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 δ₁₃ 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.     

Quantifying the carbon source of pedogenic calcite veins in weathered limestone: implications for the terrestrial carbon cycle

The continent is the second largest carbon sink on Earth’s surface.With the diversification of vascular land plants in the late Paleozoic,terrestrial organic carbon burial is represented by massive coal formation,while the development of soil profiles would account for both organic and inorganic carbon burial.As compared with soil organic carbon,inorganic carbon burial,collectively known as the soil carbonate,would have a greater impact on the long-term carbon cycle.Soil carbonate would have multiple carbon sources,including dissolution of host calcareous rocks,dissolved inorganic carbon from freshwater,and oxidation of organic matter,but the host calcareous rock dissolution would not cause atmospheric CO2drawdown.Thus,to evaluate the potential effect of soil carbonate formation on the atmospheric p CO2level,different carbon sources of soil carbonate should be quantitatively differentiated.In this study,we analyzed the carbon and magnesium isotopes of pedogenic calcite veins developed in a heavily weathered outcrop,consisting of limestone of the early Paleogene Guanzhuang Group in North China.Based on the C and Mg isotope data,we developed a numerical model to quantify the carbon source of calcite veins.The modeling results indicate that4–37 wt%of carbon in these calcite veins was derived from atmospheric CO2.The low contribution from atmospheric CO2might be attributed to the host limestone that might have diluted the atmospheric CO2sink.Nevertheless,taking this value into consideration,it is estimated that soil carbonate formation would lower 1 ppm atmospheric CO2within 2000 years,i.e.,soil carbonate alone would sequester all atmospheric CO2within 1 million years.Finally,our study suggests the C–Mg isotope system might be a better tool in quantifying the carbon source of soil carbonate.     

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).     

Geochemical features of the geothermal CO2-water-carbonate rock system and analysis on its CO2 sources--Examples from Huanglong Ravine and Kangding, Sichuan, and Xiage, Zhongdian, Yunnan

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).     

Molecular and carbon isotopic compositions of gas inclusions of deep carbonate rocks in the Tarim Basin

Gaseous components of gas inclusions in deep carbonate rocks (>5700 m) from the Tacan 1 well were analyzed by online mass spectrometry by means of either the stepwise heating technique or vacuum electromagnetism crushing. The carbon isotopic compositions of gases released by vacuum electromagnetism crushing were also measured. Although the molecular compositions of gas inclusions show differences between the two methods, the overall characteristics are that gas inclusions mainly contain CO2, whilst hydrocarbon gases, such as CH4, C2H6 and C3H8, are less abundant. The content of CO is higher in the stepwise heating experiment than that in the method of vacuum electromagnetism crushing, and there are only minor amounts of N2, H2 and O2 in gas inclusions. Methane δ13C values of gas inclusions in Lower Ordovician and Upper Cambrian rocks (from 5713.7 to 6422 m; -52‰-63‰) are similar to those of bacterial methane, but their chemical compositions do not exhibit the dry character in comparison with biogenic gases. These characteristics of deep gas inclusions may be related to the migration fractionation. Some deep natural gases with light carbon isotopic characteristics in the Tazhong Uplift may have a similar origin. The δ13C1 values of gas inclusions in Lower Cambrian rocks (7117-7124 m) are heavier (-39‰), consistent with highly mature natural gases. Carbon isotopic compositions of CO2 in the gas inclusions of deep carbonate rocks are similar (from -4‰ to -13‰) to those of deep natural gases, indicating predominantly an inorganic origin.     

A sensor array system for profiling moisture in unsaturated rock and soil

As the scope of hydrologic investigations extend deeper into the subsurface profile, and increasingly include fractured rock, there is a growing need for techniques that can accurately monitor saturation changes at a high spatial and temporal resolution in this environment. We have developed a technique, the Electrical Resistance Sensor Array System (ERSAS), to track moisture dynamics in vadose zone regions that include both fractured rock and soil. The performance of ERSAS was compared with the time domain reflectometry (TDR) technique under controlled and field conditions. We found that ERSAS was effective in determining patterns of saturation changes along vertical soil/rock profiles. Because of the small size of individual sensors, it was able to resolve travel times associated with a wetting front and peak saturation better than TDR. In addition, ERSAS is significantly cheaper than the TDR system, and the sensor arrays are relatively easier to install in the subsurface profile. Published in 2011 by John Wiley & Sons, Ltd.     

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.     

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.     

Primary dolostone related to the Cretaceous lacustrine hydrothermal sedimentation in Qingxi sag, Jiuquan Basin on the northern Tibetan Plateau

Based on comprehensive studies in petrography, petrofabric analysis and geochemistry, this paper describes a unique and rare laminated micritic ferruginous primary dolostone crystallized and precipitated from the alkaline hot brine under the conditions of the Mesozoic faulted lake basin. The main rock-forming mineral of this dolostone is ferruginous dolomite with a micritic structure. This dolomite mostly exhibits laminae of 0.1–1 mm thick and is often discovered with other minerals, such as albite, analcite, barite and dickite, which have at least two types of interbedded laminae. Petrogeochemistry reveals that this dolostone contains a large number of typomorphic elements of hydrothermal sedimentation, including Sb, Ba, Sr, Mn, and V. In addition, the LREE is in relatively high concentrations and possesses the typical REE distribution pattern with negative Eu anomaly. Oxygen isotope values (δ¹⁸O_PDB) range from 5.89‰ to 14.15‰ with an average of 9.69‰. The ratio of ⁸⁷Sr/⁸⁶Sr is between 0.711648 and 0.719546, with an average of 0.714718. These data indicate that the depositional environment is a stable, blocked, anoxic low-lying hot brine pool in the bottom of deep lake controlled by basement faults. The hydrothermal fluid is the alkaline hot brine formed by the combination of the infiltration lake water and mantle-derived magmatic water, consisting of many ions, including Ca²⁺, Mg²⁺ and Fe²⁺. Under the driving flow power of magmatic heat, gravity and compaction, the hydrothermal fluid overcame the overburden pressure and hydrostatic pressure of the lake water body, and boiled to explosion, and then the explosion shattered the original laminated micritic ferruginous primary dolostone near the vent and then formed a new type of dolostone called shattered “hydroexplosion breccias”. In the low-lying, unperturbed hot brine pool, far from the vent, the laminated micritic ferruginous primary dolostone was quickly crystallized and chemicals precipitated from the hydrotherm. This study of special rocks contributes to research into the causes of the formation of lacustrine carbonate rocks and dolostone. In particular, it provides new examples and research insights for future studies of the lacustrine dolomite from the similar Mesozoic and Cenozoic basins in China.     

Fingerprinting TCE in a bedrock aquifer using compound-specific isotope analysis

A dual isotope approach based on compound-specific isotope analysis (CSIA) of carbon (C) and chlorine (Cl) was used to identify sources of persistent trichloroethylene (TCE) that caused the shut-down in 1994 of a municipal well in an extensive fractured dolostone aquifer beneath Guelph, Ontario. Several nearby industrial properties have known subsurface TCE contamination; however, only one has created a comprehensive monitoring network in the bedrock. The impacted municipal well and many monitoring wells were sampled for volatile organic compounds (VOCs), inorganic parameters, and CSIA. A wide range in isotope values was observed at the study site. The TCE varies between -35.6‰ and -21.8‰ and from 1.6‰ to 3.2‰ for δ(13) C and δ(37) Cl, respectively. In case of cis-1,2-dichloroethene, the isotope values range between -36.3‰ and -18.9‰ and from 2.4‰ to 4.7‰ for δ(13) C and δ(37) Cl, respectively. The dual isotope approach represented by a plot of δ(13) C vs. δ(37) Cl shows the municipal well samples grouped in a domain clearly separate from all other samples from the property with the comprehensive well network. The CSIA results collected under non-pumping and short-term pumping conditions thus indicate that this particular property, which has been studied intensively for several years, is not a substantial contributor of the TCE presently in the municipal well under non-pumping conditions. This case study demonstrates that CSIA signatures would have been useful much earlier in the quest to examine sources of the TCE in the municipal well if bedrock monitoring wells had been located at several depths beneath each of the potential TCE-contributing properties. Moreover, the CSIA results show that microbial reductive dechlorination of TCE occurs in some parts of the bedrock aquifer. At this site, the use of CSIA for C and Cl in combination with analyses of VOC and redox parameters proved to be important due to the complexity introduced by biodegradation in the complex fractured rock aquifer. It is highly recommended to revisit the study when the municipal well is back into full operation.     

Determining CO_2 consumption from elemental change in soil profiles developed on carbonate and silicate rocks

To further understand the roles of carbonate and silicate rocks in regulating the atmosphere/soil CO_2level,the flux of CO_2 consumed by the chemical weathering of silicate and carbonate rocks was determined from the elemental change in soil profiles.Results showed that the chemical weathering of carbonate rocks mainly occurred at the rock-regolith interface,and that the further weathering of the residua soil on the carbonate rocks was similar to that of the granite profile.Chemical weathering of the silicate rocks occurred through the whole profiles.Therefore,CO_2 consumed per volume by the silicate profiles[M_(sr)(CO_2)]and the residues on carbonate rocks[M_(cr)(CO2)]were calculated based on the elemental weathering gradients.CO_2 consumed by carbonate protolith[M_(cp)(CO_2)]was calculated from the elemental change at the rock-regolith interface.The M_(sr)(CO_2) were about tens to thousands orders of magnitude greater than M_(cr)(CO_2).Even so,this demonstrated that the residues on carbonate rocks could be a sink of CO2_ on long-term scales.The M_(cp)(CO_2) was about four times larger than M_(sr)(CO_2),which demonstrated that carbonate rocks played a more important role in regulating the CO_2 level than the silicate rocks did during the pedogenic process of the profiles.     

Validity of radiocarbon dates on ground water

Carbonate species, dissolved in appreciable quantities in all ground waters, can be extracted and used for radiocarbon dating. The material is mainly of biogenic origin, but contains some bicarbonate produced from limestone. This causes a dilution of the radiocarbon activity of the total carbonate species in the water and a correction is necessary in order to determine absolute radiocarbon ages, i.e., the time since the waters went underground. Three methods of evaluating the limestone contributions are examined critically: carbonate species ratios, carbon-13 variations, and concurrent tritium measurements. All possess uncertainties. The largest errors occur in the carbon-13 procedure, due to the wide natural fluctuation of the stable isotope content in plants and the occurrence of isotope effects in the soil air-water carbon dioxide exchange. Comparisons of the limestone dilution correction techniques show that they produce analogous results in actual aquifer studies, but with small differences in the calculated radiocarbon ages. The reasons for these inconsistencies have not yet been unequivocally established. Two problems are: the possibility of irreversible exchange of the ground water dissolved carbonate species with limestone in the aquifer matrix, and the significance of exchange of carbon dioxide in the water with that of the soil air in the surface layer of the catchment zone. Experiments are suggested that could resolve these questions.     

Dissolved inorganic carbon sourcing using δ13CDIC from a karst influenced river system

Rivers, representing the primary conduits of dissolved inorganic carbon (DIC) from the continents to the oceans, are important components to the global carbon cycle. To better understand the complex carbon cycling dynamics within two nested, mixed lithology watersheds, two sites were studied along the karst influenced upper Green River in south‐central Kentucky, USA. Weekly samples were collected from June 2013 through May 2014 and analyzed for δ¹³C_DIC. The mixing model IsoSource was employed to better understand source partitioning differences over seasonal time spans and across the two nested basins. In both the lithologically mixed upstream basin (53% carbonate rocks, 47% siliciclastic) and carbonate rock dominated downstream basin (96% carbonate rocks in the drainage area between Greensburg and Munfordville, 78% in the total area upstream from Munfordville), DIC was primarily derived from soil respiration. The proportion of DIC from dissolved carbonate minerals derived from the downstream carbonate rock dominated basin was similar to the upstream basin, due to carbonate mineral dissolution having such a consistent effect on the overall DIC content of the river. Seasonally, soil respiration provided the most DIC from fall to winter. Early spring precipitation, combined with limited seasonal photosynthesis, shifted groundwater to be the primary source of DIC, bringing in a flush of carbonate mineral‐rich water during higher flows. This study provides insight into carbon dynamics across multiple lithologies and the important influence of seasonality using carbon isotope sourcing to determine carbonate mineral dissolution variability and aid in understanding its contribution to global carbon flux quantification. Copyright © 2015 John Wiley & Sons, Ltd.     

Dissolved inorganic carbon isotopes of a typical alpine river on the Tibetan Plateau revealing carbon sources,wetland effect and river recharge

The Nyangqu River, the largest right bank tributary of the Yarlung Zangbo River in the Qinghai–Tibet Plateau, was representative of an alpine riverine carbon cycle experiencing climate change. In this study, dissolved inorganic carbon (DIC) spatial and seasonal variations, as well as their carbon isotopic compositions (δ¹³C_DIC) in river water and groundwater were systematically investigated to provide constraints on DIC sources, recharge and cycling. Significant changes in the δ¹³C_DIC values (from −2.9‰ to −23.4‰) of the water samples were considered to be the result of different contributions of two dominant DIC origins: soil CO₂ dissolution and carbonate weathering. Three types of rock weathering (dissolution of carbonate minerals by H₂CO₃ and H₂SO₄, and silicate dissolution by H₂CO₃) were found to control the DIC input into the riverine system. In DIC cycling, groundwater played a significant role in delivering DIC to the surface water, and DIC supply from tributaries to the main stream increased from the dry season to the wet season. Notably, the depleted δ¹³C_DIC ‘peak’ around the 88.9° longitude, especially in the September groundwater samples, indicated the presence of ‘special’ DIC, which was attributed to the oxidation of methane from the Jiangsa wetland located nearby. This wetland could provide large amounts of soil organic matter available for bacterial degradation, producing ¹³C-depleted methane. Our study provided insights regarding the role of wetlands in riverine carbon cycles and highlighted the contribution of groundwater to alpine riverine DIC cycles.     

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.     

河库连续体中溶解性无机碳及其同位素的时空分异特征——以澜沧江云南段为例

河流及水库等水生态系统中的溶解性无机碳(DIC)是全球碳循环与大气、陆地和海洋之间碳相互作用的重要组成部分.以澜沧江云南段上游天然河段及下游梯级水库群形成的连续体为研究对象,分析了河库连续体表层水体中水化学特征、溶解性无机碳浓度及其碳同位素时空分布特征.研究结果表明:河库连续体水体中溶解无机碳(DIC)及其同位素(δ13 C DIC)组成特征总体表现为:DIC浓度丰水期较低,枯水期较高,平均值分别为2.59±0.44和3.30±0.37 mmol/L;δ13 C DIC值丰水期偏负、枯水期偏正,平均值分别为-8.52‰±0.38‰和-6.95‰±0.53‰,与自然河流的季节变化特征相似.水体DIC来源主要包括土壤及水体有机质分解生成的CO 2、碳酸盐风化和水气界面CO 2的交换过程.澜沧江河库连续体中DIC浓度及δ13 C DIC组成的时空异质性特征与流域岩性、土壤生物地球化学过程以及微生物活动强度等均有较大关系.当前,澜沧江梯级水库群建库时间短,梯级联合运行下调度复杂,水文条件多变,梯级水库对河流重要生源要素——碳累积影响方面的“水库效应”还不明显.     

Rhuddanian to Aeronian (Llandovery,early Silurian) carbon isotope stratigraphy throughout carbonate sequences in the upper Yangtze region,South China block

The Xiangshuyuan Formation (middle Rhuddanian to middle Aeronian stages of the Llandovery Series, lower Silurian) records a shelly fauna representing recovery after the end-Ordovician mass extinction in a well-oxygenated shallow carbonate platform of the Upper Yangtze region, South China Block. Carbon isotope stratigraphy is documented from limestone sequences of the formation at the Qiankou section, northeast Guizhou. The early Aeronian carbon isotope excursion (EACIE, with an amplitude of about 2 ‰ and peak value of 2.44 ‰) is identified in the middle and upper parts of the formation (Ozarkodina obesa conodont Biozone). The EACIE recorded herein correlates well with those in Baltica, Canada, and the United States; together with its records from organic material (δ¹³C_org) the data verify that the EACIE is a global event. The beginning of the EACIE can be used as a chemostratigraphic marker defining the Rhuddanian/Aeronian boundary in strata that lack high-resolution biostratigraphic constraints.     

Diagenetic fluid evolution and water-rock interaction model of carbonate cements in sandstone: An example from the reservoir sandstone of the Fourth Member of the Xujiahe Formation of the Xiaoquan-Fenggu area,Sichuan Province,China

Carbonate cement is the most abundant cement type in the Fourth Member of the Xujiahe Formation in the Xiaoquan-Fenggu area of the West Sichuan Depression. Here we use a systematic analysis of carbonate cement petrology, mineralogy, carbon and oxygen isotope ratios and enclosure homogenization temperatures to study the precipitation mechanism, pore fluid evolution, and distribution of different types of carbonate cement in reservoir sand in the study area. Crystalline calcite has relatively heavy carbon and oxygen isotope ratios(δ13C = 2.14‰, δ18O = -5.77‰), and was precipitated early. It was precipitated directly from supersaturated alkaline fluid under normal temperature and pressure conditions. At the time of precipitation, the fluid oxygen isotope ratio was very light, mainly showing the characteristics of a mixed meteoric water-seawater fluid(δ18O = -3‰), which shows that the fluid during precipitation was influenced by both meteoric water and seawater. The calcite cement that fills in the secondary pores has relatively lighter carbon and oxygen isotope ratios(δ13C = -2.36‰, δ18O = -15.68‰). This cement was precipitated late, mainly during the Middle and Late Jurassic. An important material source for this carbonate cement was the feldspar corrosion process that involved organic matter. The Ca2+, Fe3+ and Mg2+ ions released by the clay mineral transformation process were also important source materials. Because of water-rock interactions during the burial process, the oxygen isotope ratio of the fluid significantly increased during precipitation, by about 3‰. The dolomite cements in calcarenaceous sandstone that was precipitated during the Middle Jurassic have heavier carbon and oxygen isotope ratios, which are similar to those of carbonate debris in the sandstone(δ13C = 1.93‰, δ18O = -6.11‰), demonstrating that the two are from the same source that had a heavier oxygen isotope ratio(δ18O of about 2.2‰). The differences in fluid oxygen isotope ratios during cement precipitation reflect the influences of different water-rock interaction systems or different water-rock interaction strengths. This is the main reason why the sandstone containing many rigid particles(lithic quartz sandstone) has a relatively negative carbon isotope ratio and why the precipitation fluid in calcarenaceous sandstone has a relatively heavier oxygen isotope ratio.     

Major active faults determine the location of the Tongonan geothermal field: Evidence provided by rock alteration and stable isotope geochemistry

Abstract The influence of major active faults on rock alteration and stable isotope geochemistry is described for the Tongonan geothermal field, Leyte, the Philippines. In the Pliocene, acid alteration with characteristic iron enrichment (3 g/100 g) and calcium depletion (2 g/100 g) occurred along a Riedel shear fault in the Malitbog sector, and initial minor acid alteration also occurred along a similar shear in the Mahiao sector. Later, sodium metasomatism (5 g/100 g) coincided with the highest aquifer chloride (10 000 mg/kg) as a result of dissociation of saline magmatic fluids discharging through the reservoir rocks in the Upper Mahiao. The incursion of magmatic fluids (possibly δD 35‰, δ¹⁸O +7‰) set up a vigorous convection cell of meteoric water, which focused around low‐angle (L) shears centered in the Sambaloran sector. Meteoric water (δD ?35 to ?40‰, δ¹⁸O ?6 ± 1‰) depleted the reservoir in silica (6 g/100 g) and potassium (1–2 g/100 g). It also completely exchanged oxygen isotopes rapidly (within months) at high temperatures (300–400°C), and now does so continuously with fractured isotopically fresh or incompletely altered rock at small scales (centimeters or less) exposed by a 2 cm/year creep around the L shears to form a new component called geothermal water. Geothermal water mixes with meteoric water at lower temperatures (<300°C) to create the characteristic shift in δ¹⁸O of 6‰ at near constant δD (?35 ± 5‰). The 10‰ variation in δD is due to groundwater recharge derived from rain falling on steep terrain (5‰) and to enrichment of deuterium in boiling saline solutions (5‰); it is not due to two‐component mixing of meteoric with magmatic water. The low (～1) isotopic water/rock (W/R) ratios calculated from oxygen isotopes in previously published reports are meaningless, because the water contains four components (predominantly geothermal and meteoric water; <10% magmatic and rock water). W/R ratios of up to 1500 calculated from spring and rock chemistry are more realistic and, with a flow rate of approximately 50 L/s through a 30 km³ reservoir, can account for the estimated 3 My age of the system.