Dynamics Of Karstification: A Model Applied To Hydraulic Structures In Karst Terranes

To model the development of karst channels from primary fissures in limestone, a computer simulation of solutional widening of a fracture by calcite agressive water is proposed. The parameters defining the problem are the initial width a₀ of the fracture, its length l, and the hydraulic gradient i driving water through it. The dissolution rates limestone determine how fast enlargement of the fractures proceeds. At a calcite concentration, c, far from equilibrium, the dissolution follows a first-order rate law, F⁽¹⁾=α₀(c_eq-c); close to the equilibrium concentration, c_eq, a slow fourth-order rate law F⁽⁴⁾=β₀(c_eq-c)⁴ is valid. The results show that, at the time of initiation, the water flow through the karst channels increases slowly in time until an abrupt increase occurs. After this moment of breakthrough, the channel enlarges rapidly and evenly over its entire length by first-order kinetics. Breakthrough times have been calculated for karstification under natural conditions for low hydraulic gradients as functions of a₀, l, and i. Special attention is given to karstification in the vicinity of hydraulic structures where hydraulic gradients are high (>0.5) and channel lengths are below 200 m. We find that the breakthrough event will occur in less than 100 years, if: (i/l) > (5.3·10^?8a₀ ^?2.63P_CO2 ^?0.77) where l is in m and a₀ is in cm, (i/l) is given in m^-1, and P_CO2[atm] is the CO₂ pressure of the water entering the fracture. After this event, the channels will widen to a width of about 1 cm within only 10 years, which can cause considerable leakage near or through hydraulic structures. Finally, critical values of the parameters i, l, a₀, which give the conditions of failure in various types of hydraulic structures are discussed.     

Using non-conservative tracers to characterise karstification processes in the Merinos-Colorado-Carrasco carbonate aquifer system (southern Spain)

The systematic sampling of the chemical composition of the groundwater from five karst springs (including an overflow spring) and one outflowing borehole have permitted to determine distinctive chemical changes in the waters that reflect the geochemical processes occurring in a carbonate aquifer system from southern Spain. The analysis of the dissolution parameters revealed that geochemical evolution of the karst waters basically depends on the availability of the minerals forming aquifer rocks and the residence time within the aquifers. In the three proposed scenarios in the aquifers, which include the preferential flow routines, the more important geochemical processes taking place during the groundwater flow from the recharge to the discharge zones are: CO₂ dissolution and exsolution (outgassing), calcite net dissolution, calcite and dolomite sequential dissolution, gypsum/anhydrite and halite dissolution, de-dolomitization and calcite precipitation. A detailed analysis of the hydrochemical data set, saturation indices of the minerals and partial pressure of CO₂ in the waters joined to the application of geochemical modelling methods allowed the elaboration of a hydrogeochemical model of the studied aquifers. The developed approach contributes to a better understanding of the karstification processes and the hydrogeological functioning of carbonate aquifers, the latter being a crucial aspect for the suitable management of the water resources.     

Temperature-driven meltwater production and hydrochemical variations at a glaciated alpine karst aquifer: implication for the atmospheric CO<Subscript>2</Subscript> sink under global warming

About two hydrological years of continuous data of discharge, temperature, electrical conductivity and pH have been recorded at the Glarey spring in the Tsanfleuron glaciated karst area in the Swiss Alps, to understand how glaciated karst aquifer systems respond hydrochemically to diurnal and seasonal recharge variations, and how calcite dissolution by glacial meltwater contributes to the atmospheric CO₂ sink. A thermodynamic model was used to link the continuous data to monthly water quality data allowing the calculation of CO₂ partial pressures and calcite saturation indexes. The results show diurnal and seasonal hydrochemical variations controlled chiefly by air temperature, the latter influencing karst aquifer recharge by ice and snowmelt. Karst process-related atmospheric CO₂ sinks were more than four times higher in the melting season than those in the freezing season. This finding has implication for understanding the atmospheric CO₂ sink in glaciated carbonate rock terrains: the carbon sink will increase with increasing runoff caused by global warming, i.e., carbonate weathering provides a negative feedback for anthropogenic CO₂ release. However, this is a transient regulation effect that is most efficient when glacial meltwater production is highest, which in turn depends on the future climatic evolution.     

Review: Thermal water resources in carbonate rock aquifers

The current knowledge on thermal water resources in carbonate rock aquifers is presented in this review, which also discusses geochemical processes that create reservoir porosity and different types of utilisations of these resources such as thermal baths, geothermal energy and carbon dioxide (CO₂) sequestration. Carbonate aquifers probably constitute the most important thermal water resources outside of volcanic areas. Several processes contribute to the creation of porosity, summarised under the term hypogenic (or hypogene) speleogenesis, including retrograde calcite solubility, mixing corrosion induced by cross-formational flow, and dissolution by geogenic acids from deep sources. Thermal and mineral waters from karst aquifers supply spas all over the world such as the famous bath in Budapest, Hungary. Geothermal installations use these resources for electricity production, district heating or other purposes, with low CO₂ emissions and land consumption, e.g. Germany’s largest geothermal power plant at Unterhaching near Munich. Regional fault and fracture zones are often the most productive zones, but are sometimes difficult to locate, resulting in a relatively high exploration uncertainty. Geothermal installations in deep carbonate rocks could also be used for CO₂ sequestration (carbonate dissolution would partly neutralise this gas and increase reservoir porosity). The use of geothermal installations to this end should be further investigated.     

Étude expérimentale de la réactivité du CO2 supercritique vis-à-vis de phases minérales pures. Implications pour la séquestration géologique de CO2

Carbon dioxide sequestration in deep aquifers and depleted oilfields is a potential technical solution for reducing green-house gas release to the atmosphere: the gas containment relies on several trapping mechanisms (supercritical CO₂, CO_2(sc), dissolution together with slow water flows, mineral trapping) and on a low permeability cap-rock to prevent CO_2(sc), which is less dense than the formation water, from leaking upwards. A leakproof cap-rock is thus essential to ensure the sequestration efficiency. It is also crucial for safety assessment to identify and assess potential alteration processes that may damage the cap-rock properties: chemical alteration, fracture reactivation, degradation of injection borehole seals, etc. The reactivity of the host-rock minerals with the supercritical CO₂ fluid is one of the potential mechanisms, but it is altogether unknown. Reactivity tests have been carried out under such conditions, consisting of batch reactions between pure minerals and anhydrous supercritical CO₂, or a two-phase CO₂/H₂O fluid at 200?°C and 105/160 bar. After 45 to 60 days, evidence of appreciable mineral-fluid reactivity was identified, including in the water-free experiments. For the mixed H₂O/CO₂ experiments, portlandite was totally transformed into calcite; anorthite displayed many dissolution patterns associated with calcite, aragonite, tridymite and smectite precipitations. For the anhydrous CO₂ experiments, portlandite was totally carbonated to form calcite and aragonite; anorthite also displayed surface alteration patterns with secondary precipitation of fibrous calcite. To cite this article: O. Regnault et al., C. R. Geoscience 337 (2005).     

Assessing cave internal aerology in understanding carbon dioxide (CO<Subscript>2</Subscript>) dynamics: implications on calcite mass variation on the wall of Lascaux Cave (France)

Carbon dioxide gas is a key component in dissolution and precipitation of carbonates in karst and cave systems. Therefore, characterizing the internal aerology of a cave is essential to obtain the spatiotemporal distribution of temperature and CO₂ level. In this research, Lascaux Cave (France), an important adorned cavity, was studied. First, the spatiotemporal distribution of CO₂ and temperatures were examined using continuous monitoring at a per minute basis. High-resolution spatial measurements (14 PCO₂ locations and 27 locations for temperature) were carried out for a year in the epikarst and the cave (February 2015 to February 2016). The spatiotemporal analysis presents that air and rock temperatures vary for less than a degree Celsius (12.4–12.9 °C). These are controlled by the conduction of the external thermal waves through the overlying calcarenite massif. As a consequence, two seasonal internal aerologic regimes were identified: stratification and convection. These regimes govern the spatiotemporal distribution of the CO₂ levels (1.1–3.7%), showing that this parameter is a good natural marker of the internal air movements. Second, a method was proposed to estimate the calcite mass potentially affected by condensation water (dissolution process) and exfiltration water (precipitation process). This method, based on numerical simulations, relies on CO₂ and air and rock temperature spatiotemporal distributions in the cave. Third, the method was applied using the case of the left wall of the Hall of the Bulls (one of the most adorned part of the cave). Results showed that the calcite mass, possibly dissolved, varies from 0.0002 to 0.006 g when the mass potentially precipitated is higher (from 0.013 to 0.067 g) depending on the aerologic conditions. This method allows determining which alteration process (e.g., precipitation or dissolution) could eventually lead to the largest variation of calcite on the wall. The results can serve as useful data to the cave experts of the French Ministry of Culture and Communication in terms of Lascaux Cave management policies.     

鄂尔多斯盆地西部奥陶系风化壳岩溶作用模式

鄂尔多斯盆地下古生界马家沟组顶部遭受长期风化剥蚀,形成了以膏云岩为主的风化壳岩溶储层。通过偏光显微和超微扫描电镜深入观察了（含）膏云岩的孔隙类型及充填规律,分析了其岩溶作用特点,研究了以膏云岩为主的岩溶作用特征与传统碳酸盐岩岩溶作用特征的区别,探讨了膏云岩发育区的岩溶作用模式。结果表明:硬石膏结核和石膏晶体以其强亲水性和远高于白云石、方解石的溶解度,极易率先吸水发生溶解形成组构选择性溶蚀孔隙,导致膏云岩层蜂窝状溶孔的形成。硬石膏的高溶解度和力学不稳定性使得研究区以膏云岩、白云岩和灰云岩互层的风化壳储层以膏模孔、扩溶膏模孔及与之伴生的胀缩微裂缝为主要储集空间,孔隙大小具有明显的自限性。岩性—（含）膏云岩和沉积微相—海平面低位期潮上带（含）膏云坪沉积是储层形成的先天物质基础和环境条件,并因此直接导致（含）膏云岩储层的成层分布特征。表层膏云岩首先遭受淡水淋滤形成蜂窝状溶孔,多层成层分布膏云岩这种独特的物理化学性质使风化壳内的岩溶水以弥散性渗透为主,这是膏云岩发育区岩溶作用特征和模式与碳酸盐岩产生重要差异的根本原因。     

Carbonate weathering and connate seawater influencing karst groundwaters in the Gevas–Gurpinar–Güzelsu basins,Turkey

There are 59 springs at the Gevas–Gurp?nar–Güzelsu basins, 38 of these springs emerge from the fractured karst aquifers (recrystallized limestone and travertine) and 21 emerge from the Yuksekova ophiolites, K?rkgeçit formation and alluvium. The groundwater samples collected from 38 out of the total of 59 springs, two streams, one lake and 12 wells were analyzed physico-chemically in the year 2002. EC and TDS values of groundwater increased from the marble (high altitude) to the ophiolites and alluvium (toward Lake Van) as a result of carbonate dissolution and connate seawater. Five chemical types of groundwater are identified: Ca–Mg–HCO₃, Mg–Ca–HCO₃, Mg–Na–HCO₃, Na–Ca–HCO₃ and Mg–Ca–Na–HCO₃. The calculations and hydrochemical interpretations show that the high concentrations of Ca²⁺, Mg²⁺ and HCO₃ ^? as predominant ions in the waters are mainly attributed to carbonate rocks and high pCO₂ in soil. Most of the karst springs are oversaturated in calcite, aragonite and dolomite and undersaturated in gypsum, halite and anhydrite. The water–rock interaction processes that singly or in combination influence the chemical composition of each water type include dissolution of carbonate (calcite and dolomite), calcite precipitation, cation exchange and freshening of connate seawater. These processes contribute considerably to the concentration of major ions in the groundwater. Stable isotope contents of the groundwater suggest mainly direct integrative recharge.     

Effect of injected CO2 on geochemical alteration of the Altmark gas reservoir in Germany

Capturing CO₂ from point sources and storing it in geologic formations is a potential option for allaying the CO₂ level in the atmosphere. In order to evaluate the effect of geological storage of CO₂ on rock-water interaction, batch experiments were performed on sandstone samples taken from the Altmark reservoir, Germany, under in situ conditions of 125 °C and 50 bar CO₂ partial pressure. Two sets of experiments were performed on pulverized sample material placed inside a closed batch reactor in (a) CO₂ saturated and (b) CO₂ free environment for 5, 9 and 14 days. A 3M NaCl brine was used in both cases to mimic the reservoir formation water. For the “CO₂ free” environment, Ar was used as a pressure medium. The sandstone was mainly composed of quartz, feldspars, anhydrite, calcite, illite and chlorite minerals. Chemical analyses of the liquid phase suggested dissolution of both calcite and anhydrite in both cases. However, dissolution of calcite was more pronounced in the presence of CO₂. In addition, the presence of CO₂ enhanced dissolution of feldspar minerals. Solid phase analysis by X-ray diffraction and Mössbauer spectroscopy did not show any secondary mineral precipitation. Moreover, Mössbauer analysis did not show any evidence of significant changes in redox conditions. Calculations of total dissolved solids’ concentrations indicated that the extent of mineral dissolution was enhanced by a factor of approximately 1.5 during the injection of CO₂, which might improve the injectivity and storage capacity of the targeted reservoir. The experimental data provide a basis for numerical simulations to evaluate the effect of injected CO₂ on long-term geochemical alteration at reservoir scale.     

Geochemical controls on a calcite precipitating spring

A small spring fed stream was found to precipitate calcite by mainly inorganic processes and in a nonuniform manner. The spring water originated by rainwater falling in a 0.8 km² basin, infiltrating, and dissolving calcite and dolomite followed by dissolution of gypsum or anhydrite. The Ca²⁺/Mg²⁺ indicates that calcite is probably precipitated in the subsurface from a supersaturated solution. This water emerges from the spring still about 5 times supersaturated with respect to calcite and continues calcite precipitation. When 10 times supersaturation is reached, due to CO₂ degassing the precipitation is more rapid. The calcite accumulation from the stream with a flow of 5 l/s is calculated to be 12600 kg/yr with the highest rates in areas where CO₂ degassing is the greatest. The non-equilibrium, as shown by the high calcite supersaturation, is also reflected in a variable partitioning pattern for Sr²⁺ between the water and calcite.     

塔中西部奥陶系鹰山组古岩溶特征及主控因素

为明确塔中西部奥陶系鹰山组古岩溶储层发育及主控因素,总结鹰山组古岩溶特征及发育条件,划分了岩溶层组类型。在鹰山组古地貌恢复基础上,通过钻井、取心、测井等资料,分析丘状岩溶台地、上丘状岩溶缓坡地和下丘状岩溶缓坡地典型井岩溶缝洞特征。结合大量钻井资料分析了上述3类古地貌单元岩溶缝洞储层发育规律及主控因素。对岩溶缝洞储层发育深度分析表明,岩溶缝洞发育段主要在鹰山组顶面以下0~180 m,受3期海平面控制,发育多层缝洞。表层溶洞主要发育在0~50 m,泥质充填较强,测井GR值较高,溶洞规模多小于2 m。岩溶台地区岩溶缝洞形成受微地貌、水动力条件控制,以小规模溶洞、溶蚀孔洞、溶蚀裂缝为主,缝洞后期易充填。岩溶缓坡地岩溶缝洞形成受岩溶层组、水动力条件控制,以小溶蚀孔洞、溶蚀裂缝为主,后期不易充填。滨岸岩溶带及岩溶岛屿发育海水、混合水岩溶作用,溶蚀作用及冲蚀、侵蚀作用使该区域形成较大洞穴。     

Calcite dissolution driven by benthic mineralization in the deep-sea: in situ measurements of Ca2+, pH,pCO2 and O2

In situ measured microprofiles of Ca²⁺, pCO₂, pH and O₂ were performed to quantify the CaCO₃ dissolution and organic matter mineralization in marine sediments in the eastern South Atlantic. A numerical model simulating the organic matter decay with oxygen was used to estimate the calcite dissolution rate. From the oxygen microprofiles measured at four stations along a 1300-m isobath of the eastern African margin and one in front of the river Niger at a water depth of 2200 m the diffusive oxygen uptake (DOU) and oxygen penetration depth (OPD) was calculated. DOU rates were in the range of 0.3 to 3 mmol m⁻² d⁻¹ and showed a decrease with increasing water depth, corresponding to an increase in OPD. The calculated amount of degradated organic matter is in the range of 1 to 8.5 gC m⁻² a⁻¹. The metabolic CO₂, released from mineralization of the organic matter drives calcite dissolution in these sediments overlain by calcite-supersaturated water. Fluxes across the sediment water interface calculated from the in situ Ca²⁺ microprofiles were 0.6 mmol m⁻² d⁻¹ for two stations at a water depth of 1300 m. The ratio of calcite dissolution flux and organic C degradation is 0.53 and 0.97, respectively. The microprofiles indicate that CO₂ produced within the upper oxic sediment layer dissolves up to 85% of the calcite rain to the seafloor. Modeling our O₂, pH and Ca²⁺ profiles from one station predicted a calcite dissolution rate constant for this calcite-poor site of 1000 mol kgw⁻¹ a⁻¹ (mol per kg water and year), which equals 95% d⁻¹. This rate constant is at the upper end of reported in situ values.     

Suitability of Existing Numerical Model Codes and Thermodynamic Databases for the Prognosis of Calcite Dissolution Processes in Near-Surface Sediments Due to a CO2 Leakage Investigated by Column Experiments

Among the risks of CO₂ storage is the potential of CO₂ leakage into overlaying formations and near-surface potable aquifers. Through a leakage, the CO₂ can intrude into protected groundwater resources, which can lead to groundwater acidification followed by potential mobilisation of heavy metals and other trace metals through mineral dissolution or ion exchange processes. The prediction of pH buffer reactions in the formations overlaying a CO₂ storage site is essential for assessing the impact of CO₂ leakages in terms of trace metal mobilisation. For buffering the pH-value, calcite dissolution is one of the most important mechanisms. Although calcite dissolution has been studied for decades, experiments conducted under elevated CO₂ partial pressures are rare. Here, the first study for column experiments is presented applying CO₂ partial pressures from 6 to 43 bars and realising a near-natural flow regime. Geochemical calculations of calcite dissolution kinetics were conducted using PHREEQC together with different thermodynamic databases. Applying calcite surface areas, which were previously acquired by N₂-BET or calculated based on grain diameters, respectively, to the rate laws according to Plummer et al. (Am J Sci 278:179–216, doi:10.2475/ajs.278.2.179, 1978) or Palandri and Kharaka (US Geol Surv Open file Rep 2004–1068:71, 2004) in the numerical simulations led to an overestimation of the calcite dissolution rate by up to three orders of magnitude compared to the results of the column experiments. Only reduction of the calcite surface area in the simulations as a fitting procedure allowed reproducing the experimental results. A reason may be that the diffusion boundary layer (DBL), which depends on the groundwater flow velocity and develops at the calcite grain surface separating it from the bulk of the solution, has to be regarded: The DBL leads to a decrease in the calcite dissolution rate under natural laminar flow conditions compared to turbulent mixing in traditional batch experiments. However, varying the rate constants by three orders of magnitudes in a field scale PHREEQC model simulating a CO₂ leakage produced minor variations in the pH buffering through calcite dissolution. This justifies the use of equilibrium models when calculating the calcite dissolution in CO₂ leakage scenarios for porous aquifers and slow or moderate groundwater flow velocities. However, the selection of the thermodynamic database has an impact on the dissolved calcium concentration, leading to an uncertainty in the simulation results. The resulting uncertainty, which applies also to the calculated propagation of an aquifer zone depleted in calcite through dissolution, seems negligible for shallow aquifers of approximately 60 m depth, but amounts to 35 % of the calcium concentration for aquifers at a depth of approximately 400 m.     

Water Geochemistry of Three Mountain Streams from Carbonate Watersheds in the Southern French Alps

The chemical composition of water from three streamsflowing through a carbonate watershed wasinvestigated. Although the study area is not spatiallyvery large (a few km²), local inhomogeneitieswithin the lithology appreciably affect the chemicalcomposition of the water and the geochemical gradientas a function of elevation. The main chemical processwhich leads to the observed water chemistry is thedissolution of calcium carbonate by atmospheric andmetabolic CO₂. In the stream La Sigouste, thewater dissolves nearly pure calcite and this reactionproceeds until an equilibrium with respect to calciteis reached. In Le Lauzon stream, local inhomogeneitiesin the lithologic composition prevent theestablishment of an unambiguous weathering budgetwhile, for Le Rif de l'Arc a stoichiometric modelshows that the weathering process is adequatelyrepresented by the dissolution of calcite associatedwith a minor incongruent dissolution of chloritepresent in marls. For the two last streamssupersaturation with respect to calcite is observed.For both streams, supersaturation with respect toatmospheric CO₂ is nearly permanent. The observedaltitudinal gradients of sulfate are interpretedthrough a set of biogeochemical redox reactions.     

三峡地区泥灰质岩石斜坡带岩溶作用及其对工程稳定性的影响

泥灰质岩石岩溶是岩溶研究一个薄弱环节,将工程稳定性与岩溶作用相结合是岩溶地区地质灾害评价和治理所面临的新课题。三峡地区巴东组（T2b）泥灰质岩石的岩溶问题是新近发现的重大工程地质问题。由于构造破碎和河流切割引起岩石卸荷与松动,使岩石有利于水的渗入和岩溶作用。水是岩溶的溶剂,在峡谷斜坡地带,雨水是地表水和地下水的主要水源,地处亚热带的三峡地区雨水丰沛。通过对15个不同类型水样的化学成分测试和计算表明,雨水呈酸性,方解石的饱和指数（SI）低,具有强烈的溶蚀性,在地表和地下运移的过程中对泥灰质岩石产生了强烈的溶蚀作用。不同的地貌位置和构造层位具有不同的地表水和地下水状态,从而产生不同强度和不同形式的地表和地下岩溶。地质历史时期,岩溶作用使岩石发生成分和结构的一系列变化,从而导致岩石力学强度降低,岩体发生不均匀沉降、地裂缝、滑坡、崩塌、泥石流和地面塌陷。测试和计算还表明,不仅雨水及其转化成的地表水和地下水,而且江水和自来水均有一定的溶蚀性。将来,水的岩溶作用和水的诱发作用可能导致地基不均匀沉降、地裂缝、滑坡、崩塌、泥石流和地面塌陷,从而破坏工程稳定性。防治三峡地区地质灾害的关键在于防止水向地基的入渗。建议对三峡地区泥灰质岩石斜坡带岩溶进行深入研究。     

Carbonation of alkaline paper mill waste to reduce CO2 greenhouse gas emissions into the atmosphere

The global warming of Earth’s near-surface, air and oceans in recent decades is a direct consequence of anthropogenic emission of greenhouse gases into the atmosphere such as CO₂, CH₄, N₂O and CFCs. The CO₂ emissions contribute approximately 60% to this climate change. This study investigates experimentally the aqueous carbonation mechanisms of an alkaline paper mill waste containing about 55 wt% portlandite (Ca(OH)₂) as a possible mineralogical CO₂ sequestration process. The overall carbonation reaction includes the following steps: (1) Ca release from portlandite dissolution, (2) CO₂ dissolution in water and (3) CaCO₃ precipitation. This CO₂ sequestration mechanism was supported by geochemical modelling of final solutions using PHREEQC software, and observations by scanning electron microscope and X-ray diffraction of final reaction products. According to the experimental protocol, the system proposed would favour the total capture of approx. 218 kg of CO₂ into stable calcite/ton of paper waste, independently of initial CO₂ pressure. The final product from the carbonation process is a calcite (ca. 100 wt%)-water dispersion. Indeed, the total captured CO₂ mineralized as calcite could be stored in degraded soils or even used for diverse industrial applications. This result demonstrates the possibility of using the alkaline liquid–solid waste for CO₂ mitigation and reduction of greenhouse effect gases into the atmosphere.     

碳酸盐岩单裂隙渗流-溶蚀耦合模型及其参数敏感性分析

岩溶地下水系统是由碳酸盐岩裂隙含水介质演化形成的,系统初始的裂隙网络介质特征及边界条件决定了其演化过程。为揭示岩溶系统演化过程中裂隙介质特征和边界条件的影响程度,建立了裂隙溶蚀扩展的渗流-溶蚀耦合模型,并对不同边界条件下不同隙宽的单裂隙溶蚀扩展特征进行了模拟分析。结果表明:裂隙溶蚀扩展受水的侵蚀性(CO2分压)、水动力条件(水力梯度)、裂隙介质特征(裂隙初始隙宽)等综合作用影响,Ca2+的平衡浓度、水力梯度以及裂隙初始隙宽等参数的增加均能促进裂隙的快速扩展。在这些参数中,初始隙宽B0对岩溶发育的影响最为敏感,水力梯度J和Ca2+平衡浓度Ceq对岩溶发育具有相同的敏感性;此外,随着各参数值的不断增大,参数变化对岩溶发育的敏感程度越来越低。     

Geochemical characterization of surface water and spring water in SE Kashmir Valley,western Himalaya: Implications to water–rock interaction

Water samples from precipitation, glacier melt, snow melt, glacial lake, streams and karst springs were collected across SE of Kashmir Valley, to understand the hydrogeochemical processes governing the evolution of the water in a natural and non-industrial area of western Himalayas. The time series data on solute chemistry suggest that the hydrochemical processes controlling the chemistry of spring waters is more complex than the surface water. This is attributed to more time available for infiltrating water to interact with the diverse host lithology. Total dissolved solids (TDS), in general, increases with decrease in altitude. However, high TDS of some streams at higher altitudes and low TDS of some springs at lower altitudes indicated contribution of high TDS waters from glacial lakes and low TDS waters from streams, respectively. The results show that some karst springs are recharged by surface water; Achabalnag by the Bringi stream and Andernag and Martandnag by the Liddar stream. Calcite dissolution, dedolomitization and silicate weathering were found to be the main processes controlling the chemistry of the spring waters and calcite dissolution as the dominant process in controlling the chemistry of the surface waters. The spring waters were undersaturated with respect to calcite and dolomite in most of the seasons except in November, which is attributed to the replenishment of the CO₂ by recharging waters during most of the seasons.     

Experimental identification of CO2–oil–brine–rock interactions: Implications for CO2 sequestration after termination of a CO2-EOR project

Carbon dioxide enhanced oil recovery (CO₂-EOR) has been widely applied to the process of carbon capture, utilization, and storage (CCUS). Here, we investigate CO₂–oil–water–rock interactions under reservoir conditions (100 °C and 24 MPa) in order to understand the fluid–rock interactions following termination of a CO₂-EOR project. Our experimental results show that CO₂-rich fluid remained the active fluid controlling the dissolution–precipitation processes in an oil-undersaturated sandstone reservoir; e.g., the dissolution of feldspar and calcite, and the precipitation of kaolinite as well as solid phases comprising O, Si, Al, Na, C, and Ti. Mineral dissolution rates were reduced in the case that mineral surfaces were coated by oil. Mineral wettability and composition, and oil saturation were the main controls on the exposed surface area of grains, and mineral wettability in particular led to selective dissolution. In addition, the permeability of the reservoir decreased substantially due to the precipitation of kaolinite and solid-phase particles, and due to the clogging of less soluble mineral particles released by the dissolution of K-feldspar and carbonate cement, whereas porosity increased. The results provide insight into potential formation damage resulting from CO₂-EOR projects.     

四川盆地北缘灯影组深埋白云岩优质储层形成与保存机制

叠合盆地深埋碳酸盐岩优质储层的形成和保存机理是一个复杂而又有争议的议题。大量的地质地球化学证据表明,四川盆地北缘灯影组深埋白云岩在灯四段和灯二段末期先后发生了两期古岩溶作用,在灯影组内形成了大小不等的晶洞和次生孔隙。在后期的深埋-隆升过程中,表生期的岩溶孔洞被不同世代的矿物充填,先存的孔洞被不同程度的改造和破坏,随埋藏深度的增加先存孔洞的体积变小;同时CO2、有机酸、H2S和多期外来酸性热液流体的溶蚀改造又形成了部分新的次生孔洞;油气藏主要赋存于残余的表生岩溶孔洞和新生次生溶孔内。研究表明,灯影组深埋白云岩优质储层的形成和保存不仅受表生岩溶作用、古岩溶地貌和沉积微相的影响和控制,而且还受深埋隆升过程中多期流体充注、溶蚀-沉淀和石油热裂解的复合控制。其中,表生岩溶作用是影响优质储层形成的最为关键性因素,古岩溶地貌和沉积微相控制了优质储层的时空分布,表生岩溶作用影响的深度最深达500m左右。多期侵蚀性流体的溶蚀和石油热裂解所引起的超压使先存表生岩溶孔洞能得以保存。