To gain insight into the flow mechanisms and stress sensitivity for fractured-vuggy reservoirs,several core models with different structural characteristics were designed and fabricated to investigate the impact of ef...To gain insight into the flow mechanisms and stress sensitivity for fractured-vuggy reservoirs,several core models with different structural characteristics were designed and fabricated to investigate the impact of effective stress on permeability for carbonate fractured-vuggy rocks(CFVR).It shows that the permeability performance curves under different pore and confining pressures(i.e.altered stress conditions)for the fractured core models and the vuggy core models have similar change patterns.The ranges of permeability variation are significantly wider at high pore pressures,indicating that permeability reduction is the most significant during the early stage of development for fractured-vuggy reservoirs.Since each obtained effective stress coefficient for permeability(ESCP)varies with the changes in confining pressure and pore pressure,the effective stresses for permeability of four representative CFVR show obvious nonlinear characteristics,and the variation ranges of ESCP are all between 0 and 1.Meanwhile,a comprehensive ESCP mathematical model considering triple media,including matrix pores,fractures,and dissolved vugs,was proposed.It is proved theoretically that the ESCP of CFVR generally varies between 0 and 1.Additionally,the regression results showed that the power model ranked highest among the four empirical models mainly applied in stress sensitivity characterization,followed by the logarithmic model,exponential model,and binomial model.The concept of“permeability decline rate”was introduced to better evaluate the stress sensitivity performance for CFVR,in which the one-fracture rock is the strongest,followed by the fracture-vug rock and two-horizontalfracture rock;the through-hole rock is the weakest.In general,this study provides a theoretical basis to guide the design of development and adjustment programs for carbonate fractured-vuggy reservoirs.展开更多
The deterioration of unstable rock mass raised interest in evaluating rock mass quality.However,the traditional evaluation method for the geological strength index(GSI)primarily emphasizes the rock structure and chara...The deterioration of unstable rock mass raised interest in evaluating rock mass quality.However,the traditional evaluation method for the geological strength index(GSI)primarily emphasizes the rock structure and characteristics of discontinuities.It ignores the influence of mineral composition and shows a deficiency in assessing the integrity coefficient.In this context,hyperspectral imaging and digital panoramic borehole camera technologies are applied to analyze the mineral content and integrity of rock mass.Based on the carbonate mineral content and fissure area ratio,the strength reduction factor and integrity coefficient are calculated to improve the GSI evaluation method.According to the results of mineral classification and fissure identification,the strength reduction factor and integrity coefficient increase with the depth of rock mass.The rock mass GSI calculated by the improved method is mainly concentrated between 40 and 60,which is close to the calculation results of the traditional method.The GSI error rates obtained by the two methods are mostly less than 10%,indicating the rationality of the hyperspectral-digital borehole image coupled evaluation method.Moreover,the sensitivity of the fissure area ratio(Sr)to GSI is greater than that of the strength reduction factor(a),which means the proposed GSI is suitable for rocks with significant fissure development.The improved method reduces the influence of subjective factors and provides a reliable index for the deterioration evaluation of rock mass.展开更多
Low salinity water containing sulfate ions can significantly alter the surface wettability of carbonate rocks.Nevertheless,the impact of sulfate concentration on the desorption of oil film on the surface of carbonate ...Low salinity water containing sulfate ions can significantly alter the surface wettability of carbonate rocks.Nevertheless,the impact of sulfate concentration on the desorption of oil film on the surface of carbonate rock is still unknown.This study examines the variations in the wettability of the surface of carbonate rocks in solutions containing varying amounts of sodium sulfate and pure water.The problem is addressed in the framework of molecular dynamics simulation(Material Studio software)and experiments.The experiment’s findings demonstrate that sodium sulfate can increase the rate at which oil moisture is turned into water moisture.The final contact angle is smaller than that of pure water.The results of the simulations show that many water molecules travel down the water channel under the influence of several powerful forces,including the electrostatic force,the van der Waals force and hydrogen bond,crowding out the oil molecules on the calcite’s surface and causing the oil film to separate.The relative concentration curve of water and oil molecules indicates that the separation rate of the oil film on the surface of calcite increases with the number of sulfate ions.展开更多
In order to study the hydrocarbon generation(HCGE)characteristics of coal-bearing basins,the coal-measure source rocks of the Middle Jurassic-Lower Jurassic(MLJ)of the piedmont thrust belt in the southern margin of th...In order to study the hydrocarbon generation(HCGE)characteristics of coal-bearing basins,the coal-measure source rocks of the Middle Jurassic-Lower Jurassic(MLJ)of the piedmont thrust belt in the southern margin of the Junggar Basin in Northwest China are taken as research objects.More than 60 MLJ samples were collected from outcrops and wells.Total organic carbon(TOC),rock pyrolysis(Rock-Eval),organic petrological,vitrinite reflectance(%Ro),and hydrous pyrolysis were performed to analyze the relevant samples.The pyrolysis gases and liquid products were measured,and then the chemical composition,as well as carbon isotopes of the gases,were analyzed.The results indicate that the MLJ source rocks have the capacity for large-scale gas generation.In addition,for coal-measure source rocks,the heavier the carbon isotope of kerogen(δ^(13)C_(kerogen)),the lower the liquid hydrocarbon and hydrocarbon gas yield,and the easier it is to produce non-hydrocarbon gas.It is worth noting that when theδ^(13)C_(kerogen)in organic matter(OM)is relatively heavier,the fractionation of its products may become weaker in the evolutionary process.The vital contribution of the MLJ source rock to natural gas resources in the study area was further confirmed by comparing it with the Jurassic source gas.展开更多
Carbonate rocks are extensively used in civil infrastructure and play a critical role in geoenergy geoengineering,either as hydrocarbon reservoirs or potential repositories for CO_(2)geological storage.Carbonate genes...Carbonate rocks are extensively used in civil infrastructure and play a critical role in geoenergy geoengineering,either as hydrocarbon reservoirs or potential repositories for CO_(2)geological storage.Carbonate genesis and diagenetic overprint determine the properties of carbonate rocks.This study combines recent data gathered from Madison Limestone and an extensive dataset compiled from published sources to analyze the hydraulic and mechanical properties of limestone carbonate rocks.Physical models and data analyses recognize the inherently granular genesis of carbonate rocks and explain the strong dependency of physical properties on porosity.The asymptotically-correct power model in terms of(1-Ф/Ф*)a is a good approximation to global trends of unconfined stiffness E and unconfined compressive strength UCS,cohesive intercept in Mohr-Coulomb failure envelopes,and the brittle-toductile transition stress.This power model is the analytical solution for the mechanical properties of percolating granular structures.We adopted a limiting granular porosityФ*=0.5 for all models,which was consistent with the loosest packing of monosize spheres.The fitted power model has exponent(α=2)in agreement with percolation theory and highlights the sensitivity of mechanical properties to porosity.Data and models confirm a porosity-independent ratio between unconfined stiffness and strength,and the ratio follows a log-normal distribution with mean(E/UCS)≈300.The high angle of internal shear strength measured for carbonate rocks reflects delayed contact failure with increased confinement,and it is not sensitive to porosity.Permeability spans more than six orders of magnitude.Grain size controls pore size and determines the reference permeability k^(*)at the limiting porosityФ*=0.5.For a given grain size from fine to coarse-grained dominant carbonates,permeability is very sensitive to changes in porosity,suggesting preferential changes in the internal pore network during compaction.展开更多
Nigeria has an abundance of valuable solid minerals and rocks which can generate revenue for the government if they are fully exploited. Carbonate rock is one of such rocks that occur prominently in Igwe Igarra area o...Nigeria has an abundance of valuable solid minerals and rocks which can generate revenue for the government if they are fully exploited. Carbonate rock is one of such rocks that occur prominently in Igwe Igarra area of Edo State. Five (5) carbonate rock samples (Four marble and One Calcsilicate) were subjected to geochemical analyses. A petrographic study reveals that marble and calcsilicate contain calcite, quartz, microcline, plagioclase, biotite and opaque minerals. Geochemical data shows that carbonate rocks have variable geochemical characteristics: Igwe marble is highly Calcitic (96% - 98%) and very low in dolomite Mg(CO<sub>3</sub>). Calcsilicate rock is low in CaO (27.5%) and higher in marble. The Igwe marble is pure and contains fewer impurities compared to calcsilicate rock which makes it unideal for usage. Based on these characteristics the marble from Igwe is suitable as raw materials for the productions of glass, papers, beet sugar, aggregates, lubricants and fillers.展开更多
The Ordovician carbonate rocks of the Yingshan formation in the Tarim Basin have a complex pore structure owing to diagenetic and secondary structures. Seismic elastic parameters(e.g., wave velocity) depend on poros...The Ordovician carbonate rocks of the Yingshan formation in the Tarim Basin have a complex pore structure owing to diagenetic and secondary structures. Seismic elastic parameters(e.g., wave velocity) depend on porosity and pore structure. We estimated the average specific surface, average pore-throat radius, pore roundness, and average aspect ratio of carbonate rocks from the Tazhong area. High P-wave velocity samples have small average specific surface, small average pore-throat radius, and large average aspect ratio. Differences in the pore structure of dense carbonate samples lead to fluid-related velocity variability. However, the relation between velocity dispersion and average specific surface, or the average aspect ratio, is not linear. For large or small average specific surface, the pore structure of the rock samples becomes uniform, which weakens squirt fl ow and minimizes the residuals of ultrasonic data and predictions with the Gassmann equation. When rigid dissolved(casting mold) pores coexist with less rigid microcracks, there are significant P-wave velocity differences between measurements and predictions.展开更多
Strong heterogeneity and complex pore systems of carbonate reservoir rock make its rock physics model building and fluid substitution difficult and complex. However, rock physics models connect reservoir parameters wi...Strong heterogeneity and complex pore systems of carbonate reservoir rock make its rock physics model building and fluid substitution difficult and complex. However, rock physics models connect reservoir parameters with seismic parameters and fluid substitution is the most effective tool for reservoir prediction and quantitative characterization. On the basis of analyzing complex carbonate reservoir pore structures and heterogeneity at seismic scale, we use the gridding method to divide carbonate rock into homogeneous blocks with independent rock parameters and calculate the elastic moduli of dry rock units step by step using different rock physics models based on pore origin and structural feature. Then, the elastic moduli of rocks saturated with different fluids are obtained using fluid substitution based on different pore connectivity. Based on the calculated elastic moduli of rock units, the Hashin-Shtrikman-Walpole elastic boundary theory is adopted to calculate the carbonate elastic parameters at seismic scale. The calculation and analysis of carbonate models with different combinations of pore types demonstrate the effects of pore type on rock elastic parameters. The simulated result is consistent with our knowledge of real data.展开更多
We developed an anisotropic effective theoretical model for modeling the elastic behavior of anisotropic carbonate reservoirs by combining the anisotropic self-consistent approximation and differential effective mediu...We developed an anisotropic effective theoretical model for modeling the elastic behavior of anisotropic carbonate reservoirs by combining the anisotropic self-consistent approximation and differential effective medium models.By analyzing the measured data from carbonate samples in the TL area,a carbonate pore-structure model for estimating the elastic parameters of carbonate rocks is proposed,which is a prerequisite in the analysis of carbonate reservoirs.A workflow for determining elastic properties of carbonate reservoirs is established in terms of the anisotropic effective theoretical model and the pore-structure model.We performed numerical experiments and compared the theoretical prediction and measured data.The result of the comparison suggests that the proposed anisotropic effective theoretical model can account for the relation between velocity and porosity in carbonate reservoirs.The model forms the basis for developing new tools for predicting and evaluating the properties of carbonate reservoirs.展开更多
With a more complex pore structure system compared with clastic rocks, carbonate rocks have not yet been well described by existing conventional rock physical models concerning the pore structure vagary as well as the...With a more complex pore structure system compared with clastic rocks, carbonate rocks have not yet been well described by existing conventional rock physical models concerning the pore structure vagary as well as the influence on elastic rock properties. We start with a discussion and an analysis about carbonate rock pore structure utilizing rock slices. Then, given appropriate assumptions, we introduce a new approach to modeling carbonate rocks and construct a pore structure algorithm to identify pore structure mutation with a basis on the Gassmann equation and the Eshelby-Walsh ellipsoid inclusion crack theory. Finally, we compute a single well's porosity using this new approach with full wave log data and make a comparison with the predicted result of traditional method and simultaneously invert for reservoir parameters. The study results reveal that the rock pore structure can significantly influence the rocks' elastic properties and the predicted porosity error of the new modeling approach is merely 0.74%. Therefore, the approach we introduce can effectively decrease the predicted error of reservoir parameters.展开更多
Supercritical carbon dioxide(ScCO_(2))fracturing has great advantages and prospects in both shale gas exploitation and CO_(2)storage.This paper reviews current laboratory experimental methods and results for sedimenta...Supercritical carbon dioxide(ScCO_(2))fracturing has great advantages and prospects in both shale gas exploitation and CO_(2)storage.This paper reviews current laboratory experimental methods and results for sedimentary rocks fractured by ScCO_(2).The breakdown pressure,fracture parameters,mineral composition,bedding plane angle and permeability are discussed.We also compare the differences between sedimentary rock and granite fractured by ScCO_(2),ultimately noting problems and suggesting solutions and strategies for the future.The analysis found that the breakdown pressure of ScCO_(2)was reduced 6.52%–52.31%compared with that of using water.ScCO_(2)tends to produce a complex fracture morphology with significantly higher permeability.When compared with water,the fracture aperture of ScCO_(2)was decreased by 4.10%–72.33%,the tortuosity of ScCO_(2)was increased by 5.41%–70.98%and the fractal dimension of ScCO_(2)was increased by 4.55%–8.41%.The breakdown pressure of sandstone is more sensitive to the nature of the fracturing fluid,but fracture aperture is less sensitive to fracturing fluid than for shale and coal.Compared with granite,the tortuosity of sedimentary rock is more sensitive to the fracturing fluid and the fracture fractal dimension is less sensitive to the fracturing fluid.Existing research shows that ScCO_(2)has the advantages of low breakdown pressure,good fracture creation and environmental protection.It is recommended that research be conducted in terms of sample terms,experimental conditions,effectiveness evaluation and theoretical derivation in order to promote the application of ScCO_(2)reformed reservoirs in the future.展开更多
Carbonate rock outcrops cover 9%-16% of the continental area and are the principal source of the dissolved inorganic carbon (DIC) transferred by rivers to the oceans, a consequence their dissolution. Current estimat...Carbonate rock outcrops cover 9%-16% of the continental area and are the principal source of the dissolved inorganic carbon (DIC) transferred by rivers to the oceans, a consequence their dissolution. Current estimations suggest that the flux falls between 0.1-0.6 PgC/a. Taking the intermediate value (0.3 PgC/a), it is equal to 18% of current estimates of the terrestrial vegetation net carbon sink and 38% of the soil carbon sink. In China, the carbon flux from carbonate rock dissolution is estimated to be 0.016 PgC/a, which accounts for 21%, 87.5%-150% and 2.3 times of the forest, shrub and grassland net carbon sinks respectively, as well as 23%-40% of the soil carbon sink flux. Carbonate dissolution is sensitive to environmental and climatic changes, the rate being closely correlated with precipitation, temperature, also with soil and vegetation cover. HCO3 in the water is affected by hydrophyte photosynthesis, resulting in part of the HCO~ being converted into DOC and POC, which may enhance the potential of carbon sequestration by carbonate rock dissolution. The possible turnover time of this carbon is roughly equal to that of the sea water cycle (2000a). The uptake of atmospheric/soil CO2 by carbonate rock dissolution thus plays an important role in the global carbon cycle, being one of the most important sinks. A major research need is to better evaluate the net effect of this sink in comparison to an oceanic source from carbonate mineral precipitation.展开更多
Crustose lichens are distributed extensively in karst areas in Southern China. They can be found on the surface of carbonate rocks. Through biophysical and biochemical processes, crustose lichens reform the subsurface...Crustose lichens are distributed extensively in karst areas in Southern China. They can be found on the surface of carbonate rocks. Through biophysical and biochemical processes, crustose lichens reform the subsurface of carbonate rocks and in the meanwhile change their physical and chemical properties: (1) the mechanical strength decreases by 17.04° on average (up to 33.2°); (2) the chemical solution surface area increases from 28.26% to 75.36% (lichen microholes considered only); and (3) the water-holding capacity is greatly improved. Comparative field experiments between biokarst samples underneath crustose lichens and fresh rock samples with the same composition and texture show that the corrosional rate of carbonate rocks of the former is 1.264–1.643 times higher than that of the latter. Crustose lichens are considered as an activator of the surface corrosion of carbonate rocks.展开更多
Carbonates have been known to act as hydrocarbon source rocks, but their basic geochemical and associated hydrocarbon generation characteristics remain not well understood as they occur with argillaceous source rocks ...Carbonates have been known to act as hydrocarbon source rocks, but their basic geochemical and associated hydrocarbon generation characteristics remain not well understood as they occur with argillaceous source rocks in most cases, and the hydrocarbon generation from each rock type is di cult to distinguish, forming one of puzzling issues within the field of petroleum geology and geochemistry. To improve the understanding of this critical issue, this paper reviews recent advances in this field and provides a summary of key areas that can be studied in future. Results show that carbonate source rocks are generally associated with high-salinity environments with low amounts of terrestrial inputs and low dissolved oxygen contents. Petrographically, these source rocks are dark gray or black, fine-grained, stratified, and contain bacterial and algal bioprecursors along with some other impurities. They generally have low organic matter contents, although these can vary significantly in di erent cases(e.g., the total organic carbon contents of marine and lacustrine carbonate source rocks in China are generally 0.1%–1.0% and 0.4%–4.0%, respectively). These rocks contain type I and type II kerogen, meaning there is a lack of vitrinites. This means that assessment of the maturity of the organic matter in these sediments needs to use non-traditional techniques rather than vitrinite reflectance. In terms of molecular geochemistry, carbonate source rocks have typical characteristics indicative of generally reducing and saline environments and lower organism-dominated bioprecursors of organic matter, e.g., high contents of sulfur compounds, low Pr/Ph ratios, and dominance of n-alkanes. Most of the carbonate source rocks are typically dominated by D-type organic facies in an oxidized shallow water mass, although high-quality source rocks generally contain A-and B-type organic facies in saline lacustrine and marine-reducing environments, respectively. The hydrocarbon generation model for the carbonate source rocks can involve early, middle, and late stages, with a diversity of hydrocarbons within these rocks, which can be aggregated, adsorbed, enclosed within minerals, or present as inclusions. This in turn implies that the large-scale hydrocarbon expulsion from these rocks is reliant on brittle deformation caused by external forces. Finally, a number of aspects of these source rocks remain unclear and need further study, including the e ectiveness of carbonates as hydrocarbon source rocks, bioprecursors, and hydrocarbon generation models of carbonate source rock, and the di erences between marine and lacustrine carbonate source rocks.展开更多
Iron and manganese are the important redoxsensitive elements in the ocean. Previous studies have established a series of paleo-depositional redox proxies based on the form and content of iron in sedimentary rocks(e.g....Iron and manganese are the important redoxsensitive elements in the ocean. Previous studies have established a series of paleo-depositional redox proxies based on the form and content of iron in sedimentary rocks(e.g., degree of pyritization, FeHR/FeT, Fe/Al). These proxies were developed and applied on siliciclastic-rich marine sediments. Although marine carbonate rocks are generally considered to preserve the geochemical signals of ancient seawater, neither Fe nor Mn content in marine carbonate rocks(Fecarb, Mncarb) has been independently used as a proxy to quantify environmental cues in paleo-oceans. Both Fe and Mn are insoluble in oxic conditions(Fe_2O_3, Fe(OH)_3,MnO_2), while their reduced forms(Fe^(2+) and Mn^(2+)) are soluble. Therefore, oxic seawater should have low concentrations of dissolved Fe^(2+)and Mn^(2+), and accordingly carbonate rocks precipitated from oxic seawater should have low Fecarband Mncarb, and vice versa. To evaluate whether Fecarband Mncarbcan be used to quantify oxygen fugacity in seawater, we measured Fecarband Mncarbof Upper Devonian marine carbonate rocks collected from nine sections in South China. Fecarbof intraplatform basin samples wassignificantly higher than that of shelf samples, while shelf and basin samples had comparable Mncarb. The modeling result indicates that the dramatic difference in Fecarbcannot be explained by variation in oxygen fugacity between the shelf and basin seawater. Instead, both Fecarband Mncarb appear to be more sensitive to benthic flux from sediment porewater that is enriched in Fe^(2+)and Mn^(2+). Porewater Fe^(2+)and Mn^(2+)derive from bacterial iron and manganese reduction; flux was controlled by sedimentation rate and the depth of the Fe(Mn) reduction zone in sediments, the latter of which is determined by oxygen fugacity at the water–sediment interface. Thus, high Fecarbof the basin samples might be attributed to low sedimentation rate and/or low oxygen fugacity at the seafloor. However, invariant Mncarbof the shelf and basin samples might be the consequence of complete reduction of Mn in sediments. Our study indicates that marine carbonate rocks may not necessarily record seawater composition, particularly for benthic carbonate rocks. The influence of benthic flux might cause carbonate rocks' geochemical signals to deviate significantly from seawater values. Our study suggests that interpretation of geochemical data from carbonate rocks, including carbonate carbon isotopes, should consider the process of carbonate formation.展开更多
Previous studies have postulated the contribution of present-day low-total organic carbon (TOC) marine carbonate source rocks to oil accumulations in the Tabei Uplift, Tarim Basin, China. However, not all present-da...Previous studies have postulated the contribution of present-day low-total organic carbon (TOC) marine carbonate source rocks to oil accumulations in the Tabei Uplift, Tarim Basin, China. However, not all present-day low-TOC carbonates have generated and expelled hydrocarbons; therefore, to distinguish the source rocks that have already expelled sufficient hydrocarbons from those not expelled hydrocarbons, is crucial in source rock evaluation and resource assessment in the Tabei Uplift. Mass balance can be used to identify modern low-TOC carbonates resulting from hydrocarbon expulsion. However, the process is quite complicated, requiring many parameters and coefficients and thus also a massive data source. In this paper, we provide a quick and cost effective method for identifying carbonate source rock with present-day low TOC, using widely available Rock-Eval data. First, we identify present-day low-TOC carbonate source rocks in typical wells according to the mass balance approach. Second, we build an optimal model to evaluate source rocks from the analysis of the rocks' characteristics and their influencing factors, reported as positive or negative values of a dimensionless index of Rock-Eval data (IR). Positive IR corresponds to those samples which have expelled hydrocarbons. The optimal model optimizes complicated calculations and simulation processes; thus it could be widely applicable and competitive in the evaluation of present-day low TOC carbonates. By applying the model to the Rock-Eval dataset of the Tabei Uplift, we identify present-day iow-TOC carbonate source rocks and primarily evaluate the contribution equivalent of 11.87×10^9 t oil.展开更多
We investigated the weathering-pedogenesis of carbonate rocks and its environmental effects in subtropical regions of China. The investigation demonstrated that the weathering- pedogenesis of carbonate rocks is the pr...We investigated the weathering-pedogenesis of carbonate rocks and its environmental effects in subtropical regions of China. The investigation demonstrated that the weathering- pedogenesis of carbonate rocks is the process of a joint action of corrosion and illuviation and metasomatism in subtropical region. It is characterized by multi-stage, multi-path and multi-style. With the persisting development of weathering-pedogenesis of carbonate rocks, metasomatic pedogenesis progressively became the main process of the weathering-pedogenesis and the dominant style of formation of minerals. And it proceeds through the whole process of evolution of the weathering-pedogenesis of carbonate rocks. The stage evolution of weathering-pedogenesis of carbonate rocks and the fractionation evolution of newly produced minerals are characterized by obvious vertically zoning structures and the rules of gradation of elements geochemical characteristics in the carbonate rocks weathering profiles. The geochemical process of weathering-pedogenesis of carbonate rocks can be divided into three geochemical evolution stages, i.e., the Ca, Mg-depletion and Si, Al-enrichment stage; the Fe, Mn enrichment stage and the Si-depletion and Al-enrichment stage in the subtropical regions. Consistent with the three geochemical evolution stages, the sequence of formation and evolution of minerals can be divided into the clay mineral stage; the Fe, Mn oxide and the gibbsite stage. The influence of weathering-pedogenesis of carbonate rocks on the chemical forms of heavy elements is mainly affected via newly produced components and minerals in the process of weathering-pedogenesis, e.g., iron oxide minerals and organic matters. The important mechanism for the mobilization, transport and pollution of F and As is affected the selective adsorption and desorption of F and As on the surface of iron oxide minerals in the subtropical karst zones, i.e., the selective adsorption and desorption on mineral surfaces of newly produced minerals in the process of weathering-pedogenesis control the geochemical behavior of elements on the Earth's surface and environmental quality in subtropical regions.展开更多
The conversion of CO2 into H+ and is a relatively slow reaction. Hence, its kinetics may be rate determining in carbonate rock dissolution. Carbonic anhydrase (CA), which is widespread in nature, was used to catalyze ...The conversion of CO2 into H+ and is a relatively slow reaction. Hence, its kinetics may be rate determining in carbonate rock dissolution. Carbonic anhydrase (CA), which is widespread in nature, was used to catalyze the CO2 conversion process in dissolution experiments of limestone and dolomite. It was found that the rate of dissolution increases by a factor of about 10 after the addition of CA at a high CO2 partial pressure (Pco2) for limestone and about 3 at low Pco2 for dolomite. This shows that reappraisal is necessary for the importance of chemical weathering (including carbonate rock dissolution and silicate weathering) in the atmospheric CO2 sink and the mysterious missing sink in carbon cycling. It is doubtless that previous studies of weathering underestimated weathering rates due to the ignorance of CA as an activator in weathering, thus the contribution of weathering to the atmospheric CO2 sink is also underestimated. This finding also shows the need to examine the situ distribution and activity of CA in different waters and to investigate the role of CA in weathering.展开更多
Owing to the low contents of their acid-insoluble components, carbonate rocks tend to decrease sharply in volume in association with the formation of weathering crust. The formation of a 1 m-thick weathering crust wou...Owing to the low contents of their acid-insoluble components, carbonate rocks tend to decrease sharply in volume in association with the formation of weathering crust. The formation of a 1 m-thick weathering crust would usually consume more than ten meters to several tens of meters of thickness of parent rocks. The knowledge of how to identify the homogeneity of parent rocks is essential to understand the formation mechanism of weathering crust in karst regions, especially that of thick-layered red weathering crust. In this work the grain-size analyses have demonstrated that the three profiles studied are the residual weathering crust of carbonate rocks and further showed that there objectively exists the heterogeneity of parent rocks in the three studied weathering crusts. The heterogeneity of parent rocks can also be reflected m geochemical parameters of major elements, just as the characteristics of frequency plot of grain-size distribution. Conservative trace element ratios Zr/Hf and Nb/Ta are proven to be unsuitable for tracing the heterogeneity of parent rocks of weathering crust, but its geochemical mechanism is unclear. The authors strongly suggest in this paper that the identification of the homogeneity of parent rocks of weathering crust in karst regions is of prime necessity.展开更多
基金This work was supported by the Joint Fund of NSFC for Enterprise Innovation and Development(Grant No.U19B6003-02-06)the National Natural Science Foundation of China(Grant No.51974331)+1 种基金the Natural Science Foundation of Jiangsu Province(Grant No.BK20200525)The authors would like to sincerely acknowledge these funding programs for their financial support.Particularly,the support provided by the China Scholarship Council(CSC)during a visit of Ke Sun(File No.202106440065)to the University of Alberta is also sincerely acknowledged.
文摘To gain insight into the flow mechanisms and stress sensitivity for fractured-vuggy reservoirs,several core models with different structural characteristics were designed and fabricated to investigate the impact of effective stress on permeability for carbonate fractured-vuggy rocks(CFVR).It shows that the permeability performance curves under different pore and confining pressures(i.e.altered stress conditions)for the fractured core models and the vuggy core models have similar change patterns.The ranges of permeability variation are significantly wider at high pore pressures,indicating that permeability reduction is the most significant during the early stage of development for fractured-vuggy reservoirs.Since each obtained effective stress coefficient for permeability(ESCP)varies with the changes in confining pressure and pore pressure,the effective stresses for permeability of four representative CFVR show obvious nonlinear characteristics,and the variation ranges of ESCP are all between 0 and 1.Meanwhile,a comprehensive ESCP mathematical model considering triple media,including matrix pores,fractures,and dissolved vugs,was proposed.It is proved theoretically that the ESCP of CFVR generally varies between 0 and 1.Additionally,the regression results showed that the power model ranked highest among the four empirical models mainly applied in stress sensitivity characterization,followed by the logarithmic model,exponential model,and binomial model.The concept of“permeability decline rate”was introduced to better evaluate the stress sensitivity performance for CFVR,in which the one-fracture rock is the strongest,followed by the fracture-vug rock and two-horizontalfracture rock;the through-hole rock is the weakest.In general,this study provides a theoretical basis to guide the design of development and adjustment programs for carbonate fractured-vuggy reservoirs.
基金supported by the National Key R&D Program of China(Grant Nos.2021YFB3901403 and 2023YFC3007203).
文摘The deterioration of unstable rock mass raised interest in evaluating rock mass quality.However,the traditional evaluation method for the geological strength index(GSI)primarily emphasizes the rock structure and characteristics of discontinuities.It ignores the influence of mineral composition and shows a deficiency in assessing the integrity coefficient.In this context,hyperspectral imaging and digital panoramic borehole camera technologies are applied to analyze the mineral content and integrity of rock mass.Based on the carbonate mineral content and fissure area ratio,the strength reduction factor and integrity coefficient are calculated to improve the GSI evaluation method.According to the results of mineral classification and fissure identification,the strength reduction factor and integrity coefficient increase with the depth of rock mass.The rock mass GSI calculated by the improved method is mainly concentrated between 40 and 60,which is close to the calculation results of the traditional method.The GSI error rates obtained by the two methods are mostly less than 10%,indicating the rationality of the hyperspectral-digital borehole image coupled evaluation method.Moreover,the sensitivity of the fissure area ratio(Sr)to GSI is greater than that of the strength reduction factor(a),which means the proposed GSI is suitable for rocks with significant fissure development.The improved method reduces the influence of subjective factors and provides a reliable index for the deterioration evaluation of rock mass.
基金supported by CNPC-CZU Innovation Alliancethe Research Start-Up Fund of Changzhou University.
文摘Low salinity water containing sulfate ions can significantly alter the surface wettability of carbonate rocks.Nevertheless,the impact of sulfate concentration on the desorption of oil film on the surface of carbonate rock is still unknown.This study examines the variations in the wettability of the surface of carbonate rocks in solutions containing varying amounts of sodium sulfate and pure water.The problem is addressed in the framework of molecular dynamics simulation(Material Studio software)and experiments.The experiment’s findings demonstrate that sodium sulfate can increase the rate at which oil moisture is turned into water moisture.The final contact angle is smaller than that of pure water.The results of the simulations show that many water molecules travel down the water channel under the influence of several powerful forces,including the electrostatic force,the van der Waals force and hydrogen bond,crowding out the oil molecules on the calcite’s surface and causing the oil film to separate.The relative concentration curve of water and oil molecules indicates that the separation rate of the oil film on the surface of calcite increases with the number of sulfate ions.
基金financially supported by Xinjiang Oilfield Company of China(Grant No.2020-C4006)。
文摘In order to study the hydrocarbon generation(HCGE)characteristics of coal-bearing basins,the coal-measure source rocks of the Middle Jurassic-Lower Jurassic(MLJ)of the piedmont thrust belt in the southern margin of the Junggar Basin in Northwest China are taken as research objects.More than 60 MLJ samples were collected from outcrops and wells.Total organic carbon(TOC),rock pyrolysis(Rock-Eval),organic petrological,vitrinite reflectance(%Ro),and hydrous pyrolysis were performed to analyze the relevant samples.The pyrolysis gases and liquid products were measured,and then the chemical composition,as well as carbon isotopes of the gases,were analyzed.The results indicate that the MLJ source rocks have the capacity for large-scale gas generation.In addition,for coal-measure source rocks,the heavier the carbon isotope of kerogen(δ^(13)C_(kerogen)),the lower the liquid hydrocarbon and hydrocarbon gas yield,and the easier it is to produce non-hydrocarbon gas.It is worth noting that when theδ^(13)C_(kerogen)in organic matter(OM)is relatively heavier,the fractionation of its products may become weaker in the evolutionary process.The vital contribution of the MLJ source rock to natural gas resources in the study area was further confirmed by comparing it with the Jurassic source gas.
基金This research was supported by the KAUST Endowment at King Abdullah University of Science and Technology,Saudi Arabia.We thank Gabrielle.E.Abelskamp in Energy GeoEngineering Laboratory at King Abdullah University of Science and Technology for editing the manuscript.
文摘Carbonate rocks are extensively used in civil infrastructure and play a critical role in geoenergy geoengineering,either as hydrocarbon reservoirs or potential repositories for CO_(2)geological storage.Carbonate genesis and diagenetic overprint determine the properties of carbonate rocks.This study combines recent data gathered from Madison Limestone and an extensive dataset compiled from published sources to analyze the hydraulic and mechanical properties of limestone carbonate rocks.Physical models and data analyses recognize the inherently granular genesis of carbonate rocks and explain the strong dependency of physical properties on porosity.The asymptotically-correct power model in terms of(1-Ф/Ф*)a is a good approximation to global trends of unconfined stiffness E and unconfined compressive strength UCS,cohesive intercept in Mohr-Coulomb failure envelopes,and the brittle-toductile transition stress.This power model is the analytical solution for the mechanical properties of percolating granular structures.We adopted a limiting granular porosityФ*=0.5 for all models,which was consistent with the loosest packing of monosize spheres.The fitted power model has exponent(α=2)in agreement with percolation theory and highlights the sensitivity of mechanical properties to porosity.Data and models confirm a porosity-independent ratio between unconfined stiffness and strength,and the ratio follows a log-normal distribution with mean(E/UCS)≈300.The high angle of internal shear strength measured for carbonate rocks reflects delayed contact failure with increased confinement,and it is not sensitive to porosity.Permeability spans more than six orders of magnitude.Grain size controls pore size and determines the reference permeability k^(*)at the limiting porosityФ*=0.5.For a given grain size from fine to coarse-grained dominant carbonates,permeability is very sensitive to changes in porosity,suggesting preferential changes in the internal pore network during compaction.
文摘Nigeria has an abundance of valuable solid minerals and rocks which can generate revenue for the government if they are fully exploited. Carbonate rock is one of such rocks that occur prominently in Igwe Igarra area of Edo State. Five (5) carbonate rock samples (Four marble and One Calcsilicate) were subjected to geochemical analyses. A petrographic study reveals that marble and calcsilicate contain calcite, quartz, microcline, plagioclase, biotite and opaque minerals. Geochemical data shows that carbonate rocks have variable geochemical characteristics: Igwe marble is highly Calcitic (96% - 98%) and very low in dolomite Mg(CO<sub>3</sub>). Calcsilicate rock is low in CaO (27.5%) and higher in marble. The Igwe marble is pure and contains fewer impurities compared to calcsilicate rock which makes it unideal for usage. Based on these characteristics the marble from Igwe is suitable as raw materials for the productions of glass, papers, beet sugar, aggregates, lubricants and fillers.
基金supported by the Natural Science Foundation of China(No.41274138)
文摘The Ordovician carbonate rocks of the Yingshan formation in the Tarim Basin have a complex pore structure owing to diagenetic and secondary structures. Seismic elastic parameters(e.g., wave velocity) depend on porosity and pore structure. We estimated the average specific surface, average pore-throat radius, pore roundness, and average aspect ratio of carbonate rocks from the Tazhong area. High P-wave velocity samples have small average specific surface, small average pore-throat radius, and large average aspect ratio. Differences in the pore structure of dense carbonate samples lead to fluid-related velocity variability. However, the relation between velocity dispersion and average specific surface, or the average aspect ratio, is not linear. For large or small average specific surface, the pore structure of the rock samples becomes uniform, which weakens squirt fl ow and minimizes the residuals of ultrasonic data and predictions with the Gassmann equation. When rigid dissolved(casting mold) pores coexist with less rigid microcracks, there are significant P-wave velocity differences between measurements and predictions.
基金sponsored jointly by the National Natural Science Foundation of China(No.41074098)the Key State Science and Technology Project(2011ZX05023-005-005)China University of Petroleum(Beijing) Fund(KYJJ2012-05-08)
文摘Strong heterogeneity and complex pore systems of carbonate reservoir rock make its rock physics model building and fluid substitution difficult and complex. However, rock physics models connect reservoir parameters with seismic parameters and fluid substitution is the most effective tool for reservoir prediction and quantitative characterization. On the basis of analyzing complex carbonate reservoir pore structures and heterogeneity at seismic scale, we use the gridding method to divide carbonate rock into homogeneous blocks with independent rock parameters and calculate the elastic moduli of dry rock units step by step using different rock physics models based on pore origin and structural feature. Then, the elastic moduli of rocks saturated with different fluids are obtained using fluid substitution based on different pore connectivity. Based on the calculated elastic moduli of rock units, the Hashin-Shtrikman-Walpole elastic boundary theory is adopted to calculate the carbonate elastic parameters at seismic scale. The calculation and analysis of carbonate models with different combinations of pore types demonstrate the effects of pore type on rock elastic parameters. The simulated result is consistent with our knowledge of real data.
基金supported by the National Natural Science Foundation of China(No.41274136)
文摘We developed an anisotropic effective theoretical model for modeling the elastic behavior of anisotropic carbonate reservoirs by combining the anisotropic self-consistent approximation and differential effective medium models.By analyzing the measured data from carbonate samples in the TL area,a carbonate pore-structure model for estimating the elastic parameters of carbonate rocks is proposed,which is a prerequisite in the analysis of carbonate reservoirs.A workflow for determining elastic properties of carbonate reservoirs is established in terms of the anisotropic effective theoretical model and the pore-structure model.We performed numerical experiments and compared the theoretical prediction and measured data.The result of the comparison suggests that the proposed anisotropic effective theoretical model can account for the relation between velocity and porosity in carbonate reservoirs.The model forms the basis for developing new tools for predicting and evaluating the properties of carbonate reservoirs.
基金sponsored by the National Nature Science Foundation of China (Grant No.40904034 and 40839905)
文摘With a more complex pore structure system compared with clastic rocks, carbonate rocks have not yet been well described by existing conventional rock physical models concerning the pore structure vagary as well as the influence on elastic rock properties. We start with a discussion and an analysis about carbonate rock pore structure utilizing rock slices. Then, given appropriate assumptions, we introduce a new approach to modeling carbonate rocks and construct a pore structure algorithm to identify pore structure mutation with a basis on the Gassmann equation and the Eshelby-Walsh ellipsoid inclusion crack theory. Finally, we compute a single well's porosity using this new approach with full wave log data and make a comparison with the predicted result of traditional method and simultaneously invert for reservoir parameters. The study results reveal that the rock pore structure can significantly influence the rocks' elastic properties and the predicted porosity error of the new modeling approach is merely 0.74%. Therefore, the approach we introduce can effectively decrease the predicted error of reservoir parameters.
基金funded by the National Natural Science Foundation of China(Grant Nos.42141009,41825018,41888101 and 41902289)the Key Research Program of the Institute of Geology and Geophysics,CAS(Grant No.IGGCAS-202201)the Second Tibetan Plateau Scientific Expedition and Research Program(STEP)(Grant No.2019QZKK0904)。
文摘Supercritical carbon dioxide(ScCO_(2))fracturing has great advantages and prospects in both shale gas exploitation and CO_(2)storage.This paper reviews current laboratory experimental methods and results for sedimentary rocks fractured by ScCO_(2).The breakdown pressure,fracture parameters,mineral composition,bedding plane angle and permeability are discussed.We also compare the differences between sedimentary rock and granite fractured by ScCO_(2),ultimately noting problems and suggesting solutions and strategies for the future.The analysis found that the breakdown pressure of ScCO_(2)was reduced 6.52%–52.31%compared with that of using water.ScCO_(2)tends to produce a complex fracture morphology with significantly higher permeability.When compared with water,the fracture aperture of ScCO_(2)was decreased by 4.10%–72.33%,the tortuosity of ScCO_(2)was increased by 5.41%–70.98%and the fractal dimension of ScCO_(2)was increased by 4.55%–8.41%.The breakdown pressure of sandstone is more sensitive to the nature of the fracturing fluid,but fracture aperture is less sensitive to fracturing fluid than for shale and coal.Compared with granite,the tortuosity of sedimentary rock is more sensitive to the fracturing fluid and the fracture fractal dimension is less sensitive to the fracturing fluid.Existing research shows that ScCO_(2)has the advantages of low breakdown pressure,good fracture creation and environmental protection.It is recommended that research be conducted in terms of sample terms,experimental conditions,effectiveness evaluation and theoretical derivation in order to promote the application of ScCO_(2)reformed reservoirs in the future.
基金supported by the National Natural Scientific Foundation of China(Grant No.40872213)the projects from the China Geological Survey(Grant Nos. 1212010911062 and S-2010-KP03-07-02)+1 种基金from the Ministry of Land and Resources(Grant No.201211086-05)IGCP 598:Environmental Change and Sustainability Karst Systems
文摘Carbonate rock outcrops cover 9%-16% of the continental area and are the principal source of the dissolved inorganic carbon (DIC) transferred by rivers to the oceans, a consequence their dissolution. Current estimations suggest that the flux falls between 0.1-0.6 PgC/a. Taking the intermediate value (0.3 PgC/a), it is equal to 18% of current estimates of the terrestrial vegetation net carbon sink and 38% of the soil carbon sink. In China, the carbon flux from carbonate rock dissolution is estimated to be 0.016 PgC/a, which accounts for 21%, 87.5%-150% and 2.3 times of the forest, shrub and grassland net carbon sinks respectively, as well as 23%-40% of the soil carbon sink flux. Carbonate dissolution is sensitive to environmental and climatic changes, the rate being closely correlated with precipitation, temperature, also with soil and vegetation cover. HCO3 in the water is affected by hydrophyte photosynthesis, resulting in part of the HCO~ being converted into DOC and POC, which may enhance the potential of carbon sequestration by carbonate rock dissolution. The possible turnover time of this carbon is roughly equal to that of the sea water cycle (2000a). The uptake of atmospheric/soil CO2 by carbonate rock dissolution thus plays an important role in the global carbon cycle, being one of the most important sinks. A major research need is to better evaluate the net effect of this sink in comparison to an oceanic source from carbonate mineral precipitation.
文摘Crustose lichens are distributed extensively in karst areas in Southern China. They can be found on the surface of carbonate rocks. Through biophysical and biochemical processes, crustose lichens reform the subsurface of carbonate rocks and in the meanwhile change their physical and chemical properties: (1) the mechanical strength decreases by 17.04° on average (up to 33.2°); (2) the chemical solution surface area increases from 28.26% to 75.36% (lichen microholes considered only); and (3) the water-holding capacity is greatly improved. Comparative field experiments between biokarst samples underneath crustose lichens and fresh rock samples with the same composition and texture show that the corrosional rate of carbonate rocks of the former is 1.264–1.643 times higher than that of the latter. Crustose lichens are considered as an activator of the surface corrosion of carbonate rocks.
基金jointly funded by the National Science and Technology Major Project of China (Grant No. 2016ZX05003-005)National Natural Science Foundation of China (Grant Nos. 41472100 and 41322017)
文摘Carbonates have been known to act as hydrocarbon source rocks, but their basic geochemical and associated hydrocarbon generation characteristics remain not well understood as they occur with argillaceous source rocks in most cases, and the hydrocarbon generation from each rock type is di cult to distinguish, forming one of puzzling issues within the field of petroleum geology and geochemistry. To improve the understanding of this critical issue, this paper reviews recent advances in this field and provides a summary of key areas that can be studied in future. Results show that carbonate source rocks are generally associated with high-salinity environments with low amounts of terrestrial inputs and low dissolved oxygen contents. Petrographically, these source rocks are dark gray or black, fine-grained, stratified, and contain bacterial and algal bioprecursors along with some other impurities. They generally have low organic matter contents, although these can vary significantly in di erent cases(e.g., the total organic carbon contents of marine and lacustrine carbonate source rocks in China are generally 0.1%–1.0% and 0.4%–4.0%, respectively). These rocks contain type I and type II kerogen, meaning there is a lack of vitrinites. This means that assessment of the maturity of the organic matter in these sediments needs to use non-traditional techniques rather than vitrinite reflectance. In terms of molecular geochemistry, carbonate source rocks have typical characteristics indicative of generally reducing and saline environments and lower organism-dominated bioprecursors of organic matter, e.g., high contents of sulfur compounds, low Pr/Ph ratios, and dominance of n-alkanes. Most of the carbonate source rocks are typically dominated by D-type organic facies in an oxidized shallow water mass, although high-quality source rocks generally contain A-and B-type organic facies in saline lacustrine and marine-reducing environments, respectively. The hydrocarbon generation model for the carbonate source rocks can involve early, middle, and late stages, with a diversity of hydrocarbons within these rocks, which can be aggregated, adsorbed, enclosed within minerals, or present as inclusions. This in turn implies that the large-scale hydrocarbon expulsion from these rocks is reliant on brittle deformation caused by external forces. Finally, a number of aspects of these source rocks remain unclear and need further study, including the e ectiveness of carbonates as hydrocarbon source rocks, bioprecursors, and hydrocarbon generation models of carbonate source rock, and the di erences between marine and lacustrine carbonate source rocks.
基金supported by National Science Foundation of China (Nos. 41172001 and 41772015 to Sun and No. 41772359 to Shen)
文摘Iron and manganese are the important redoxsensitive elements in the ocean. Previous studies have established a series of paleo-depositional redox proxies based on the form and content of iron in sedimentary rocks(e.g., degree of pyritization, FeHR/FeT, Fe/Al). These proxies were developed and applied on siliciclastic-rich marine sediments. Although marine carbonate rocks are generally considered to preserve the geochemical signals of ancient seawater, neither Fe nor Mn content in marine carbonate rocks(Fecarb, Mncarb) has been independently used as a proxy to quantify environmental cues in paleo-oceans. Both Fe and Mn are insoluble in oxic conditions(Fe_2O_3, Fe(OH)_3,MnO_2), while their reduced forms(Fe^(2+) and Mn^(2+)) are soluble. Therefore, oxic seawater should have low concentrations of dissolved Fe^(2+)and Mn^(2+), and accordingly carbonate rocks precipitated from oxic seawater should have low Fecarband Mncarb, and vice versa. To evaluate whether Fecarband Mncarbcan be used to quantify oxygen fugacity in seawater, we measured Fecarband Mncarbof Upper Devonian marine carbonate rocks collected from nine sections in South China. Fecarbof intraplatform basin samples wassignificantly higher than that of shelf samples, while shelf and basin samples had comparable Mncarb. The modeling result indicates that the dramatic difference in Fecarbcannot be explained by variation in oxygen fugacity between the shelf and basin seawater. Instead, both Fecarband Mncarb appear to be more sensitive to benthic flux from sediment porewater that is enriched in Fe^(2+)and Mn^(2+). Porewater Fe^(2+)and Mn^(2+)derive from bacterial iron and manganese reduction; flux was controlled by sedimentation rate and the depth of the Fe(Mn) reduction zone in sediments, the latter of which is determined by oxygen fugacity at the water–sediment interface. Thus, high Fecarbof the basin samples might be attributed to low sedimentation rate and/or low oxygen fugacity at the seafloor. However, invariant Mncarbof the shelf and basin samples might be the consequence of complete reduction of Mn in sediments. Our study indicates that marine carbonate rocks may not necessarily record seawater composition, particularly for benthic carbonate rocks. The influence of benthic flux might cause carbonate rocks' geochemical signals to deviate significantly from seawater values. Our study suggests that interpretation of geochemical data from carbonate rocks, including carbonate carbon isotopes, should consider the process of carbonate formation.
基金supported by the China Postdoctoral Science Foundation (grant No. 2017M611108)the National Science and Technology Major Project of China (grant No. 2016ZX05006006-001)the National Basic Research Program of China (grant Nos. 2011CB2011-02 and 2014CB239100)
文摘Previous studies have postulated the contribution of present-day low-total organic carbon (TOC) marine carbonate source rocks to oil accumulations in the Tabei Uplift, Tarim Basin, China. However, not all present-day low-TOC carbonates have generated and expelled hydrocarbons; therefore, to distinguish the source rocks that have already expelled sufficient hydrocarbons from those not expelled hydrocarbons, is crucial in source rock evaluation and resource assessment in the Tabei Uplift. Mass balance can be used to identify modern low-TOC carbonates resulting from hydrocarbon expulsion. However, the process is quite complicated, requiring many parameters and coefficients and thus also a massive data source. In this paper, we provide a quick and cost effective method for identifying carbonate source rock with present-day low TOC, using widely available Rock-Eval data. First, we identify present-day low-TOC carbonate source rocks in typical wells according to the mass balance approach. Second, we build an optimal model to evaluate source rocks from the analysis of the rocks' characteristics and their influencing factors, reported as positive or negative values of a dimensionless index of Rock-Eval data (IR). Positive IR corresponds to those samples which have expelled hydrocarbons. The optimal model optimizes complicated calculations and simulation processes; thus it could be widely applicable and competitive in the evaluation of present-day low TOC carbonates. By applying the model to the Rock-Eval dataset of the Tabei Uplift, we identify present-day iow-TOC carbonate source rocks and primarily evaluate the contribution equivalent of 11.87×10^9 t oil.
基金the Ministry of Science and Technology of China(Grant No.2006CB403200)National Natural Science Foundation of China(Grant No.49463011,49833002 and 49962002)+2 种基金the open foundation projects of the State Key Laboratory of Environmental Geochemistry(in the years of 1993 and 1995)Engineering Project for Cross-century Qualified Scientific and Technological Personnel of Guizhou Province (2000-2004)Science Foundation of Guizhou Province.
文摘We investigated the weathering-pedogenesis of carbonate rocks and its environmental effects in subtropical regions of China. The investigation demonstrated that the weathering- pedogenesis of carbonate rocks is the process of a joint action of corrosion and illuviation and metasomatism in subtropical region. It is characterized by multi-stage, multi-path and multi-style. With the persisting development of weathering-pedogenesis of carbonate rocks, metasomatic pedogenesis progressively became the main process of the weathering-pedogenesis and the dominant style of formation of minerals. And it proceeds through the whole process of evolution of the weathering-pedogenesis of carbonate rocks. The stage evolution of weathering-pedogenesis of carbonate rocks and the fractionation evolution of newly produced minerals are characterized by obvious vertically zoning structures and the rules of gradation of elements geochemical characteristics in the carbonate rocks weathering profiles. The geochemical process of weathering-pedogenesis of carbonate rocks can be divided into three geochemical evolution stages, i.e., the Ca, Mg-depletion and Si, Al-enrichment stage; the Fe, Mn enrichment stage and the Si-depletion and Al-enrichment stage in the subtropical regions. Consistent with the three geochemical evolution stages, the sequence of formation and evolution of minerals can be divided into the clay mineral stage; the Fe, Mn oxide and the gibbsite stage. The influence of weathering-pedogenesis of carbonate rocks on the chemical forms of heavy elements is mainly affected via newly produced components and minerals in the process of weathering-pedogenesis, e.g., iron oxide minerals and organic matters. The important mechanism for the mobilization, transport and pollution of F and As is affected the selective adsorption and desorption of F and As on the surface of iron oxide minerals in the subtropical karst zones, i.e., the selective adsorption and desorption on mineral surfaces of newly produced minerals in the process of weathering-pedogenesis control the geochemical behavior of elements on the Earth's surface and environmental quality in subtropical regions.
基金Financial supports for this research was provided by the National Nature Science Foundation of China(Grant 40073026)Ministry of Science and Technology of China(Grant 164)+1 种基金Natural Science Foundation of Guangxi(Grant 9824021)Ministry of Land and Resources of China(Grant 9806)and Bremen University of Germany.
文摘The conversion of CO2 into H+ and is a relatively slow reaction. Hence, its kinetics may be rate determining in carbonate rock dissolution. Carbonic anhydrase (CA), which is widespread in nature, was used to catalyze the CO2 conversion process in dissolution experiments of limestone and dolomite. It was found that the rate of dissolution increases by a factor of about 10 after the addition of CA at a high CO2 partial pressure (Pco2) for limestone and about 3 at low Pco2 for dolomite. This shows that reappraisal is necessary for the importance of chemical weathering (including carbonate rock dissolution and silicate weathering) in the atmospheric CO2 sink and the mysterious missing sink in carbon cycling. It is doubtless that previous studies of weathering underestimated weathering rates due to the ignorance of CA as an activator in weathering, thus the contribution of weathering to the atmospheric CO2 sink is also underestimated. This finding also shows the need to examine the situ distribution and activity of CA in different waters and to investigate the role of CA in weathering.
基金This work was jointly supported by the Knowledge-Innovation Project of the Institute of Geochemistry,the“Westerm Light”Program sponsored by the Chinese Academy of Sciencesthe National Natural Science Foundation of China grants 49833002,40273015 and 40371012.
文摘Owing to the low contents of their acid-insoluble components, carbonate rocks tend to decrease sharply in volume in association with the formation of weathering crust. The formation of a 1 m-thick weathering crust would usually consume more than ten meters to several tens of meters of thickness of parent rocks. The knowledge of how to identify the homogeneity of parent rocks is essential to understand the formation mechanism of weathering crust in karst regions, especially that of thick-layered red weathering crust. In this work the grain-size analyses have demonstrated that the three profiles studied are the residual weathering crust of carbonate rocks and further showed that there objectively exists the heterogeneity of parent rocks in the three studied weathering crusts. The heterogeneity of parent rocks can also be reflected m geochemical parameters of major elements, just as the characteristics of frequency plot of grain-size distribution. Conservative trace element ratios Zr/Hf and Nb/Ta are proven to be unsuitable for tracing the heterogeneity of parent rocks of weathering crust, but its geochemical mechanism is unclear. The authors strongly suggest in this paper that the identification of the homogeneity of parent rocks of weathering crust in karst regions is of prime necessity.