Quantitative analysis of the clay minerals in the Shurijeh Reservoir Formation using combined X-ray analytical techniques

The Shurijeh Reservoir Formation of Neocomian age is represented by a sandstone sequence, occasionally interbedded with shale, in the Gonbadli gas field, Kopet-Dagh Basin, Northeastern Iran. In this study X-ray diffraction (XRD) and X-ray fluorescence (XRF) techniques were used together to characterize the Shuirjeh clay minerals in 76 core samples collected from two deep Gonbadli wells. The results of XRF analysis showed high percentages of silicon and moderate to low percentages of aluminum, sulfur, calcium, potassium, sodium, magnesium, and iron in both wells. The XRD analysis indicated that the above elements were concentrated in the form of quartz, anhydrite, dolomite, calcite, plagioclase, K-feldspar, hematite, and clay minerals. Further XRD examination of the clay fraction revealed that illite, chlorite, and kaolinite were the major types of clay minerals. Unlike, glauconite, smectite, and a mixed layer clays of both the illite–smectite and chlorite–smectite types were observed only in very few samples. The percentages of individual clay minerals were determined using external standard calibration curves and successfully validated by a system of simultaneous linear equations acquired from detailed elemental information based on the XRF analysis. The error reached ± 5% for the main mineral constituent and ± 15% for minor minerals. A local regression relationship was also derived, based on the XRF elemental information, which can be used to estimate the clay contents of other Shurijeh drilled wells with data of pulsed-neutron spectroscopy tools. According to the proposed quantitative approach, the amount of illite varied considerably, reaching 18.3%. In contrast, the amounts of kaolinite and chlorite were generally small, i.e., less than 8.4%. The amount of total clay minerals changed greatly from a minimum of 5% to a maximum of 32.5%. An increase in illite with increasing burial depth and temperature was an obvious indication of deep burial diagenesis in this formation.     

Alteration mineralogy,lithochemistry and stable isotope geochemistry of the Murgul (Artvin,NE Turkey) volcanic hosted massive sulfide deposit: Implications for the alteration age and ore forming fluids

The Murgul (Artvin, NE Turkey) massive sulfide deposit is hosted dominantly by Late Cretaceous calc-alkaline to transitional felsic volcanics. The footwall rocks are represented by dacitic flows and pyroclastics, whereas the hanging wall rocks consist of epiclastic rocks, chemical exhalative rocks, gypsum-bearing vitric tuff, purple vitric tuff and dacitic flows. Multi-element variation diagrams of the hanging wall and footwall rocks exhibit similar patterns with considerable enrichment in K, Rb and Ba and depletion in Nb, Sr, Ti and P. The chondrite-normalized rare earth element (REEs) patterns of all the rocks are characterized by pronounced positive/negative Eu anomalies as a result of different degrees of hydrothermal alteration and the semi-protected effects of plagioclase fractionation.Mineralogical results suggest illite, illite/smectite + chlorite ± kaolinite and chlorite in the footwall rocks and illite ± smectite ± kaolinite and chlorite ± illite in the hanging wall rocks. Overall, the alteration pattern is represented by silica, sericite, chlorite and chlorite–carbonate–epidote–sericite and quartz/albite zones. Increments of Ishikawa alteration indexes, resulting from gains in K₂O and losses in Na₂O and the chlorite–carbonate–pyrite index towards to the center of the stringer zone, indicate the inner parts of the alteration zones. Calculations of the changes in the chemical mass imply a general volume increase in the footwall rocks. Abnormal volume increases are explained by silica and iron enrichments and a total depletion of alkalis in silica zone. Relative K increments are linked to the sericitization of plagioclase and glass shards and the formation of illite/smectite in the sericite zone. In addition, Fe enrichment is always met by pyrite formation accompanied by quartz and chlorite. Illite is favored over chlorite, smectite and kaolinite in the central part of the ore body due to the increase in the (Al + K)/(Na + Ca) ratio. Although the REEs were enriched in the silicification zone, light REEs show depletion in the silicification zone and enrichment in the other zones in contrast to the heavy REEs' behavior. Hydrothermal alteration within the hanging wall rocks, apart from the gypsum-bearing vitric tuffs, is primarily controlled by chloritization with proportional Fe and Mg enrichments and sericitization.The δ¹⁸O and δD values of clay minerals systematically change with increasing formation temperature from 6.6 to 8.7‰ and − 42 to − 50‰ for illites, and 8.6 and − 52‰ for chlorite, respectively. The O- and H-stable isotopic data imply that hydrothermal-alteration processes occurred at 253–332 °C for illites and 136 °C for chlorite with a temperature decrease outward from the center of the deposit. The positive δ³⁴S values (20.3 to 20.4‰) for gypsum suggest contributions from seawater sulfate reduced by Fe-oxide/-hydroxide phases within altered volcanic units. Thus, the hydrothermal alteration possibly formed via a dissolution–precipitation mechanism that operated under acidic conditions. The K–Ar dating (73–62 Ma) of the illites indicates an illitization process from the Maastrichtian to Early Danian period.     

Composition,nucleation, and growth of iron oxide concretions

Iron oxide concretions are formed from post depositional, paleogroundwater chemical interaction with iron minerals in porous sedimentary rocks. The concretions record a history of iron mobilization and precipitation caused by changes in pH, oxidation conditions, and activity of bacteria. Transport limited growth rates may be used to estimate the duration of fluid flow events. The Jurassic Navajo Sandstone, an important hydrocarbon reservoir and aquifer on the Colorado Plateau, USA, is an ideal stratum to study concretions because it is widely distributed, well exposed and is the host for a variety of iron oxide concretions.Many of the concretions are nearly spherical and some consist of a rind of goethite that nearly completely fills the sandstone porosity and surrounds a central sandstone core. The interior and exterior host-rock sandstones are similar in detrital minerals, but kaolinite and interstratified illite–smectite are less abundant in the interior. Lepidocrocite is present as sand-grain rims in the exterior sandstone, but not present in the interior of the concretions.Widespread sandstone bleaching resulted from dissolution of early diagenetic hematite grain coatings by chemically reducing water that gained access to the sandstone through fault conduits. The iron was transported in solution and precipitated as iron oxide concretions by oxidation and increasing pH. Iron diffusion and advection growth time models place limits on minimum duration of the diagenetic, fluid flow events that formed the concretions. Concretion rinds 2 mm thick and 25 mm in radius would take place in 2000 years from transport by diffusion and advection and in 3600 years if transport was by diffusion only. Solid concretions 10 mm in radius would grow in 3800 years by diffusion or 2800 years with diffusion and advection.Goethite (α-FeO (OH)) and lepidocrocite (γ-FeO (OH)) nucleated on K-feldspar grains, on illite coatings on sand grains, and on pore-filling illite, but not on clean quartz grains. Model results show that regions of detrital K-feldspar in the sandstone that consume H⁺ more rapidly than diffusion to the reaction site determine concretion size, and spacing is related to diffusion and advection rates of supply of reactants Fe²⁺, O₂, and H⁺.     

Dawsonite formation in the Beier Sag,Hailar Basin,NE China tuff: A natural analog for mineral carbon storage

We determined the rock types, the authigenic minerals, the paragenetic sequence, and the origin of dawsonite in pyroclastic rocks from the Yimin Formation of Beier Sag in the Hailar Basin, China. Dawsonite, a diagenetic mineral, is thought to result from a large influx of CO₂ and, therefore, this system represents a natural analogue for in-situ mineral carbon storage. The studied host rocks are mainly tuffs/tuffaceous sandstones which now contain up to 70 vol% authigenic carbonates, including dawsonite, ankerite, and siderite. The initial alteration of the tuffs yielded minor siderite. Kaolinite, illite and mixed illite/smectite then formed as product phases. Dawsonite and quartz subsequently precipitated in response to CO₂ influx apparently coupled to feldspar and perhaps kaolinte dissolution. Dawsonite reaches a maximum 25 vol% of the bulk rock. Mass balance suggests that this CO₂ influx was coupled to the external import of sodium and export of SiO₂. Ankerite and additional siderite precipitated during the late-stage alkaline diagenesis. The carbon isotope values of the dawsonite are in the range −4.1‰ to −2.2‰, indicating the magmatic origin of the CO₂. Vitrinite reflectance and thermal gradient constraints suggest that the dawsonite at this location formed at a temperature of ∼75 °C.     

The Effects of Diagenesis on the Reservoir Characters in Ridge sandstone of Jurassic Jumara dome,Kachchh, Western India

Ridge sandstone of Jurassic Jumara dome of Kachchh was studied in an attempt to quantify the effects of diagenetic process such as compaction, cementation and dissolution on reservoir properties. The average framework composition of Ridge sandstone is Q₈₀F₁₇L₃, medium-to coarse grained and subarkose to arkose. Syndepositional silty to clayey matrix (3% average) is also observed that occurs as pore filling. The diagenetic processes include compaction, cementation and precipitation of authigenic cements, dissolution of unstable grains and grain replacement and development of secondary porosity. The major cause of intense reduction in primary porosity of Ridge sandstone is early cementation which include silica, carbonate, iron, kaolinite, illite, smectite, mixed layer illite-smectite and chlorite, which prevents mechanical compaction. The plots of COPL versus CEPL and IGV versus total cement suggest the loss of primary porosity in Ridge sandstone is due to cementation. Cements mainly iron and carbonate occurs in intergranular pores of detrital grains and destroys porosity. The clay mineral occurs as pore filling and pore lining and deteriorates the porosity and permeability of the Ridge sandstone. The reservoir quality of the studied sandstone is reduced by clay minerals (kaolinite, illite, smectite, mixed layer illitesmectite, chlorite), carbonate, iron and silica cementation but on the other hand, it is increased by alteration and dissolution of the unstable grain, in addition to partial dissolution of carbonate cements. The potential of the studied sandstone to serve as a reservoir is strongly related to sandstone diagenesis.     

鄂尔多斯盆地伊金霍洛旗附近二叠系石千峰组岩石学、地球化学特征及其固碳能力分析

鄂尔多斯盆地是我国CO2地下埋藏的潜在目标区,位于伊金霍洛旗附近的中神监X井与CO2地下注入井中神注1井相邻,两者钻遇地层系统和岩石组合一致。为对示范区储层的固碳潜力和泥岩改造状况做出预测,为CO2地质储存的数值模拟研究提供基础地质信息和相关数据,通过偏光显微镜、扫描电镜、X射线衍射、X射线荧光等多种技术手段,开展了中神监X井石千峰组的岩石学和地球化学特征研究。结果表明石千峰组的砂岩岩石类型主要为长石岩屑砂岩和岩屑长石砂岩;泥岩主要由石英、粘土矿物和长石组成,其中,粘土矿物主要为伊利石,其次为蒙皂石、高岭石和绿泥石。预测在CO2注入后的流体-砂岩长期相互作用过程中,石千峰组砂岩可以通过形成片钠铝石、方解石、铁白云石和菱铁矿等固碳矿物,形成对CO2泄露而言的矿物圈闭,进而实现CO2的长期和安全封存;红色泥岩夹层将发生金属离子活化,导致泥岩褪色。     

Carbonate dissolution in Mesozoic sand- and claystones as a response to CO2 exposure at 70 °C and 20 MPa

The response to CO₂ exposure of a variety of carbonate cemented rocks has been investigated using pressurised batch experiments conducted under simulated reservoir conditions, 70 °C and 20 MPa, and with a durations of up to14 months. Calcite, dolomite, ankerite and siderite cement were present in the unreacted reservoir rocks and caprocks. Core plugs of the reservoir rocks were used in order to investigate the alterations in situ. Crushing of the caprock samples was necessary to maximise reactions within the relatively short duration of the laboratory experiments. Synthetic brines were constructed for each batch experiment to match the specific formation water composition known from the reservoir and caprock formations in each well. Chemical matched synthetic brines proved crucial in order to avoid reactions due to non-equilibra of the fluids with the rock samples, for example observations of the dissolution of anhydrite, which were not associated with the CO₂ injection, but rather caused by mismatched brines.Carbonate dissolution as a response to CO₂ injection was confirmed in all batch experiments by both petrographical observations and geochemical changes in the brines. Increased Ca and Mg concentrations after 1 month reaction with CO₂ and crushed caprocks are ascribed to calcite and dolomite dissolution, respectively, though not verified petrographically. Ankerite and possible siderite dissolution in the sandstone plugs are observed petrographically after 7 months reaction with CO₂; and are accompanied by increased Fe and Mn contents in the reacted fluids. Clear evidence for calcite dissolution in sandstone plugs is observed petrographically after 14 months of reaction with CO₂, and is associated with increased amounts of Ca (and Mg) in the reacted fluid. Dolomite in sandstones shows only minor dissolution features, which are not clearly supported by increased Mg content in the reacted fluid.Silicate dissolution cannot be demonstrated, either by chemical changes in the fluids, as Si and Al concentrations remain below the analytical detection limits, nor by petrographical changes, as partly dissolved feldspar grains and authigenic analcime are present in the sediments prior to the experiments. It is noteworthy, that authigenic K-feldspar and authigenic albite in sandstones show no signs of dissolution and consequently seem to be stable under the experimental conditions.     

Geochemical monitoring of clays for diagenetic evolution of the Paleozoic–Lower Mesozoic sequence in the northern Arabian plate: Hazro and Amanos regions,Southeastern Turkey

Clay minerals in the diagenetic/very low-grade metamorphic–sedimentary series from southeastern Anatolia in Turkey were analyzed to determine their mineralogical and chemical compositions. In the Amanos region, the lowermost unit is composed of metaclastics with primary clastic textures, as well as slaty cleavages and chlorite-mica stacks including volcanic rock intercalations. The Lower Cambrian is composed of mainly very low-grade metamorphic clastic rocks, while the Ordovician units have siliciclastic and carbonate rocks. In the Hazro region, the Late Silurian–Lower Triassic units are represented by highly diagenetic carbonate and clastic rocks. All of the rock units include illite. In addition, chlorite, mixed-layered illite–chlorite and chlorite–vermiculite are present in the Amanos region, while calcite, dolomite, kaolinite, mixed-layered illite–smectite (I–S) and glauconite occur in the Hazro region. The illites are characterized by the dominance of 2M₁ polytype in the Amanos samples; and 1M_d + 2M₁ in the Hazro samples. The I–S, glauconite and kaolin have R1 and R3, 1M and kaolinite polytypes, respectively. The illites have greater tetrahedral and lower octahedral substitutions than the I–S. Total trace element contents, elemental substitutions and chondrite-normalized trace element and REE values decrease toward illite–I–S–kaolinite. There are obvious fractionations for some major – trace and rare earth elements with respect to each other and clear enrichment with respect to the chondrite, with strong anomalies of positive for Gd and negative for P, K and Eu in the clay minerals. The textural, morphological and geochemical data indicate that kaolinite and I–S in the Hazro area occur in supergene conditions with due to a full neoformation mechanism, whereas illites in the Amanos region represent the hypogene origin. In brief, the K₂O contents, ratios of Eu/Eu^* and La_N/Lu_N and δ¹⁸O and δD values of I–S and illite exhibit notable relationships with increasing diagenetic/metamorphic grade.     

Experimental Study of Cement - Sandstone/Shale - Brine - CO2 Interactions

Background

Reactive-transport simulation is a tool that is being used to estimate long-term trapping of CO₂, and wellbore and cap rock integrity for geologic CO₂ storage. We reacted end member components of a heterolithic sandstone and shale unit that forms the upper section of the In Salah Gas Project carbon storage reservoir in Krechba, Algeria with supercritical CO₂, brine, and with/without cement at reservoir conditions to develop experimentally constrained geochemical models for use in reactive transport simulations.

Results

We observe marked changes in solution composition when CO₂ reacted with cement, sandstone, and shale components at reservoir conditions. The geochemical model for the reaction of sandstone and shale with CO₂ and brine is a simple one in which albite, chlorite, illite and carbonate minerals partially dissolve and boehmite, smectite, and amorphous silica precipitate. The geochemical model for the wellbore environment is also fairly simple, in which alkaline cements and rock react with CO₂-rich brines to form an Fe containing calcite, amorphous silica, smectite and boehmite or amorphous Al(OH)₃.

Conclusions

Our research shows that relatively simple geochemical models can describe the dominant reactions that are likely to occur when CO₂ is stored in deep saline aquifers sealed with overlying shale cap rocks, as well as the dominant reactions for cement carbonation at the wellbore interface.     

Key factors controlling the gas adsorption capacity of shale: A study based on parallel experiments

This article performed a series of parallel experiments with numerical modeling to reveal key factors affecting the gas adsorption capacity of shale, including shale quality, gas composition and geological conditions. Adsorption experiments for shales with similar OM types and maturities indicate that the OM is the core carrier for natural gas in shale, while the clay mineral has limited effect. The N₂ and CO₂ adsorption results indicate pores less than 3 nm in diameter are the major contributors to the specific surface area for shale, accounting for 80% of the total. In addition, micropores less than 2 nm in diameter are generated in large numbers during the thermal evolution of organic matter, which substantially increases the specific surface area and adsorption capacity. Competitive adsorption experiments prove that shale absorbs more CO₂ than CH₄, which implies that injection CO₂ could enhance the CH₄ recovery, and further research into N₂ adsorption competitiveness is needed. The Langmuir model simulations indicate the shale gas adsorption occurs via monolayers. Geologically applying the adsorption potential model indicates that the adsorption capacity of shale initially increases before decreasing with increasing depth due to the combined temperature and pressure, which differs from the changing storage capacity pattern for free gases that gradually increase with increasing depth at a constant porosity. These two tendencies cause a mutual conversion between absorbed and free gas that favors shale gas preservation. During the thermal evolution of organic matter, hydrophilic NSO functional groups gradually degrade, reduce the shale humidity and increase the gas adsorption capacity. The shale quality, gas composition and geological conditions all affect the adsorption capacity. Of these factors, the clay minerals and humidity are less important and easily overshadowed by the other factors, such as organic matter abundance.     

Clay mineral variations in Holocene terrestrial sediments from the Indus Basin

We employed X-ray diffraction methods to quantify clay mineral assemblages in the Indus Delta and flood plains since ~ 14 ka, spanning a period of strong climatic change. Assemblages are dominated by smectite and illite, with minor chlorite and kaolinite. Delta sediments integrate clays from across the basin and show increasing smectite input between 13 and 7.5 ka, indicating stronger chemical weathering as the summer monsoon intensified. Changes in clay mineralogy postdate changes in climate by 5–3 ka, reflecting the time needed for new clay minerals to form and be transported to the delta. Samples from the flood plains in Punjab show evidence for increased chemical weathering towards the top of the sections (6–< 4 ka), counter to the trend in the delta, at a time of monsoon weakening. Clay mineral assemblages within sandy flood-plain sediment have higher smectite/(illite + chlorite) values than interbedded mudstones, suggestive of either stronger weathering or more sediment reworking since the Mid Holocene. We show that marine records are not always good proxies for weathering across the entire flood plain. Nonetheless, the delta record likely represents the most reliable record of basin-wide weathering response to climate change.     

Phosphate removal from water by naturally occurring shale,sandstone, and laterite: The role of iron oxides and of soluble species

Aqueous phosphate removal by three geomaterials from Ivory Coast was evaluated to determine their potential application as low-cost phosphate adsorbents in wastewater treatment. Batch experiments showed that phosphate uptake strongly depended on pH. Laterite and sandstone dissolution was less pronounced compared to shale. A correlation between concentrations of aqueous cation species released from shale and phosphate uptake was observed. The kinetics were well described using the pseudo-second-order model. Isotherms displayed a saturation level on shale, while phosphate uptake continuously increased for laterite and sandstone. The removal efficiency decreased in the following ranking order: laterite > sandstone > shale. Laterite was also the most efficient adsorbent in column experiments. The high phosphate removal efficiency of laterite (8.3 mg PO₄ g^?1) was attributed to the presence of superparamagnetic low grain sizes of goethite. Laterite is a particularly promising material for further investigation in wastewater treatment technology such as constructed wetlands.     

Genetic investigation and comparison of Kartaldağ and Madendağ epithermal gold deposits in Çanakkale,NW Turkey

Two epithermal gold deposits (Kartaldağ and Madendağ) located in NW Turkey have been characterized through the detailed examinations involving geologic, mineralogical, fluid inclusion, stable isotope, whole-rock geochemistry, and geochronology data.The Kartaldağ deposit (0.01–17.65 ppm Au), hosted by Eocene dacite porphyry, is associated with four main alteration types with characteristic assemblage of: i) chlorite/smectite–illite ± kaolinite, ii) quartz–kaolinite, iii) quartz–alunite–pyrophyllite, iv) quartz–pyrite, the last being characterized by three distinct quartz generations comprising massive/vuggy (early), fine–medium grained, vug-lining (early), and banded, colloform, comb (late) textures. Observed sulfide minerals are pyrite, covellite, and sphalerite. Oxygen and sulfur isotope analyses, performed on quartz (δ¹⁸O_(quartz): 7.93 to 8.95‰ and calculated δ¹⁸O_(H2O): − 7.95 to 1.49‰) and pyrite (δ³⁴S_(pyrite): − 4.8‰ and calculated δ³⁴S_(H2S): − 6.08 to − 7.20‰) separates, suggest a meteoric water source for water in the hydrothermal fluid, and an igneous source for the sulfur dissolved in ore-related fluids. Microthermometric analyses of primary fluid inclusion assemblages performed on quartz (late quartz generation) yield temperatures (Th) dominantly in the range of 245–285 °C, and generally low salinity values at 0 to 1.7 wt.% NaCl eq. Based on the quartz textures and the associated base metal concentrations, along with fluid inclusion petrography, the early vug-lining quartz is considered to have been associated with the mineralization possibly through a boiling and a late mixing process at > 285 °C.The Madendağ deposit (0.27–20.60 ppm Au), hosted by Paleozoic mica schists, is associated with two main alteration types: sericite–illite–kaolinite, and quartz–pyrite dominated by two distinct quartz generations i) early colloform, comb and banded quartz and ii) late quartz, forming the cement in hydrothermal breccia. Whereas oxygen isotope analyses of quartz (δ¹⁸O_(quartz): 9.55 to 18.19‰ and calculated δ¹⁸O_(H2O): − 2.97 to 5.54‰) suggest varying proportions of meteoric and magmatic sources for the ore bearing fluid, sulfur isotope ratios (δ³⁴S_(pyrite): − 2.2‰ and calculated δ³⁴S_(H2S): (− 3.63) to (− 3.75) ‰) point to an essentially magmatic source for sulfur with or without contribution from sedimentary sources. Microthermometric analysis carried out on primary fluid inclusion populations of a brecciated sample (early quartz), give a temperature (Th) range of 235–255 °C and 0.0 to 0.7 wt.% NaCl eq. salinity. Based on the textural relationship, base metal and high gold contents, the ore precipitation stage is associated with late stage quartz formation via a possible boiling process.The presence of alunite, pyrophyllite and kaolinite, vuggy quartz and covellite suggest a high-sulfidation type of epithermal deposit for Kartaldağ. On the other hand, Madendağ is identified as an adularia-sericite type owing to the presence of significant sericite, neutral pH clays (mostly illite, chlorite/smectite, and kaolinite), low temperature quartz textures (e.g., colloform, comb, and banded quartz), and limited sulfide minerals.Given the geographical proximity of Kartaldağ and Madendağ deposits, the similar temperature and salinity ranges obtained from their fluid inclusions, and the similar ages of igneous rocks in both deposits (Kartaldağ: 40.80 ± 0.36 to 42.19 ± 0.45 Ma, Madendağ: 43.34 ± 0.85 Ma) the mineralizing systems in both deposits are considered to be genetically related.     

Geotechnical characterization of marine sediments in the Ulleung Basin,East Sea

The geotechnical characteristics of Ulleung Basin sediments are explored using depressurized samples obtained at 2100 m water depth and 110 m below the sea floor. Geotechnical index tests, X-ray diffraction, and SEM images were obtained to identify the governing sediment parameters, chemical composition and mineralogy. We use an instrumented multi-sensor oedometer cell to determine the small-strain stiffness, zero-lateral strain compressibility and electromagnetic properties, and a triaxial device to measure shear strength. SEM images show a sediment structure dominated by microfossils, with some clay minerals that include kaolinite, illite, and chlorite. The preponderant presence of microfossils determines the high porosity of these sediments, defines their microstructure, and governs all macroscale properties. The shear wave velocity increases as the vertical effective stress increases; on the other hand, porosity, permittivity, electrical conductivity, and hydraulic conductivity decrease with increasing confinement. All these parameters exhibit a bi-linear response with effective vertical stress due to the crushable nature of microfossils. Well-established empirical correlations used to evaluate engineering parameters do not apply for these diatomaceous sediments which exhibit higher compressibility than anticipated based on correlations with index properties. Settlements will be particularly important if gas production is attempted using depressurization because this approach will cause both hydrate dissociation and increase in effective stress.     

Mineral equilibria and geothermometry of the Dalaman–Köyceğiz thermal springs,southern Turkey

The Dalaman and Köyceğiz thermal springs are from karstic limestones belonging to Upper Cretaceous to Burdigalian Beydağları autochthon and Carboniferous to Lutetian Lycian nappes. They have measured temperatures of 24– 41 °C, specific electrical conductivities of 14,310–45,600 μS/cm, and are dominated by Na (1550–8500 mg/kg) and Cl (2725–15,320 mg/kg). The heat source of the geothermal systems of the area is tectonic related and the occurrence of the thermal springs is related to the young normal faults. Meteoric waters and seawaters recharge the reservoir rocks, are heated at depth with increasing geothermal gradient, and move up to the surface through the fractures and faults by convection trend and emerge as thermal springs. While thermal waters move up to the surface, they mix with different proportions of seawater and cold fresh waters. The seawater contribution to the thermal waters varies from 24% to 78%. Lake waters in the area are connected with thermal waters. Consequently, their chemical composition is influenced by the chemistry of thermal waters. Chemical equilibrium modelling based on measured outlet temperatures and measured pH shows that all the waters are oversaturated with respect to quartz and K-mica and undersaturated with respect to Al(OH)₃, anorthite, gypsum, siderite and SiO₂(a). Albite, alunite, aragonite, Ca-montmorillonite, calcite, chalcedony, chlorite, dolomite, Fe(OH)₃(a), fluorite, gypsum, illite, K-feldspar, kaolinite and sepiolite minerals are mostly oversaturated or undersaturated. Mineral saturation studies of the thermal springs indicate that dolomite, chalcedony and quartz are most likely to cause scaling at outlet conditions. Assessments from various chemical geothermometers, and Na–K–Mg ternary and mineral equilibrium diagrams suggest that the reservoir temperature is around 65–90 °C. The temperatures obtained from quartz, quartz-steam loss, Mg/Li geothermometers and mineral equilibrium diagrams give the most reasonable results.     

海拉尔盆地乌尔逊凹陷幔源CO2充注对下白垩统砂岩储层质量的影响

海拉尔盆地乌尔逊凹陷下白垩统含片钠铝石砂岩部分记录了幔源CO_2-砂岩相互作用历史.为揭示幔源CO_2充注对储层质量的影响,通过偏光显微镜、扫描电镜观察和孔隙度、渗透率数据研究了海拉尔盆地乌尔逊凹陷含片钠铝石砂岩的岩石学和储层特征.幔源CO_2的充注导致了长石的部分溶解和片钠铝石及铁白云石的沉淀.长石的溶解形成了次生孔隙.片钠铝石以针状晶形为特征,其集合体呈束状、簇状、扇状和玫瑰花状.部分片钠铝石呈板状.片钠铝石以充填孔隙为主,少量交代长石和其他骨架碎屑颗粒.片钠铝石局部被铁白云石交代,说明铁白云石的形成晚于片钠铝石.片钠铝石的含量为1%～20%.相同深度段的含片钠铝石砂岩(n=597,h=1309.15～2140.71m)与普通砂岩(n=1550,h=1323.72～2141.3m)的孔隙度、渗透率数据统计表明,含片钠铝石砂岩的物性整体上低于普通砂岩,说明CO_2的充注导致了储层质量的改变.片钠铝石含量-孔隙度和片钠铝石含量-渗透率之间的关系,揭示片钠铝石含量是引起储层质量改变的主要因素.片钠铝石含量10%似乎是储层质量发生变化的界限,当片钠铝石含量＞10%,随片钠铝石含量增加,砂岩的孔隙度和渗透率降低;当片钠铝石含量＜10%,随片钠铝石含量增加,部分砂岩的孔隙度和渗透率表现出增加趋势.作者认为,片钠铝石含量高的砂岩长期处于高CO_2分压成岩环境,而片钠铝石含量低的砂岩则处于高CO_2分压成岩环境的时间相对较短.     

鄂尔多斯盆地东缘C-P煤系致密砂岩储层敏感性分析

鄂尔多斯盆地临兴地区上古生界致密砂岩储集层中矿物组成多样、孔隙结构复杂且黏土矿物含量高,直接影响储层改造和开发效果。文章基于X 衍射、铸体薄片、气测孔渗、压汞和敏感性实验,系统研究了储层敏感性及其影响因素。结果表明研究区砂岩中石英和岩屑含量高,长石含量较低,以岩屑砂岩、岩屑石英砂岩、长石岩屑砂岩和石英砂岩为主。黏土矿物主要为伊利石、高岭石、绿泥石以及伊/蒙混层;储层普遍低孔低渗,孔隙结构较差。速敏以太原组最强,山西组最弱,与伊利石+绿泥石含量正相关,高岭石含量负相关。水敏下石盒子组最强,太原组最弱,与伊/蒙混层含量正相关。盐敏与水敏有类似特点,与伊/蒙混层含量表现出正相关。酸敏山西组最强,下石盒子组最弱,与绿泥石和铁白云石矿物含量正相关。碱敏性山西组最强,太原组最弱,受长石、石英和高岭石含量影响。相关认识有助于指导研究区钻井、压裂等施工工艺选择和排采控制。     

Ferric iron in sediments as a novel CO2 mineral trap: CO2–SO2 reaction with hematite

Thermodynamic simulations of reactions among SO₂-bearing CO₂-dominated gas, water and mineral phases predict that Fe^III in sediments should be converted almost entirely to dissolved Fe^II and siderite (FeCO₃), and that SO₂ should simultaneously be oxidized to dissolved sulfate. The reactions are however, subject to kinetic constraints which may result in deviation from equilibrium and the precipitation of other metastable mineral phases. To test the prediction, a laboratory experiment was carried out in a well stirred hydrothermal reactor at 150 °C and 300 bar with hematite, 1.0 m NaCl, 0.5 m NaOH, SO₂ in quantity sufficient to reduce much of the iron, and excess CO₂. The experiment produced stable siderite and metastable pyrite and elemental S. Changes in total dissolved Fe are consistent with nucleation of pyrite at ∼17 h, and nucleation of siderite at ∼600 h. Dissolution features present on elemental S at the conclusion of the experiment suggest nucleation early in the experiment. The experiment did not reach equilibrium after ∼1400 h, as indicated by coexistence of hematite with metastable pyrite and elemental sulfur. However, the results confirm that Fe^III can be used to trap CO₂ in siderite if partly oxidized S, as SO₂, is present to reduce the Fe with CO₂ in the gas phase.     

Wetting weakening of tertiary sandstones—microscopic mechanism

The micromechanism accounting for wetting weakening of tertiary sandstones was studied. It was found that intragranular fracture prevails for all dry sandstones. However, when the sandstone is wet, intergranular fracture occurs for Type B sandstones. Therefore, one sandstone from Type A sandstones, MS1, and another from Type B, TK, were selected to further investigate the nature of the matrix. It was found that (1) for both sandstones, the major mineral components of the matrix are illite and kaolinite except that the MS1 sandstone has more chlorite; (2) leaching of matrix induced an increase of porosity and consequently results in leaching softening; and (3) among the mineral composition, chlorite is easiest to be dissolved and leached out and induces a more significant increase of porosity, which, in turn, results in a more significant leaching softening.     

Charging time of tight gas in the Upper Paleozoic of the Ordos Basin,central China

The Upper Paleozoic section contains a tight gas sandstone reservoir (of 2.75 × 10¹² m³) in the Ordos Basin, central China. The measured porosities (< 10%) and permeabilities (generally < 1 mD) are the result of significant mechanical and chemical compaction and precipitation of carbonate, quartz and authigenic clay cements. Fluid inclusion geochemistry and kinetic modeling (generation of gaseous components and δ¹³C₁) were integrated to constrain the timing of gas charge into the tight reservoir. The modeling results indicate that the natural gases in the present reservoir are similar to gases liberated from quartz inclusions in both composition and stable carbon isotope values and also similar to gas generated from Upper Paleozoic coal. The similar geochemistry suggests that an important phase of quartz cementation must have occurred after gas emplacement in the reservoirs during regional uplift at the end of the Cretaceous. The latest carbonate cement, postdating quartz cementation, consumed most of the late CO₂ generated from coal at high maturity (R_O > 1.7%) and reduced the reservoir quality dramatically. On the contrary, tight sandstones from non-producing areas have fluid inclusions that were trapped in quartz cements much earlier. These data indicate that natural gas migrated into the Upper Paleozoic reservoir when it still retained high porosity and permeability. The reservoir continued to experience porosity and permeability reduction from continued quartz and carbonate cementation after gas charging due to low gas saturation. Comparison of the relative timing of gas charging with that of sandstone cementation can help to predict areas of risk during tight gas exploration and development.