Alteration Of Clay Minerals Research Articles

Investigating the impact of paleoclimatic conditions and diagenesis on the genesis of Permian Continental Red Beds: A case study from the Bohemian Massif, Czechia

The processes responsible for reddening of Continental Red Beds (CRBs) and the relationship between color variation and paleoenvironmental conditions are presented focusing on a comprehensive multi-proxy study of Permian sediments in the Bohemian Massif, Czechia. The investigation incorporates facies analysis, quantitative color assessment using diffuse Vis-spectral reflectance (DRS), optical and electron microprobe microscopy, bulk-rock (XRF and XRD), and in-situ geochemistry (laser-ablation ICP-MS). Results indicate a progressive drying trend from the Cisuralian to Guadalupian series in studied continental red sediments. Different facies indicate the change of the sedimentary environment from a deep lacustrine environment (lower part of Rudník Member, Cisuralian) to a fluvial floodplain and eolian environment (Trutnov Formation, Guadalupian). Examination of the three major categories (white, gray–green and red sediments) identified in the studied continental red beds indicates that diagenetic alteration of clay minerals and biotite was the main source of iron fueling the growth of hematite responsible for their red color. Early diagenetic processes and paleoenvironmental conditions, particularly the oxidizing or reducing conditions play a key role in the red sediment formation. It is suggested that later diagenetic stages are incapable of coloring non-red, iron-rich sediments formed in deep anoxic lacustrine environments. Microbial activities and reducing fluids have been identified as the main factors in the formation of gray–green sediments forming distinct reduction zones. The reduction spots formed during the early stages of diagenesis (eodiagenesis), and they were likely never red. In contrast, reduction strips, initially exhibiting a red hue, underwent a color change during more advanced stages of diagenesis (mesodiagenesis).

Modes of occurrence of gallium in Al-Ga-rich coals in the Jungar Coalfield, Ordos Basin, China: Insights from LA-ICP-MS data

Owing to the concern about supply of Ga, it has been attracted much attention for the modes of occurrence of Ga in Al-Ga-rich coal-hosted deposits. However, the modes of occurrence of Ga in coal were mainly investigated using indirect methods, which may cause uncertainties. In this study, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) spot and mapping analysis were used to directly characterize the concentration of Ga within the host minerals including kaolinite and boehmite, and to investigate the distribution of Ga in organic matter in the Carboniferous Al-Ga-rich coal from the Haerwusu Mine in the Jungar Coalfield of the Ordos Basin, North China. Microscope observation and scanning electron microscope - energy dispersive spectrometry (SEM-EDS) analysis were performed, along with petrographical and mineralogical investigations. Eight types of kaolinite and three types of boehmite particles from coal, erosional-sourced mudstone, and tonstein were identified, classified, and selected for the determination of in-situ elemental compositions.The results showed that the concentration of Ga in the selected minerals varies, with the following order from highest to lowest: colloidal boehmite (90.38 ppm), low-Al (Al2O3/SiO2) clastic kaolinite (84.67 ppm), high-Al clastic kaolinite (55.49 ppm), Na-bearing kaolinite (49.94 ppm), fine-grained boehmite (47.13 ppm), high-Al cryptocrystalline kaolinite (40.25 ppm), low-Al cryptocrystalline kaolinite (38.78 ppm), and low-Al vermicular kaolinite (29.67 ppm), high-Al vermicular kaolinite (28.37 ppm), K-bearing kaolinite (19.44 ppm), and clastic boehmite and cell-filling kaolinite (below detection limit). LA-ICP-MS mapping demonstrated that a certain proportion of Ga could be associated with organic matter, concentrating on vitrinite. Notably, the concentration of Ga in clastic kaolinite and colloidal boehmite was found to be substantially higher compared to the whole-rock coal and erosional-sourced mudstone samples, indicative of their dominant host minerals for Ga. Conversely, the concentration of Ga in K-bearing or Na-bearing kaolinite which had experienced transformation from primary kaolinite is much lower than that in clastic kaolinite, while the concentration of Ga in fine-grained boehmite, which had altered from kaolinite, surpassed that of its corresponding kaolinite layer. These findings suggest that gallium could have undergone migration during the evolution or alteration of clay minerals.

Caprock integrity at Çanakkale-Tuzla hydrothermal system inferred from magnetotelluric modeling using particle swarm optimization

The impermeable caprock within a geothermal system serves the purpose of effectively sealing the reservoir, resulting in the elevation of both pressure and temperature. This sealing mechanism plays a crucial role in the long-term preservation of the system, while also contributing to its overall sustainability. Caprock failure subsequent to seismic activity near a geothermal site can lead to the permeation of the caprock structure, resulting in diminished sealing capabilities and a decline in the reservoir temperature. Additionally, this process alters the geochemical composition of the water by creating a hydrothermal mixture zone that disrupts the resistivity structure of the caprock, which is typically characterized by low resistivity values due to its substantial clay content and mineral alteration. This study focuses on investigating the integrity of the caprock at ơnakkale-Tuzla geothermal field in Turkey, where the water temperature and conductivity were reported to have decreased after a moderate magnitude earthquake and subsequent aftershocks. For this purpose, we performed magnetotelluric (MT) measurements, a method known for its sensitivity to geochemical reactions. These measurements were conducted along two parallel profiles that encompassed a total of 32 stations. Particle swarm optimization (PSO) technique was employed to overcome subtle difficulties associated with conventional inversion methods when modeling the MT data of complex formations. This is the first study that overcomes the difficulties emanating from the caprock failure by modeling MT data using PSO. Our modeling approach produced resistivity images that we interpreted as the signature of the failed caprock following the earthquake at the study site. Our results appear to confirm the documented geochemical changes or hydrothermal mixture zone about caprock structure.

Aeolian dust accretion outpaces erosion in the formation of Mediterranean alpine soils. New evidence from the periglacial zone of Mount Olympus, Greece

AbstractSoil formation in Mediterranean periglacial karst landscapes remains poorly understood as the interplay between local and allochthonous sources of parent materials, and mineral alteration and pedogenesis, as dominant post‐depositional processes, depends on a variety of climatic and environmental factors. Herein, we investigate the balance between erosion and aeolian dust accretion in the formation of an alpine soil profile in the periglacial zone of Mount Olympus in Greece. We applied a wide range of analytical methods to 23 samples, from a soil profile developed in a glaciokarstic plateau, from colluvial sediment horizons interbedded in postglacial scree slopes of different maturity and formation age and from modern Sahara dust samples deposited on the snowpack. Colluvial sediment horizons exhibit high concentrations of carbonate gravel and calcite‐rich sand and represent the local erosion products. The soil B horizon developed on the glaciokarstic plateau, contains high amounts of fine earth and is rich in quartz, mica, plagioclase, clays and Fe–Ti oxides. Based on physical and textural characteristics, the soil profile is partitioned in a surficial weathered Bw and an illuvial Bt horizon that overlies the local regolith composed of fragmented glacial till and slope wash deposits. Radiogenic isotope systematics, textural and mineralogical analysis show that the contribution of aeolian (Sahara and locally sourced) dust to the development of the soil B horizon ranges between 50% and 65%. Cryoturbation results in fine earth translocation from Bw to the Bt horizon, whereas weak pedogenetic modifications of detrital (aeolian and bedrock‐derived) minerals result in magnetic mineral weathering and secondary clay formation. Our findings reveal that aeolian dust accretion from Saharan and lcal sources is the dominant process in providing alpine soil parent material and that cryoturbation, weak pedogenesis and clay mineral alteration occur within the Mediterranean periglacial zone of Mount Olympus.

Assessment of image ratio technique: Targeting structural features and mineralization characteristics in the southwestern part of the Sokoto Basin in Nigeria using Landsat 8 imagery

Landsat 8 used multispectral images to map surface structures and validate the existence of suspected mineral alteration zones in the southwestern part of the Sokoto Basin in Nigeria. The area falls within contrasting sedimentary, metasediment, metamorphic, and older granitoid lithologies. The processing and analysis of the Landsat 8 imagery involving false color composite (FCC), band ratio, and principal component analysis (PCA) were implemented in the visible near-infrared and short-wave infrared bands of Landsat 8. PCA highlighted areas with high concentrations of clay minerals and iron oxides using RGB composite bands 7, 5, and 3. Moreover, PCA enhanced iron oxide, hydroxyl-bearing minerals, and likely prospective zones mainly constrained in amphibolite, phyllite, quartzite, and alluvial deposits that have undergone metamorphism and metasedimentation within Yegiwa and Kurege. It identified iron ore and clay mineral alteration, suggesting the occurrence of manganese, goethite, and carbonate minerals around Maburo and Derrena. The observed alteration zones and their associated quartz veins are usually consistent with the main NE–SW provincial structural trend dipping to the northwest zone. However, field verification validates rock units typically consisting of muscovite, hornblende, manganite, tourmaline, quartz vein, and granitic rocks. Accordingly, remote-sensing and field verification served as a guide for future subsurface structural investigation and in-depth geophysical exploration.

Implication of the diagenetic evolution, litho- and microfacies types on the storage capacity of the carbonate rocks in West Esh El Mallaha area, SW onshore Gulf of Suez, Egypt

The present study shed the light on the main litho- and microfacies of the Upper Cretaceous- Miocene sequence exposed at West Esh El Mallaha area (Egypt) with more focus on the carbonate rocks. Delineating the implication of the recorded facies and the diagenetic processes on the storage capacity of the entire sequence is among the prime targets of this study. The studied Esh El Mallaha sequence includes the Nubia, Duwi, Dakhla, Tarawan, Esna, Thebes, Abu Gerfan, Gharamul and Gemsa Formations, from older to younger respectively. The carbonate rocks exposed in the studied sequence were deposited in shallow marine, lagoonal outer ramp and environments with high energy and/or open marine conditions. These depositional environments are represented by ten microfacies types: lime-mudstone, foraminiferal wackestone, bioclastic wackestone, algal wackestone/packstone, foraminiferal packstone, bioclastic packstone/grainstone, phosphatic packstone/grainstone, oolitic and bioclastic grainstone, oyster rudstone and bafflestone. Aggrading neomorphism, calcite cementation (drusy calcite, pseudosparite, and poikilotopic calcite), silicification (silica cementation in the form of amorphous silica, micro-quartz, chalcedony and spherulitic quartz), compaction, clay mineral alteration, dissolution, fracturing and dolomitization are the main diagenetic processes recorded in the studied section.The storage capacity of the different rock units were primarily obliterated by multi-cementation phases by calcite, silica and/or clay minerals. Nonetheless, fracturing, dissolution and dolomitization enhanced the storage capacity and can be considered the main storage capacity-enhancing features in the studied sequence. These diagenetic features are more abundant in the studied Duwi, Thebes, Abu Gerfan and Gharamul Formations. This achievement indicates that the studied Upper Cretaceous- Miocene carbonate sequence may be promising in its subsurface extensions in the Gulf of Suez and other analogues in Egypt.

Complexity of clay minerals and its effects on silicon dynamics in hypersaline coastal wetland soils, Brazil

Context Tidal dynamics and high evaporative rates in hypersaline tidal flat (HTF) soils favour a range of clay reactions and the formation of complex clay assemblages. HTFs have a geochemical environment conducive to mineral reactions, and therefore, clay mineral alteration controls essential nutrients in coastal wetlands. Aims The crystallochemical characteristics of clay minerals from two HTFs were studied to provide insights into the complexity of fine clay assemblages in HTF soils and their effects on Si biogeochemistry. Methods The fine clay fraction (<0.2 μm) from these HTFs were investigated using X-ray diffraction (XRD) modelling, XRF, FTIR, TEM–EDS, and silicon sequential extractions. Key results The results have indicated the presence of endmembers and R0 mixed-layered minerals such as kaolinite, smectite, illite, kaolinite–smectite (K–S), kaolinite–illite (K–I), illite–smectite (I–S), and illite–vermiculite (I–V). In general, K–S was the dominant mineral in the samples, occurring in a range of kaolinite layers. Alteration of detrital kaolinite to other mixed-layered minerals occurs in soils, leading to silicon removal from the soil solution because of mineral genesis. There is Mg enrichment at the expense of Al in the samples, and bio-opal appears to be the source of Si for the kaolinite alteration process. Conclusions Our findings indicate that clay authigenesis is an important factor controlling Si dynamics in HTF soils, acting as a sink of Si during the formation of new clay phases. Implications Chemical reactions involving clay minerals are critical for deepening our understanding of the biogeochemistry of wetland soils.

The role of parent lithology in nanoscale clay-mineral transformations in a subtropical monsoonal climate

Abstract Clay minerals are among the most important reactive components of soil systems, acting as a bridge linking organic and inorganic components. Lithology is a key factor in clay-mineral genesis and transformation, yet it has received scant attention to date at the nanoscale. Inferences regarding pedogenic clay-mineral transformations based on X-ray diffraction (XRD) are sometimes speculative, whereas mineralogic relationships documented by high-resolution transmission electron microscopy (HRTEM) are more robust due to direct evidence from lattice-fringe observations. In this contribution, the mineralogical and geochemical characteristics of four soils derived from different parent rock types (a gneiss, an Fe-rich siltstone, a sandstone, and a dolostone) from subtropical China were determined using HRTEM, XRD, and geochemical elemental data. The predominance of 2:1 clay minerals and kaolinite in the investigated soils is typical of subtropical climatic settings. Lattice-fringe images suggest the prevalence of topotactic transformations during clay-mineral alteration. Two distinct alteration pathways were observed in the investigated soils, one starting with chlorite and the other with illite, with convergence of mineralogic compositions toward kaolinite and crystalline iron and aluminum (oxyhydr)oxides. In the early stages of weathering, chlorite transformed into expandable clays through a continuous, solid-state mechanism with corrensite and/or randomly interstratified chlorite-vermiculite/chlorite-smectite as intermediate products. Unlike chlorite, which tends to form a 1:1 regularly interstratified phase, the weathering of illite commonly starts at layer edges. Under subtropical monsoonal climates, the precursor minerals in host rocks and aeolian materials determine the starting composition and, to a certain extent, the trajectory of clay-mineral transformation over time. With advanced weathering, mineralogic convergence toward kaolinite and Fe/Al-(oxyhydr)oxides tends to obscure the initial substrate composition. This study advances our understanding of the role of parent lithology in clay-mineral evolution at the nanoscale.

Diagenetic evolution of the lower Yaojia Formation of Songliao Basin, China: Impact on reservoir quality

The oil-bearing layer in the first member of the Upper Cretaceous Yaojia Formation (K2y1) in the middle of the Changling Sag of the southern Songliao Basin, northeast China, has low-permeability and is deemed to be an unconventional reservoir. Therefore, better evaluation of reservoir quality and related controlling factors are crucial for the reduction in exploration risk and sustainable development. The current study integrates diagenesis, sequence stratigraphy, and sedimentary facies to decipher their influence on reservoir quality using core and thin section observations, X-ray diffraction, scanning electron microscopy, fluid inclusion, and carbon and oxygen isotope analyses. The K2y1 is composed of shallow delta sediments of transgressive system (TST) and lowstand system (LST) tracts. The depositional microfacies of the sandstones include TST deltaic front underwater distributary channels and sheet sands, and LST deltaic plain distributary channels, distributary channel intersections, and crevasse splays. The sandstones are dominantly fine-grained moderately sorted feldspathic litharenites and lithic arkoses with silt. Early diagenetic events included compaction, development of smectite, and alteration of feldspar and kaolinite whereas mesogenetic alteration included feldspar dissolution, precipitation of quartz and carbonate cements, and clay mineral alteration. The reservoir quality of the K2y1 sandstones is generally poor, exhibiting variations among different deltaic depositional facies within the LST and TST. The (underwater) distributary channel (intersection) sandstones, particularly those of the LST, have relatively higher reservoir quality owing to their larger grain size, better sorting, lower carbonate cement content, mixed-layer I/S and illite, and greater occurrence of chlorite.

Origin and diagenetic priming of a potential slow-slip trigger zone in volcaniclastic deposits flanking a seamount on the subducting plate, Hikurangi margin, New Zealand

ABSTRACT Slow-slip megathrust events in the Hikurangi forearc region may be related to seamount subduction. IODP Expedition 375 drilled the flank of Tūranganui Knoll, a Cretaceous seamount east of the subduction zone containing units analogous to intervals associated with subducted seamounts. Detailed investigations of the volcaniclastic Unit V at Site U1520, based on scanned core images, petrographic observations, point-counting, and μXRF mapping, reveal that it is a mafic volcaniclastic succession rich in clay minerals which are products of a multiphased history of diagenetic alteration. This unit is interpreted as resulting from downslope transport of volcaniclastic debris from submarine eruptions. In contrast, most volcanic clasts recovered at the nearby Site U1526, near the top of Tūranganui Knoll, are interpreted as products of subaerial eruptions reworked by wave action. This shallow water sedimentary package experienced minimal clay-mineral alteration and more extensive early carbonate cementation. Differences in the clast origins, depositional settings and diagenetic histories of these volcaniclastic units highlight the heterogeneity of volcanic systems on the Hikurangi Plateau. However, the presence of voluminous hydrous clays within thick, altered flanking volcaniclastic units at Site U1520 provides a ready source for excess pore fluids that may enable slow-slip events along the Hikurangi subduction zone.

XRD and TEM analyses of a simulated leached rare earth ore deposit: Implications for clay mineral contents and structural evolution

The types, contents, and microstructures of clay minerals play important roles in controlling the adsorption and desorption of ion-absorbed type rare earth ores and heavy metals. By selecting a typical rare earth ore profile, we conducted a leaching experiment and used XRD (X-ray diffraction) and TEM (Transmission electron microscopy) analyses to determine the clay mineral types and microstructural changes after various leaching periods. The XRD phase analyses showed that the main minerals in the simulated rare earth ore were quartz, potassium feldspar, kaolinite, and illite. TEM images showed that the mineral aggregates were broken, disintegrated, and transformed by the leaching process, and a large number of moire fringes were visible. With continuous leaching, REEs (Rare Earth Elements) were gradually re-solved and leached. The results of the leaching experiment indicate that fine-grained minerals in rare earth ores, such as potassium feldspar and clay minerals, migrated downward with the leaching solution. Leaching also promoted the alteration of potassium feldspar to clay minerals, as well as mutual alteration of clay minerals. Under acidic or neutral conditions during the early stage, potassium feldspar was altered to kaolinite or illite, whereas during the middle and late stages of leaching it was altered as follows: illite → mixed-layer illite–kaolinite → kaolinite → mixed-layer kaolinite–illite → illite. This transformation has an important effect on the release of REEs and heavy metals and provides insights into improving the leaching process and explaining heavy metal pollution in rare earth mining areas.

Compaction control on diagenesis and reservoir quality development in red bed sandstones: a case study of Permian Rotliegend sandstones

Authigenic minerals formed during diagenesis in conjunction with compaction by burial have long been known to lead to porosity-loss of sandstones, and a subsequent deterioration in reservoir quality. The diagenetic impact on reservoir quality and permeability heterogeneity measured horizontal and vertical to bedding was characterized in three fluvio-eolian Lower Permian Rotliegend outcrops from the Flechtingen High, the northern Hesse Basin (both Germany) and the Vale of Eden (UK) using point-counting, polarized light-microscopy, helium pycnometry and permeability measurements. Results show significant porosity (10 to 35%) and permeability (0.01 to 10,000 mD) ranges largely independent of depositional environment. The major control on reservoir quality in Cornberg Sandstones are dolomite and siderite cementation in conjunction with illitization and illite and kaolinite cementation, leading together with quartz cementation to a mostly cemented IGV and poorest reservoir quality (avg. horizontal permeability: 0.96 mD). Flechtingen Sandstones are most intensely compacted due to the lack of significant early diagenetic cement phases and continuous illitic grain-to-grain coatings, which inhibited intense quartz cementation but enhanced chemical compaction at quartz grain contacts, resulting in intermediate reservoir quality (avg. horizontal permeability: 34.9 mD). Penrith Sandstones lack significant authigenic phases besides quartz due to carbonate dissolution during uplift. They show the least amount of detrital feldspars and clay minerals, leading to no major reservoir quality reduction by burial diagenetic clay mineral alterations, resulting in the highest reservoir quality (avg. horizontal permeability: 5900 mD). Additional results highlight higher horizontal to vertical permeability ratios kh/kv in less homogeneous sandstones of < 10 mD of 10, and in more homogenous, higher permeable sandstones > 1000 mD of 1. Although detrital and authigenic sample compositions vary throughout the studied areas, the general effect of grain coatings coverages on syntaxial cement inhibition and chemical compaction can be delineated. This study increases the understanding of porosity reduction in sandstones, as it confirms the necessity to differentiate between the illitic grain-to-grain coatings and illitic grain-to-IGV coatings. As a result, the enhancing effect of illite on chemical compaction on quartz grain-grain boundaries can be better constrained, as well as the effect of grain coatings on quartz cementation. This is relevant for reservoir quality and risk assessment in hydrocarbon and geothermal plays as well as in storage.

Mixed-Layer Illite-Smectite in Pennsylvanian-Aged Paleosols: Assessing Sources of Illitization in the Illinois Basin

Mixed-layer illite-smectite (I-S) from a new set of Pennsylvanian-aged Illinois Basin underclays, identified as paleosols, are investigated to assess the impact of (1) regional diagenesis across the basin and (2) the extent to which ancient environments promoted illitization during episodes of soil formation. Interpretations from Reichweite Ordering and Δ° 2θ metrics applied to X-ray diffraction patterns suggest that most I-S in Illinois Basin paleosols are likely the product of burial diagenetic processes and not ancient soil formation processes. Acid leaching from abundant coal units and hydrothermal brines are likely diagenetic mechanisms that may have impacted I-S in Pennsylvanian paleosols. These findings also suggest that shallowly buried basins (&lt;3 km) such as the Illinois Basin may still promote clay mineral alteration through illitization pathways if maximum burial occurred in the deep past and remained within the diagenetic window for extended periods of time. More importantly, since many pedogenic clay minerals may have been geochemically reset during illitization, sources of diagenetic alteration in the Illinois Basin should be better understood if Pennsylvanian paleosol minerals are to be utilized for paleoclimate reconstructions.

Cation-Exchange Capacity Distribution within Hydrothermal Systems and Its Relation to the Alteration Mineralogy and Electrical Resistivity

Cation-exchange capacity (CEC) measurements are widely used to quantify the smectite content in altered rocks. Within this study, we measure the CEC of drill cuttings in four wells from three different high-temperature geothermal areas in Iceland. The CEC measurements in all four wells show similar depth/temperature related pattern, and when comparing the CEC with electrical resistivity logs, we could show that the low resistivity zone coincides with CEC values &gt;5 meq/100 g. The measurements show, in general, an exponential decrease of the CEC with increasing depth. At the facies boundary between the mixed-layer clay and epidote-chlorite zone, the CEC reaches a steady state at about 5 meq/100 g and below that it only decreases slightly within a linear trend with increasing depth. The facies boundary overlaps with the transition where the electrical resistivity logs show an increase in resistivity. It is shown that the measured CEC can be related to the clay mineral alteration within the geothermal system and the CEC reflects the smectite component within the interstratified chlorite/smectite minerals for similar alteration degree. Furthermore, CEC was measured in seven core samples from different alteration zones that had previously been studied in detail with respect to petrophysical and conductivity properties. The results show a clear correlation between CEC and the iso-electrical point, which describes the value of the pore fluid conductivity where transition from surface conductivity to pore fluid conductivity occurs. The presented study shows that the CEC within hydrothermal altered basaltic systems mimics the expandable clay mineral alteration zones and coincides with electrical logs. The presented method can, therefore, be an easy tool to quantify alteration facies within geothermal exploration and drilling projects.

Characterization of feed coals and coal combustion byproducts from the Wyodak-Anderson coal zone, Powder River Basin, Wyoming

The U.S. Geological Survey (USGS) determined the physical and chemical properties of more than 260 feed coal and coal combustion byproducts from two coal-fired power plants. These plants utilized a low-sulfur (0.23-0.47 wt. % S) and low ash (4.9-6.3 wt. % ash) subbituminous coal from the Wyodak-Anderson coal zone in the Tongue River Member of the Paleocene Fort Union Formation, Powder River Basin, Wyoming. Fifty-three samples of bituminous coal were collected and analyzed from a Kentucky power plant, which used several sources of bituminous coals from the Appalachian and Illinois Basins. Based on scanning electron microscopy (SEM) and X-ray diffraction (XRD) analyses of feed coal samples collected and analyzed from 1996 through the late 2000s, two mineral suites were identified: (1) a primary or detrital suite consisting of quartz (including beta-form grains), biotite, feldspar, and minor zircon; and (2) a secondary authigenic mineral suite containing alumino-phosphates (crandallite and gorceixite), kaolinite, carbonates (calcite and dolomite), quartz, anatase, barite, and pyrite. The detrital mineral suite is interpreted, in part, to be of volcanic origin, whereas the authigenic mineral suite is interpreted, in part, to be the result of the alteration of the volcanic minerals. The mineral suites have contributed to the higher amounts of barium, calcium, magnesium, phosphorus, sodium, strontium, and titanium in the Powder River Basin feed coals in comparison to eastern US coals. XRD analysis indicates that (1) fly ash is mostly aluminate glass, perovskite, lime, gehlenite, quartz, and phosphates with minor amounts of periclase, anhydrite, hematite, and spinel group minerals; and (2) bottom ash is predominantly quartz, plagioclase (albite and anorthite), pyroxene (augite and fassaite), rhodonite, and akermanite, and spinel group minerals. Microprobe and SEM analyses of fly ash samples revealed quartz, zircon, and monazite, euhedral laths of corundum with merrillite, hematite, dendritic spinels/ferrites, wollastonite, and periclase. The abundant calcium and magnesium mineral phases in the fly ash are attributed to the alteration of carbonate, clay, and phosphate minerals in the feed coal during combustion. The calcium- and magnesium-rich and alumino-phosphate mineral phases in the coal combustion byproducts can be attributed to volcanic minerals deposited in peat-forming mires. Dissolution and alteration of these detrital volcanic minerals occurred either in the peat-forming stage or during coalification and diagenesis, resulting in the authigenic mineral suite. The presence of free lime (CaO) in fly ash produced from Wyodak-Anderson coal acts as a self-contained “scrubber” for SO3, where CaO + SO3 form anhydrite either during combustion or in the upper parts of the boiler. Considering the high lime content in the fly ash and the resulting hydration reactions after its contact with water, there is little evidence that major amounts of leachable metals are mobilized in the disposal or utilization of this fly ash.

Phyllosilicate mineral dissolution upon alkaline treatment under aerobic and anaerobic conditions

The dissolution of phyllosilicate minerals exposed to high-pH environments was studied to quantify the influence of alkaline treatments and variable redox conditions on clay dissolution including incongruent dissolution phenomena. The objective of this research was to systematically quantify mineral dissolution with variable alkaline treatments and redox conditions for the first time. This study is focused on the dissolution of phyllosilicate minerals (illite, muscovite, and montmorillonite) under anaerobic and aerobic conditions using comparative solutions (sodium hydroxide and ammonium hydroxide) at similar hydroxide concentration. Our batch data show that there is a rapid decrease in aluminum dissolution (<240 h) and slow increase in silica dissolution over time (up to 1440 h). This trend was particularly evident for montmorillonite for which the greatest dissolution was observed with ammonium hydroxide treatment, likely due to intercalation of the polyatomic cation ammonium into the mineral's expandable layers. When comparing alkaline treatments, the strong base sodium hydroxide dissolved more of the mica minerals, illite and muscovite, likely due to ion-pairing between the silicate tetrahedra [SiO4]n- and Na+ cations in solution compared with weak base NH4OH treatment. In addition, the decreasing redox changes in the absence of oxygen were similar, although the sodium hydroxide treatment had greater variability. For all investigated phyllosilicates, the calculated aqueous aluminum and silicon ratios over time were significantly different from the minerals' stoichiometric ratios. As a result, we conclude that incongruent dissolution occurred and suggest formation of secondary precipitates. Understanding the potential for clay mineral alterations from interaction with alkaline solutions has implications for in situ remediation, mining operations, and waste interactions within the subsurface. This research shows that incongruent dissolution in phyllosilicate minerals occurs and will likely lead to secondary precipitation which may have long term physical and chemical impacts in the subsurface.

Clay Mineral Alteration in Oil and Gas Fields: Integrated Analyses of Surface Expression, Soil Spectra, and X-Ray Diffraction Data

Subsurface hydrocarbon occurrences can be detected by clay mineral (CM) alteration at the surface as a consequence of hydrocarbon migration. This study analyzed CM alteration in an oil and gas (O&G) field in the West Tugu field, located in the northwest Java Basin of Indonesia. Landsat 8 OLI data acquired on 25 September 2015 and soil spectral reflectance (SSR) data recorded using analytical spectral devices (ASD) in March 2017 were processed using clay indices to analyze CM alteration. Soil samples from a field survey of the same area were also analyzed using X-ray diffraction (XRD) to identify their CM compositions. CM distribution was empirically modeled by integrating the SSR bands re-sampled to Landsat 8 OLI (SSRL) bands and the CM composition using the best subset regression method and regression analyses. The resulting model was applied to Landsat 8 OLI images to map the surface CM alteration. The results show that CM alteration observed in the O&G field is an indicator of hydrocarbon microseepage at the surface. These results can be used as a technique to identify prospective regions that contain hydrocarbons and differentiate from those that are barren, and could be useful for increasing the rate of drilling success.

Clay Minerals and Micromorphology of the Loess Paleosols, Kashmir Valley, India

Loess paleosols have been often studied to reconstruct late Quaternary past climate changes. In the present study, textural analysis, TOC, CaCO3 content, micromorphology and clay mineralogy of the three loess paleosol profiles from three sites (Choori, Alochibagh and Burzahama), from Kashmir valley are presented. Based on the dates of Burzahama section, the exposed loess paleosols are approximately dated to 45ka. Textural analyses suggest that the sediments are largely fine silt followed by silty loam and silty clay loam. The fine sand component in the loess and paleosols indicate that winds in the valley were strong, but in phases the wind velocity was low. The paleosols are much thicker than loess layers and form several horizons within the lithosections. The increase of CaCO3 content indicates that it has leached in phases and along with total organic carbon (TOC) resulted in mild pedogenesis with variations in the rate of pedogenesis within the paleosols and forming pedocomplexes. Micromorphology of the loess-paleosols indicates the presence of calcite nodules with iron oxide coating indicating sub-aerial weathering and pedogenesis. The presence of channel structures in loess paleosols formed due to root traces and pores probably during the warmer periods. The replacement of chlorite by smectite clays in loess paleosols suggests that the alteration of clay minerals probably took place in cold, dry, warmer climatic conditions in low wind regime.

Characterization of quartz in the Wufeng Formation in northwest Hunan Province, south China and its implications for reservoir quality

Quartz is one of the most important and common minerals in marine shales. This is especially true for the Wufeng-Longmaxi and Niutitang Formations in south China. However, the type, origin and formation mechanism of the quartz in these marine shales are as yet unclear. Thirteen samples of Ordovician shale from the Wufeng Formation in northwest Hunan Province were collected for this study. The quartz within the Wufeng shale was characterized through a series of experiments employing scanning electron microscopy with cathodoluminescence, nitrogen physisorption, X-ray diffraction, and geochemical analysis. The results were then used to assess the implications of the quartz component for reservoir quality. Three quartz types were identified based on scanning electron microscopy and cathodoluminescence imaging. Type I quartz has a relatively large grain size and exhibits bright luminescence, indicative of a terrigenous origin, whereas Type II and Type III quartz is authigenic and has dull or no luminescence. Type II quartz has small grain sizes and may be mainly biogenic in origin. This type of quartz may have formed during early diagenesis, with the silica being sourced from the dissolution of siliceous organisms. Type III quartz generally appears as dark rims on Type I quartz grains; the silica may have been derived from clay mineral alteration, with quartz-formation occurring during middle or late diagenesis. The authigenic quartz (Types II and III quartz) likely formed as a cement and would be expected to generate brittle behavior. The shale with a high content of authigenic quartz has a high Young's modulus and low Poisson's ratio. The biogenic authigenic quartz (Type II quartz) was pore-filling and formed during shallow burial. It would thus have been able to resist further compaction and provide a rigid framework within which the primary pores in the shale could be preserved, controlling the distribution of organic matter and the development of organic pores. The biogenic authigenic quartz has positive relationships with porosity and pore volume and specific surface area. Shale that was high in biogenic quartz had high porosity and adsorption capacity. The characterization of quartz in marine shales has significance for shale gas exploration and development and provides a new angle for evaluating the fracability and storage capacity of shale gas reservoirs.

Optimum design of water-based drilling fluid in shale formations in Khangiran oilfields

In this study, an environmentally friendly water-based drilling fluid is designed to replace the oil-based drilling fluids. This drilling fluid has desirable properties in drilling water sensitive formations. New drilling fluid additives have been used to prepare this new drilling fluid. The most important properties of this new drilling fluid are controlling the mud filtrate and pressure invasion to the formation, clay mineral alteration and activity reduction, improvement of the integrity of drilling cuttings, reduction in formation damage, stability at high temperatures, stability in acidity changes and the compatibility by drilling fluids dilution during drilling operation. The lubricity and shale cuttings recovery of this fluid are better than other similar water based drilling fluids. Application of this fluid can protect the environment and drilling personnel in addition to being economically advantageous.