 g C·m⁻²·a⁻¹), 34.33% (79 g C·m⁻²·a⁻¹) and 5.4% (92 g C·m⁻²·a⁻¹). However, for a given parameter optimization method, a temperature-dependent model (T_model) and the models derived from a temperature and water-dependent model (TW_model) are 1.31% (17.8 g C·m⁻²·a⁻¹), 2.1% (5.7 g C·m⁻²·a⁻¹), and 0.26% (4.3 g C·m⁻²·a⁻¹), respectively, which suggested that the optimization methods are more important than the ecological models in influencing uncertainty in estimated carbon fluxes. (4) The relative uncertainty of CO₂ flux derived from OLS is higher than that from MLE, and the uncertainty is related to timescale, that is, the larger the timescale, the smaller the uncertainty. The relative uncertainties of R_eco, NEE and GEE are 4%−8%, 7%−22% and 2%−4% respectively at annual timescale. Supported by the National Natural Science Foundation of China (Grant No. 30570347), Innovative Research International Partnership Project of the Chinese Academy of Sciences (Grant No. CXTD-Z2005-1) and National Basic Research Program of China (Grant No. 2002CB412502)     

Continuous gas monitoring in the West Bohemian earthquake area,Czech Republic: First results

Two stations monitoring concentrations of carbon dioxide and radon in soil gas (Oldřišská and Novy Kostel) and one station monitoring flow of carbon dioxide at a mofette (Soos) have been operated in the area of the West Bohemian earthquake swarms. We present preliminary results obtained on the base of four-year observations. We found that data are not influenced considerably by barometric pressure. Although the CO₂ concentration varies greatly, the long-term trends at stations Oldřišská and Novy Kostel are similar, which indicates that the CO₂ flow is controlled by common geogenic processes. Also temporal trends of CO₂ and Rn concentrations in soil gas at individual stations are analogous. We found diurnal variations of both CO₂ concentration in soil gas and the CO₂ flow at mofettes due to the earth tides. A response to tides of semi-diurnal period is insignificant in CO₂ concentration and only weak in the CO₂ flow. We also examined possible pre-seismic, co-seismic and post-seismic effects of the intensive 2008 earthquake swarm on the CO₂ concentration at Oldřišská and Novy Kostel, and on the CO₂ flow at Soos. However, all potential indications were insignificant and there has not been proven any influence of the swarm on the CO₂ concentration as well as on the CO₂ flow. Nevertheless, a gradual decrease of amplitudes of diurnal variations before the swarm and the lowest amplitudes during the swarm is a noteworthy phenomenon, which might indicate the strain changes of the rock associated with earthquake swarm.     

Effect of supercritical CO2 on carbonates: Savonnières sample case study

CO₂ geosequestration is an efficient way to reduce greenhouse gas emissions into the atmosphere. Carbonate rock formations are one of the possible targets for CO₂ sequestration due to their relative abundance and ability to serve as a natural trapping reservoir. The injected supercritical CO₂ can change properties of the reservoir rocks such as porosity, permeability, tortuosity, and specific surface area due to dissolution and precipitation processes. This, in turn, affects the reservoir characteristics, i.e., their elastic properties, storage capacity, stability, etc. The tremendous progresses made recently in both microcomputed X‐ray tomography and high‐performance computing make numerical simulation of physical processes on actual rock microstructures feasible. However, carbonate rocks with their extremely complex microstructure and the presence of microporosity that is below the resolution of microcomputed X‐ray tomography scanners require novel, quite specific image processing and numerical simulation approaches. In the current work, we studied the effects of supercritical CO₂ injection on microstructure and elastic properties of a Savonnières limestone. We used microtomographic images of two Savonnières samples, i.e., one in its natural state and one after injection and residence of supercritical CO₂. A statistical analysis of the microtomographic images showed that the injection of supercritical CO₂ led to an increase in porosity and changes of the microstructure, i.e., increase of the average volume of individual pores and decrease in the total number of pores. The CO₂ injection/residence also led to an increase in the mean radii of pore throats, an increase in the length of pore network segments, and made the orientation distribution of mesopores more isotropic. Numerical simulations showed that elastic moduli for the sample subjected to supercritical CO₂ injection/residence are lower than those for the intact sample.     

Coal-generated oil in Tuha Basin

The Turpan-Harmi (abbreviated to Tuha below) Basin is a typical basin of coal-generated oil accumulation in China. The Middle-Lower Jurassic coal measures are considered the main source beds. Hence, both desmocollinite and suberinite are considered the contributors for coal-generated oil. Principal geochemical features of the crude oil in the Tuha Basin are rich in alkanes (70%—80%), high pristane/phytane ratio (6—8), abundant heavy carbon isotope (δ¹³C PDB= -26%–-23%) and absolute GP sterane predominance. The hydrocarbon generation process from the coal series is characterized by multistages, early generation and early expulsion.     

Soil H<Subscript>2</Subscript> and CO<Subscript>2</Subscript> Surveys at Several Active Faults in Japan

Soil H₂ and CO₂ surveys were carried out along seven active faults and around the aftershock region of the 2000 Tottori-ken Seibu earthquake in Japan. Diffuse CO₂ effluxes were also measured along one fault and around the 2000 aftershock region. The results show highly variable H₂ concentration in space and time and it seems that the maximum H₂ concentration at each active fault correlates with fault activity as exemplified by the time of the latest big earthquakes. Even though observed H₂ concentrations in four faults were markedly lower than those collected previously in the latter half of the 1970s, it is evident that the higher H₂ concentrations in this study are due to the addition of the fault gases. Comparing the chemical composition of trapped gases (H₂: 5–20% and CO₂/H₂: 0.5–12) in fractured rocks of drill cores bored at the Nojima fault, a soil gas sample with the highest H₂ concentration showed large amounts of the trapped fault gas, diluted with atmospheric component. The profile experiment across a fracture zone at the Yamasaki fault showed higher H₂ concentrations and lower CO₂/H₂ ratios as was observed in soil gas from the fracture zone. A few days after the 2000 Tottori-kei Seibu earthquake, no CO₂ effluxes related to the occurrence of earthquakes were observed at the aftershock region. However, only above the epicenter zone, relatively high H₂ concentrations in soil gases were observed.     

Diffuse Emission of CO2 from Showa-Shinzan, Hokkaido, Japan: A Sign of Volcanic Dome Degassing

Two soil CO₂ efflux surveys were carried out in September 1999 and June 2002 to study the spatial distribution of diffuse CO₂ degassing and estimate the total CO₂ output from Showa-Shinzan volcanic dome, Japan. Seventy-six and 81 measurements of CO₂ efflux were performed in 1999 and 2002, respectively, covering most of Showa-Shinzan volcano. Soil CO₂ efflux data showed a wide range of values up to 552 g m^-2 d^-1. Carbon isotope signatures of the soil CO₂ ranged from -0.9‰ to -30.9‰, suggesting a mixing between different carbon reservoirs. Most of the study area showed CO₂ efflux background values during the 1999 and 2002 surveys (B = 8.2 and 4.4 g m^-2 d^-1, respectively). The spatial distribution of CO₂ efflux anomalies for both surveys showed a good correlation with the soil temperature, indicating a similar origin for the extensive soil degassing generated by condensation processes and fluids discharged by the fumarolic system of Showa-Shinzan. The total diffuse CO₂ output of Showa-Shinzan was estimated to be about 14.0–15.6 t d^-1 of CO₂ for an area of 0.53 km².     

Carbon isotopes in eclogite and apatite separate from Huangzhen and Shima in SE Dabie

The carbon isotope compositions of high- and ultrahigh-pressure eclogite and apatite separate from Huangzhen and Shima in SE Dabie Mountains were analyzed by EA-MS online technique. The δ13C values of the eclogites cover a wide range of -30.7‰ - +1.5‰, whereas those of apatites only have a small range of -28.1‰--21.0‰. Some of the eclogites with the high δ13C values suffered retrogressive alteration by CO2-bearing fluids. The low δ13C values of the apatites indicate that the eclogites contain surficial carbon of organic origin. It is concluded that protoliths of the eclogites were exposed to the surface of the Earth, and that the carbon-bearing fluid was depleted in 13C during the eclogite-facies metamorphism.     

The chemical anomalous behaviors of water-marble rock system under action of ultrasound

By the experiment, it is confirmed that water-marble rock system shows obviously chemical anomalous behaviors: the relevant minerals which formed marble rock are resolved fast, water becomes alkaline, meanwhile H₂ emission appears under action of ultrasound; based on rock identification by microscope and chemical analysis of water and rock, the mechanism of above chemical reaction is analyzed and discussed. The Chinese version of this paper appeared in the Chinese edition ofActa Seismologica Sinica,15 498–507, 1993. This study was supported by the Chinese Joint Seismological Science Foundation.     

Geochemische und 13C/12C-isotopenchemische Untersuchung zur Herkunft der Kohlensäure in mineralhaltigen Wässern Nordhessens (Deutschland)

Geochemical and ¹³C/¹²C-isotopical Investigation of Mineral Waters in Northern Hessia (Germany) and the Origin of their CO₂ Content The dissolved carbonate originates from three sources: 1. biogenetic soil-CO₂, 2. volcanic CO₂ related to the evaporites of the Zechstein formation, and 3. carbonate derived from the dissolution of limestones and dolomites. Miocenic basaltic melts penetrated the evaporites of the Zechstein, and the related CO₂ was trapped in the intra- and intergranulars of the salt minerals. Circulating meteoric waters dissolve the salt minerals releasing CO₂ gas. Thus, the occurrence of basalt is related to the CO₂ contents of the evaporites, and the dissolution of only small amounts of salts rich in CO₂ may result in a high concentration of carbonic acid. In waters rich in carbonate, where volcanic CO₂ dominates over the other two sources of carbon, a δ¹³C-value of “salt-CO₂” of about –1‰ (PDB) is obtained. Water with less dissolved carbonate species have smaller quantities of salt-CO₂ down to about 20%.     

The δ13C–δ18O variations in marble in the Hida Belt,Japan

Marble has a great potential to understand a history of various geological events occurring during tectonic processes. In order to decode metamorphic–metasomatic records on C–O isotope compositions of marble at mid-crustal conditions, we conducted a C–O–Sr isotope study on upper amphibolite-facies marbles and a carbonate–silicate rock from the Hida Belt, which was once a part of the crustal basement of the East Asian continental margin. Carbon and oxygen isotope analyses of calcite from marbles (Kamioka area) and a carbonate–silicate rock (Wadagawa area) show a large variation of δ¹³C [VPDB] and δ¹⁸O [VSMOW] values (from −4.4 to +4.2 ‰ and +1.6 to +20.8 ‰, respectively). The low δ¹³C values of calcites from the carbonate–silicate rock (from −4.4 to −2.9 ‰) can be explained by decarbonation (CO₂ releasing) reactions; carbon–oxygen isotope modeling suggests that a decrease of δ¹³C strongly depends on the amount of silicate reacting with carbonates. The occurrence of metamorphic clinopyroxene in marbles indicates that all samples have been affected by decarbonation reactions. All δ¹⁸O values of calcites are remarkably lower than the marine-carbonate values. The large δ¹⁸O variation can be explained by the isotope exchange via interactions between marble, external fluids, and/or silicates. Remarkably low δ¹⁸O values of marbles that are lower than mantle value (~+5 ‰) suggest the interaction with meteoric water at a later stage. Sr isotope ratios (⁸⁷Sr/⁸⁶Sr = 0.707255–0.708220) might be close to their protolith values. One zircon associated with wollastonite in a marble thin-section yields a U–Pb age of 222 ± 3 Ma, which represents the timing of the recrystallization of marble, triggered by H₂O-rich fluid infiltration at a relatively high-temperature condition. Our isotope study implies that the upper amphibolite-facies condition, like the Hida Belt, might be appropriate to cause decarbonation reactions which can modify original isotope compositions of marble if carbonates react with silicates.     

粤东五华河流域的化学风化与CO2吸收

基于对粤东五华河干流和支流水体的物理、化学组成测试数据,应用质量平衡法和相关分析法探讨湿热山地丘陵地区岩石化学风化过程对大气CO₂的吸收.结果表明:五华河水体的总溶解性固体含量(77.11 mg/L)接近于世界河流的平均值(65 mg/L);离子组成以Ca²⁺、Na⁺和HCO₃^-为主,可溶性Si次之.五华河流域化学径流组成主要源自硅酸盐矿物化学风化过程的贡献,碳酸盐矿物的贡献较少;大气和土壤CO₂是流域内岩石化学风化的主要侵蚀介质.与同一气候带其他河流相比较,五华河流域岩石化学风化过程对大气CO₂的吸收通量(2.14×105mol/(km²·a))较低,这主要是由于流域内缺乏碳酸盐岩所导致.     

Ground penetrating radar imaging of cap rock, caliche and carbonate strata

Field experiments show ground penetrating radar (GPR) can be used to image shallow carbonate stratigraphy effectively in a variety of settings. In south Florida, the position and structure of cap rock cover on limestone can be an important control on surface water flow and vegetation, but larger scale outcrops (tens of meters) of cap rock are sparse. GPR mapping through south Florida prairie, cypress swamp and hardwood hammock resolves variations in thickness and structure of cap rock to 3 m and holds the potential to test theories for cap rock–vegetation relationships. In other settings, carbonate strata are mapped to test models for the formation of local structural anomalies. A test of GPR imaging capabilities on an arid caliche (calcrete) horizon in southeastern Nevada shows depth penetration to 2 m with resolution of the base of caliche. GPR profiling also succeeds in resolving more deeply buried (5 m) limestone discontinuity surfaces that record subaerial exposure in south Florida.     

Gas contents and CO2 isotope studies on fluid inclusion in ultra-high pressure metamorphic rock from Shuanghe area, Dabie Mountain

Step heating experiments on ultra-high pressure (UHP) mcks from the Dabie Mountain shows a majority of CO₂ in fluid inclusion (excluding H₂O); CO is also a significant component, with a small content of N₂ and CH₄. Carbon isotopic composition of CO₂ in fluid of metamorphic climax stage (-25%0- -30%0) is different from that of mantle carbon, indicating that UHP rocks did not experience obvious transformation by mantle fluids despite their subduction depth. CO₂ was derived from carbon matter in the pmtoliths of UHP rocks in a relatively confined system, showing that the UHP rocks subsided quickly and uplifted quickly from the mantle. Current organization: Research Institute of Petroleum Exploration and Development, Beijing 100083, China.