Dissolution Of Calcite Cement Research Articles

Carbonate dissolution enhances particulate iron sulfide mobilization during water-shale interaction

The interaction between shale and water in the environment can lead to the mobilization of micrometer-sized iron sulfide (pyrite) grains. Because these grains often contain high concentrations of toxic elements, including arsenic, this process can pose a significant hazard. While previous studies have suggested that calcite dissolution plays a major role in iron sulfide mobilization, the relationship between rock composition and the release of particulate matter is unclear. Here, we performed laboratory experiments that simulated water–rock interaction in the subsurface on 5 different shale formations: Eagle Ford, Marcellus, Mancos, and Barnett from the USA, and Ein Zeitim from Israel. We used high resolution imaging to evaluate the impact of a reactive fluid on the shale surface, and used image analysis software to determine the rate of iron sulfide grain mobilization. Comparison of the shale surfaces before and after the experiments showed that the dissolution of calcite cement had a major impact on sulfide mobilization: grains that were primarily surrounded by calcite cement were up to 85 times more likely to be mobilized than grains embedded in the shale matrix, which compromises a complex mixture of submicrometer-scale phases, including phyllosilicates, organics, and carbonates. By contrast, iron sulfide embedded in organic matter typically remained cemented in place. This suggests that while calcite dissolution is a crucial phase in facilitating iron sulfide detachment in shales, organic matter might act as an adhesive that suppresses particulate mobilization. However, the adhesive effect of organic matter is only likely to be of secondary importance. Overall, our results indicate that during hydraulic fracturing operations, which involve the injection of fluid into shales in the subsurface, formations with high levels of carbonate cement are more likely to release particulate iron sulfide, thereby reducing the quality of flowback water and potentially increasing treatment costs.

Geochemical assessment of mineral sequestration of carbon dioxide in the midcontinent rift

AbstractThis study examines the potential of Midcontinent Rift rocks to facilitate long‐term CO2 sequestration by providing the necessary Ca and Mg for carbonate mineralization. Surface samples were collected from the Oronto and Bayfield‐Jacobsville Groups around Lake Superior and used for petrography and X‐ray diffraction to determine their mineral composition. Also, X‐ray fluorescence was also used to assess their bulk chemical composition. The samples were then exposed to CO2 and deionized water in Teflon‐lined vessels at 90°C, and the resulting leachate fluids were analyzed for the cation released during the testing. SEM microscopy was used to examine the samples for potential mineralization of carbonate minerals. The Oronto Group sediments consist primarily of feldspathic to feldspathic lithic arenites with a chlorite‐dominated matrix, and the primary porosity is blocked by calcite and hematite cement. The Bayfield–Jacobsville sequences are porous quartz arenites to feldspathic quartz arenites that do not contain significant accumulation of Ca‐, Mg‐, and Fe‐bearing minerals. The leachate fluids obtained from Oronto Group samples exhibit a maximum Ca release rate (5.2 × 10−4 mole/cm2.day), indicating rapid calcite cement dissolution and increased porosity and permeability. SEM/EDS microanalysis revealed areas where pore‐filling calcite was preferentially dissolved. Longer‐term rock‐water reactions resulted in induced carbonate mineralization, as evidenced by calcite crystals observed in a sample reacted for 102 days. © 2024 Society of Chemical Industry and John Wiley & Sons, Ltd.

Diagenetic History and Timing of Cu and Zn-Pb Sulfide Mineralization in the Permian Kupferschiefer System, Saale Subbasin, Eastern Germany

Abstract The Southern Permian basin in central Europe contains a number of important high-grade sediment-hosted Cu deposits. Laterally extensive stratabound Cu and Zn-Pb sulfide mineralized rocks are located at a major stratigraphic redox boundary, where coarse-grained continental sandstones of the uppermost Rotliegend Group are overlain by carbonaceous mudstones (T1) and limestones (Ca1) of the Zechstein Formation. This study investigates the diagenetic evolution and style of sulfide mineralization in three drill cores that intersect Cu and Zn-Pb sulfide mineralized rocks at three locations (Sangerhausen, Allstedt, and Wallendorf) in the Saale subbasin (Eastern Germany), which is located at the southern margin of the Southern Permian basin. We combine macro- to microscale petrographic data (binocular, transmitted and reflected light, and scanning electron microscopy) with quantitative X-ray diffractometry and bulk-rock geochemical analyses. Petrographic results show extensive, primary-porosity-occluding, early diagenetic calcite cementation that predates both the diagenetic alteration of detrital clasts and sulfide mineralization. The highest-grade Cu and Zn-Pb sulfides (bornite, sphalerite, and galena) replace the calcite cement, with subordinate replacement of dolomite and detrital clasts. Quantitative mineralogical and geochemical data demonstrate that the highest base metal (Cu, Zn, and Pb) concentrations are associated with carbonate-rich samples, mostly as disseminated mineralization in the middle T1. Bulk-rock geochemical results show enrichment and covariation of redox-sensitive trace elements (RSTEs, e.g., Mo) with total organic carbon content toward the lower T1, consistent with highly reducing depositional conditions. Overall, the distribution and dissolution of calcite cement across this stratigraphic redox boundary provided the main control on the lateral migration of base metal-bearing fluids and high-grade Cu and Zn-Pb sulfide mineralization in the Saale subbasin.

Pore network characteristics as a function of diagenesis: Implications for epigenic karstification in shallow-water carbonates

Karst processes may be critical for developing secondary porosity and permeability within carbonate reservoirs and aquifers. Karstification can significantly influence reservoir storage capacity and subsurface fluid flow. This study investigates the interplay between fluid-flow pathways and diagenesis in an epigenic karst setting in Cretaceous shallow-water carbonate rocks, Potiguar Basin, Brazil. The results indicate that dissolution occurred at all diagenetic stages, but the last stage is the most important because it is related to the most recent subaerial exposure. Dissolution produced during the last karst stage occurred in the vadose and phreatic environments, leading to the precipitation of isopachous, blocky and syntaxial cements. Dissolution affected the original pore network within the matrix and localized on preexisting discontinuities such as stylolites, fractures, and bedding surfaces. The resulting karst cavities are classified as vugs, channels and caverns, varying from a few millimeters to hundreds of meters in size. In epigenic karst systems, high porosity percentages are commonly due to moldic, intragrain/intrafossil and intercrystal porosities. The results of our study show how such porosities can be connected to fractures, veins and stylolites at the microscale. Karst dissolution can further increase porosity and the overall rock permeability due to aragonite and calcite cement dissolution during eodiagenesis, microfractures and stylolites dissolution during mesodiagenesis and all cements, fractures and stylolites during telodiagenesis.

Origin of carbonate cements in Ben Nevis sandstones of Jeanne d’Arc Basin: Insights from geochemistry

The Ben Nevis sandstones in the Jeanne d’Arc Basin in offshore eastern Newfoundland have abundant carbonate cements, and are the primary hydrocarbon reservoirs of the White Rose Oilfield. A multiapproach of petrographic, carbon and oxygen isotopic, and in situ geochemical analyses were applied to investigate the origin of the carbonate cements in the Ben Nevis sandstones (quartzose to litho-quartzose, Well F-04). Petrographic examinations reveal five generations of cements that occur in concretions, which are (from earliest to latest), siderite, early calcite cement (C1), recrystallized fossil (Crf), sparry fossil-filling calcite (Cf), and late calcite cement (C2). The comparable carbon (3.6‰ VPDB) and oxygen isotopic (−1.3‰ VPDB) compositions of siderite to those of the bivalve shells (δ13C = 3.6 ± 0.6‰ VPDB and δ18O = −1.7 ± 0.5‰ VPDB, respectively) indicate an early precipitation from suboxic water near the sediment-seawater interface. The well-preserved intergranular volumes (IGVs up to 41%) and low δ18O (−3.3 ± 1.1‰ VPDB) as well as comparable δ13C values (3.6 ± 0.6‰ VPDB) of the early poikilotopic calcite (C1) argue for a pre-compaction precipitation at a shallow burial setting with carbon derived mainly from the dissolution of bioclasts. The later calcite cement (C2) precipitated during progressive burial with involvement of organic carbon as indicated by its depleted δ18O (−6.7 ± 2.0‰ VPDB) and δ13C (1.8 ± 1.3‰ VPDB) values, and the reduced IGVs (28.2%), as well as the consistent depletion of Sr with enrichment of Mn. The dissolution of aragonitic bioclasts, was likely the main source of Ca for calcite, which is consistent with the high Sr content of C1 (1369 ± 597 ppm), Crf (2005 ± 472 ppm), Cf (1354 ± 48 ppm) and C2 (1831 ± 696 ppm). The parallel shale normalized (REESN) patterns of the cements and the way they mimic, to some extent, that both of seawater and meteoric water, suggest that the diagenetic fluid is bracketed by those of the early Cretaceous marine and meteoric waters, as reflected by the estimated δ18OSW composition of parent fluid for C1. The consistent Eu anomalies of carbonate cements and the increasing δ18OSW composition of pore water during C2 precipitation reflect the evolution of the diagenetic fluids in siliciclastic intervals during progressive burial.The secondary porosity development as the main contributor to the present reservoir porosity seem to be closely related to the dissolution of calcite cements, especially in the lower part of the Ben Nevis interval. The meteoric water influx from the overlying unconformities may have induced the dissolution of calcite concretions.

Reservoir quality evaluation using sedimentological and petrophysical characterization of deep-water turbidites: A case study of Tariki Sandstone Member, Taranaki Basin, New Zealand

The current study aims to ascertain the reservoir characteristics of the Tariki Sandstone Member of the Otaraoa Formation, Taranaki Basin, New Zealand. This study was carried out by integrating the comprehensive petrophysical evaluation, sedimentological and petrographic studies, as well as well log analysis by using data from six wells. The porosity-permeability relationship is used to divide the samples of the Tariki Sandstone Member into reservoir and non-reservoir facies. A thorough petrophysical analysis shows that the maximum porosity values fluctuate between 16.6% and 22.1%, while permeability ranges from 102 mD to 574 mD, which indicates fair to good reservoir quality. Moreover, the Tariki sandstone represents six hydraulic flow units with a high reservoir quality index and flow zone indicator representing good reservoir characteristics. The pore size varies between nano and megapores with dominant macropores. Based on the sedimentological and petrographic analysis, the Tariki Sandstone Member is classified as a combination of subarkose, arkose, and lithic arkose with fine to medium and moderately to moderately well-sorted grains. The main diagenetic factor affecting the reservoir quality is cementation, which occupied all the pores with calcite. On the bright side, the secondary pores are developed due to the dissolution of calcite cement and few grains. The well log analysis demonstrates the presence of low clay volume ranging from 0.3% to 3.1%, fair to good effective porosity values between 13.6% and 15.9%, net pay thickness from 18.29 m to 91.44 m, and hydrocarbon saturation from 56% to 77.9%. The findings from this study revealed that the Tariki Sandstone Member possesses fair to good reservoir quality and hydrocarbon potential, which indicate submarine fans as appealing hydrocarbon reservoirs. This study can be used in similar depositional environments elsewhere in the world.

Metal Mobilization From CO2 Storage Cap-Rocks: Experimental Reactions With Pure CO2 or CO2 SO2 NO

CO2 geological storage will be needed as part of the transition to lower greenhouse gas emissions. During CO2 storage, the mobilization of metals from minerals to formation water via CO2 water rock reactions may be a concern for water quality. The sources, behavior, and fate of metals, however, are not well understood. Metals in minerals of calcite cemented sandstone, feldspar-rich sandstone, and ironstone seal drill cores from a target storage site were characterized. The cores were reacted with low-salinity water and pure supercritical CO2 or impure CO2 with SO2 and nitric oxide (NO), under reservoir conditions. Calcite cemented core underwent calcite dissolution with chlorite, plagioclase, and sulfide alteration. The highest concentrations of calcium and manganese were released in the reaction of calcite cemented sandstone seal, with the lowest mobilized arsenic concentration. Pure CO2 reaction of the feldspar-rich sandstone seal resulted in calcite dissolution, with plagioclase, chlorite, kaolinite, illite, and sulfides corroded. Impure CO2 reaction of the feldspar-rich sandstone led to additional corrosion of apatite, pyrite, and sphalerite cements. Generally, dissolved iron, lead, zinc, and arsenic were released and then re-precipitated in oxide minerals or adsorbed. Calcium, manganese, and strontium were released primarily from calcite cement dissolution. Plagioclase corrosion was a second source of dissolved strontium, and chlorite dissolution a second source of manganese. Although sulfides contained higher concentrations of metals, the higher reactivity of carbonates meant that the latter were the main sources contributing to dissolved metal concentrations. The mineral content of the seal cores, and the injected gas mixture, had an impact on the type and concentration of metals released. The ubiquitous presence of carbonate minerals means that this study is applicable to understanding the potential risk factors for water quality changes, and the mobilization and fate of environmentally regulated metals, in both CO2 storage complexes and overlying drinking water aquifers worldwide.

Identification and quantitative evaluation of pores and throats of a tight sandstone reservoir (Upper Triassic Xujiahe Formation, Sichuan Basin, China)

Pores and throats are the key parameters for determining the pore structure and fluid flow behavior in tight sandstone reservoirs. In this paper, pores and throats of the tight sandstone reservoir of the Upper Triassic Xujiahe Formation in the northern Sichuan Basin were investigated using classical petrography, scanning electron microscopy, and confocal laser scanning microscopy. In addition, a method of pore as well as throat identification and quantitatification using high-pressure mercury injection (HPMI) measurements was worked out. The results show that clay mineral-related pores are well developed in lithic sandstone and feldspathic lithic sandstone in addition to pores produced by dissolution of calcite cement and clastic grains. Intergranular pores are connected by lamellar, curved lamellar, and narrow pore throats. The pores and throats associated with intragranular dissolution and clay minerals are mostly tube shaped. The rapid-increasing and slow-increasing profiles of the mercury injection curves represent the dominance of pores and throats, respectively, allowing to differentiate pores and throats. Calculations show, in addition to fractured lithic sandstone, that has micron-sized pore–throat systems, the other lithic sandstones possess dominatly nano-sized pore–throat systems. In case of feldspathic lithic sandstones, micron-sized and nano-sized pore throat systems are equally important. In micron-sized pore throat dominated reservoirs, the pore volume is slightly larger than the throat volume, whereas for the nano-sized pore throat system, the pore volume is considerably larger than the throat volume. The key factors that are favorable for the formation of lithic sandstone pore throat systems are early calcite dissolution, lithic fragments dissolution, and early chlorite cementation. In contrast the key factors that are favorable for the formation of feldspathic lithic sandstone pore throat systems are dissolution of feldspars and lithic fragments.

Secondary porosity development in incised valley sandstones from two wells from the Flemish Pass area, offshore Newfoundland

In this study we discuss the diagenetic processes that have contributed to the preservation of anomalously high secondary porosity (20–30%) and associated high permeability in relative deeply buried (2–3 km) Tithonian-aged stacked incised valley reservoir sandstone intervals (informally named Ti-2 and Ti-3) in the Flemish Pass area, offshore Newfoundland. These incised valley sandstones are bounded by thick organic-rich and/or organic-lean siltstone and mudstone deltaic deposits. Here we use a multi disciplinary approach including thin section petrography, cathodoluminescence (CL) petrography, programmed pyrolysis, and organic petrology to examine the controls on organic matter and secondary porosity development in the studied sandstones. The incised valley sandstones are dominated by litharenites, sublitharenites, and feldspathic litharenites. The most significant early diagenetic pore-occluding event is pervasive poikilotopic calcite cementation that arrested the affects of mechanical compaction preserving framework grains in point contact. Secondary porosity formed by dissolution of the calcite cement is commonly speculated to be related to thermal maturation of organic matter (OM) and associated generation of short-chained carboxylic acid (SCCA). %VRo data shows the OM to be immature (0.5%) therefore the estimated burial temperature of the sediment likely never got above approximately 60 °C in the late diagenesis to early catagenesis stage. This thermal maturity is consistent with the pre-oil generation window and the onset of SCCA generation allowing early calcite dissolution to take place. It is likely a second phase of meteoric water flushing took place, however, the scale of investigation of this study was not adequate to verify meteoric water flushing as a mechanism for calcite cement dissolution.

Implementing the Variability of Crystal Surface Reactivity in Reactive Transport Modeling

Current reactive transport model (RTM) uses transport control as the sole arbiter of differences in reactivity. For the simulation of crystal dissolution, a constant reaction rate is assumed for the entire crystal surface as a function of chemical parameters. However, multiple dissolution experiments confirmed the existence of an intrinsic variability of reaction rates, spanning two to three orders of magnitude. Modeling this variance in the dissolution process is vital for predicting the dissolution of minerals in multiple systems. Novel approaches to solve this problem are currently under discussion. Critical applications include reactions in reservoir rocks, corrosion of materials, or contaminated soils. The goal of this study is to provide an algorithm for multi-rate dissolution of single crystals, to discuss its software implementation, and to present case studies illustrating the difference between the single rate and multi-rate dissolution models. This improved model approach is applied to a set of test cases in order to illustrate the difference between the new model and the standard approach. First, a Kossel crystal is utilized to illustrate the existence of critical rate modes of crystal faces, edges, and corners. A second system exemplifies the effect of multiple rate modes in a reservoir rock system during calcite cement dissolution in a sandstone. The results suggest that reported variations in average dissolution rates can be explained by the multi-rate model, depending on the geometric configurations of the crystal surfaces.

Lithofacies, depositional, and diagenetic controls on the reservoir quality of the Mississippian mixed siliciclastic-carbonate system, eastern Anadarko Basin, Oklahoma, USA

In the eastern Anadarko Basin of central Oklahoma, the variability of Mississippian lithofacies, diagenetic products, and reservoir quality is critical for reservoir development. We have investigated lithofacies variability based on sedimentological characteristics and diagenetic alteration through integration of core and thin sections by using optical microscope, scanning electron microscope, energy dispersive X-ray diffraction spectroscope, and electron probe microanalyzer-cathodoluminescence analyses. Based on detailed descriptions of five cores (approximately 260 m [approximately 850 ft]) and analysis of 34 thin sections, we concluded that the Mississippian strata consists of eight lithofacies that represent wave-influenced nearshore with restricted embayment (lagoon) and channel or lobe deposits. We observed diagenetic alteration including calcite cementation, mechanical compaction, albitization, quartz cementation, silicification, dolomitization, Fe-dolomite cementation, pyritization, and dissolution. A paragenesis scheme suggests that quartz cementation occurred earlier compared to albitization and Fe-dolomite cementation. The Fe-dolomite is the latest authigenic mineral formed, whereas the quartz and calcite cement can be attributed to earlier diagenesis. The calcite, quartz, and Fe-dolomite cementation might have potentially increased the brittleness index and frackability of the rocks. The reservoir quality is relatively good in the channel or lobe deposits and is generally poor in the upper shoreface to upper offshore environments. The reservoir quality is significantly reduced by clays, calcite cement, and mechanical compaction. However, the dissolution of calcite cement and detrital grains tends to improve reservoir quality by forming secondary pores. We prove that understanding the characteristic of lithofacies variation, depositional environments, and diagenetic alterations of the Mississippian strata is crucial for optimal development of the Mississippian reservoirs in the eastern Anadarko Basin. We develop a predictive framework that aids in reservoir characterization.

Dissolution of Different Reservoir Rocks by Organic Acids in Laboratory Simulations: Implications for the Effect of Alteration on Deep Reservoirs

Organic acids are important agents in the alteration of deep reservoirs. It is difficult, however, to assess the impact of organic acid alteration on deep reservoirs because different dissolution processes may occur during diagenesis. This study simulated the dissolution of three different types of reservoir rocks by acetic acid in a closed system and compared the mineral and elemental composition, surface morphology, pore structure, and water chemistry variations of the initial and altered samples. The study demonstrated that both micrite and sucrosic dolostone are strongly dissolved, losing about 20%–30% of their initial rock sample weights. Observation under SEM showed that the limestone dissolved homogenously, whereas the dolostone showed honeycomb-like dissolution. Both carbonate samples showed the development of large voids, including holes and cavities of micrometer scale, but nanopores of various sizes were blocked. In contrast, lithic arkose was heterogeneously altered, losing a weight proportion of about 13% by dissolution of calcite cement. These micrometer-scale microfissures were developed, but those nanometer-scale pores just varied in a narrow range of sizes. The volume increase in all three reservoir types is mainly attributed to the dissolution of carbonate minerals. In deep reservoirs, in situ generated organic acids can enlarge existing cavities in carbonates and develop microfissures in sandstones. The microfissure porosity in sandstone is limited but can increase through other geological processes such as overpressure. More importantly, these acids can maintain the acidity of pore waters, inhibit the precipitation of dissolved minerals, and help to preserve reservoir porosity. Although temperature plays an insignificant role in laboratory simulations, it influences both the generation and destruction processes of organic acids in deep reservoirs on geologic time scales and, thus, warrants further attention. The results provide a basis for recognizing the typical patterns of organic acid dissolution on different reservoir rocks and further suggest the potential role of organic acids in the formation and preservation of secondary porosity in deeply buried reservoirs.

Source and Reservoir Characteristics of the Eocene Mangahewa Formation in Taranaki Basin, New Zealand: Their implications on petroleum system

The Middle to Late Eocene Mangahewa Formation in the Taranaki Basin has been evaluated for its petroleum system (source potential and reservoir qualities). The Mangahewa Formation is generally interpreted as an alternating marginal to shallow marine environment, with lithologies consisting of sandstone, siltstone, mudstone and bitumonius coal. The pyrolysis results show very good source rock generative potential with total organic carbon content of 0.8-90.02 wt. % and hydrogen index values in the range of 54- 491 mg HC/g TOC, with a predominance of oil- and/or gas-prone, mixed Type II-III kerogen. Organic petrographical data reveal that the humic nature of coals being rich in perhydrous vitrinite whereas shales are rich in alginite and bituminite desplaying frequent of migrabitumens. Biomarker analysis suggests predominantly terrigenous origin, whereas pyrolysis Tmax data (414–447°C) and other maturity indicators such as biomarkers and vitrinite reflectance indicates immature and mature samples. Petrographic analyses show that the occurrence of compaction and cementation is succeeded by leaching of feldspars and dissolution of calcite cement. The reservoir samples exhibit largely good reservoir quality with porosity being the dominant feature. The average porosity value is 15.7%, with 21.4% average water saturation. The source and reservoir units are part of a complete petroleum system of the Mangahewa Formation, with the overlying Turi Formation seal rock. The petroleum processes of maturation, generation, and migration which started since Lower Miocene (18.8 Ma) have been recorded in many stratigraphic traps within the Mangahewa Formation or other faulted structural traps due to migration. The generation process is expected to continue to the present day as the source continues to attain maturity while it does not yet reach the peak generation.

Influence of chemical zoning on sandstone calcite cement dissolution: The case of manganese and iron

Chemical zoning of crystals is often found in nature. Crystal zoning can play a role in a mineral's thermodynamic stability and in its kinetic response in the presence of fluids. Dissolution experiments at far-from-equilibrium conditions were performed using a sandstone sample containing calcite cement crystal patches. The surface normal retreat of the calcite crystals was obtained by vertical scanning interferometry (VSI) in their natural position in the rock. Dissolution rate maps showed contrasting surface dissolution areas within the crystals, in the same locations where electron microprobe (EMP) maps showed the presence of manganese (Mn) and iron (Fe) substitutions for calcium in the calcite structure. Iron zoning was only identified in combination with manganese. Maximum registered manganese contents were 1.9(9) wt% and iron were 2(1) wt%. Manganese zoning of only 0.9(5) wt% resulted in around 40% lower dissolution rates than the adjacent pure calcite zones. The combination of both Mn and Fe cation substitutions resulted in one order of magnitude lower dissolution rates compared to pure calcite in the same sample. These results show that mineral zoning can significantly affect reaction rates, a parameter that needs better understanding for the improvement of kinetic geochemical models at the pore scale.

High pressure jet drilling effect in chalk and alteration of local geomechanics properties surrounding the radial hole

This study presents an improved understanding of how high-velocity fluid jet affects the mechanical properties of chalk, building a solid ground for the borehole stability analysis. Our laboratory experiments on water and acid-aided water jet-drilling of chalk samples have shown that high-pressure jet drilling alters the local mechanical properties of the chalk, resulting in a significant weakening of strength properties (tensile, uniaxial/triaxial compressive and pore collapse stress) in close proximity of the jet hole. Acid-aided water has even more impact on chalk matrix as revealed by Scanning Electron Microscopy (SEM) analysis. Numerous micro-perforations are found on the surface of microsparites (calcite). However, no extensive dissolution of calcite cement was observed in the chalk matrix. Results show that mechanical properties degradation is the outcome of both dissolution of the cementation and micro-perforations created on the calcite surface.

Weathering mechanism of arenite sandstone with sparse calcite cement content

We conducted a multifaceted analysis of the weathering zones of arenite, containing a minute amount of calcite cement, based on mineralogical, chemical, and physical properties. The survey targeted sandstone with mudstone interbeds belonging to the Cretaceous Izumi Group. The survey revealed that the weathering mechanism is a chain reaction; the most important process is the pore opening between the grains caused by the dissolution of calcite cement in the initial stage of weathering. Subsequently, the pores between the grains connect and widen, separating the sand grains within the sandstone. This primary weathering action may be a major difference from wacke. During calcite dissolution in the initial stage, sulfuric acid generated by pyrite oxidation in sandstone plays an important role. Chlorite breaks down as calcite dissolves; however, iron resulting from the breakdown disappears only after the pore water has been replaced by acidic water.Sandstones with advanced diagenesis are dense and hard, and it was previously assumed that thick weathering zones could not develop because they were less susceptible to weathering. However, we discovered that weathering caused arenite with a minute amount of calcite cement to disintegrate into grains down to a depth of 30 m. The surface layer of the weathered arenite lost fine particle fraction and crept to form a fragile soil layer susceptible to landslides.

Forecast estimation of sandstone collectors transformation of Lower-Karmalinsky bituminous deposit during its development by the SAGD method

In order to increase hydrocarbon reserves in recent years, begun to actively involve natural bitumens in the development. On the territory of Tatarstan, one of the experimental sites for testing various technologies for the extraction of bitumen is the Lower-Karmalinsky bitumen deposit. Currently, on the field is testing the SAFD method. According to this technology for the extraction of hydrocarbons, steam is pumped in large volumes at a temperature of about + 180°C. Superheated steam reduces the viscosity of hydrocarbons, making them mobile. However, focusing on the reduction of bitumen viscosity, the problem of mineral phase’s transformation due to anthropogenic impact in reservoir is not taken into account. In this work, using thermodynamic modeling, it was shown that the injection of superheated steam into the formation of bitumen-saturated sandstone will lead to the dissolution of calcite cement. Moreover, depending on the salinity of the injected water in the form of steam, the dissolution of carbonates will occur at different temperatures. To improve the technological characteristics and to increase the recoverability of bitumen from reservoir, it is recommended to pump hot water with as little mineralization as possible into sandstone layers. Temperature intervals were established, which should be followed in the process of technological development of bitumen collectors at the stage of heating the reservoir and at the stage of extracting water-bitumen solutions.

Secondary alterations of deep buried Lower Carboniferous terrigenous rocks in some areas of the Dnieper-Donets basin

Problematics. Due to the ambiguous understanding of the nature and void space distribution within reservoir rocks, prediction of prospective deep buried and low permeable reservoirs becomes more uncertain. There are many factors influencing on the pore space, such as primary rock composition, hydrogeological regime, tectonic processes, geological time, epigenetic processes etc. Moreover, in explanation of different factors the influence of secondary reservoirs formation, systematization problems become more essential. Either, it is important to identify ‘working’ conditions of influencing factors to make the prediction of hydrocarbon deposits at great depth more certain. Finding universal criteria of prospective secondary reservoir rocks identification will allow us to enhance the discovery rate of deep buried hydrocarbon deposits. Analysis of previous studies. Many researches were devoted to epigenetic processes in the second part of XXth century. There were described major secondary alterations which may occur at great depth. Recent publications showed the expansion of previous knowledge about epigenetic processes and their influence on the secondary deep buried reservoir formation. Some scientists state that major influencing factors on reservoir quality are tectonic and primary mineral composition, others bring epigenetic imposed processes to the top of influencing factors. Purpose. The purpose of the research is to study secondary alterations and find possible zonation based on the alteration intensity of Carboniferous (Viséan and Serpukhovian) rocks within Central part of the Dnieper-Donets basin. Methods. During this research we studied 43 thin sections of Carboniferous sandstones from cores of Central part of the Dnieper-Donets basin, using polarizing microscope. Alteration stage analyses were used for determination of mineral sequence transformations. Results. Carboniferous (Viséan and Serpukhovian) sandstones discovered by deep wells within Solokhivsko-Dykanskyi and Berezivsko-Kotelevskyi archs in Central part of the Dnieper-Donets depression have been studied. Microscopic studies have shown widespread development of imposed epigenetic alterations in terrigenous rocks. The involvement of laboratory evaluation of porosity and permeability, as well as the values of formation temperatures, allowed us to determine the main trends of secondary processes effect on reservoir properties of rocks. It is shown that the development of secondary microfracturing, kaolinitization and sideritization increases the value of porosity and permeability. Dissolution, regeneration and redeposition of quartz are accompanied by calcitization and lead to the significant decrease of the reservoir properties of terrigenous rocks and formation of secondary epigenetic seals. Sideritization facilitates the development of secondary reservoirs at great depth, meanwhile calcitization leads to decrease of the pore space. Bitumoids and pyrite presence may be the evidence of hydrocarbon migration process. Combination of the research results with thermobaric data retrieved directly from borehole measurements as well as theoretically calculated on Bilske gas condensate field shows that formation of epigenetic seal in the temperature interval of 110-120 °C is caused by quartz dissolution and intensive calcitization of terrigenous rocks. Consequently, secondary reservoir rocks below the epigenetic seal have local spreading caused by microfracturing, sideritization and calcitization. Specific secondary sandy reservoirs of Berezivske gas condensate field are located within 110 and 120 °C isotherm. They occurred in acid environment leading to dissolution of calcite cement and intense sandstone kaolinitization. Such favorable conditions for secondary porosity formation may occur as a result of possible tectonic movements inversion which triggered the development of regressive epigenesis.

Thermodynamic modeling of water vapor influence on development process of the lower-Karmalinsky bituminous deposit by the sagd method

The development of the Lower-Karmalinsky bituminous deposit is currently made by the SAGD method. However, focusing on the reduction of bitumen viscosity, the problem of mineral phase’s transformation at the reservoir due to anthropogenic impact overlooked. In this work, using thermodynamic modeling, shown that the injection of superheated steam into bitumen-saturated sandstone layer will lead to the dissolution of calcite cement.

Pore scale modelling of calcite cement dissolution in a reservoir sandstone matrix

Long-term evolution of permeability and tortuosity due to porosity changes evoked by reactivity of aqueous solutions is of paramount importance for predicting water-rock interaction. This challenge is best tackled by introducing reactive transport modelling on the pore-scale, where the modeling domain is a high-resolution tomographic image of the porous media. We suggest to use a voxel based Navier-Stokes-Brinkman solver in a finite volume formulation coupled to the thermodynamic equilibrium code PhreeqC. High-performance parallelized computations using this coupled numerical reactive transport solver are performed directly on the voxel grid of the segmented micro-CT scans. Retreat of the calcite cement in a sandstone matrix due to dissolution reactions can be directly visualized by digital rock physics experiments.