Transformation Of Smectite Research Articles

Direct evidence of transformation from smectite to palygorskite: TEM investigation

Palygorskite clays sampled from palygorskite clay deposits in Jiangsu and Anhui provinces were investigated by transmission electron microscopy (TEM). Many intergrowth phenomena of special ultra-microstructure between smectite and palygorskite were found. The ultra-microstructure indicates that palygorsite fiberrous crystals grow along (001) of primary smectite through structural transformation and decomposition of the primary smectite. According to field investigation and X-ray diffraction (XRD) analyses, the transformation mechanism and process can be described as: formation of smectite from basalt weathering deposited in localization basin; evaporation of lake water in aridity environment causing pH increase and concentration of magnesium ion in interstice water of sediment smectite in the lake basin. Under alkaline conditions, magnesium ion occupied interlayer positions of the smectite. Because of the misfit between magnesium octahedral sheet and smectite layer, magnesium ion interaction with smectite layers caused the smectite to transform into palygorskite, and resulted in the formation of smectite and palygorskite complex particulates, and even smaller secondary smectite crystal plates. The transformation of smectite structure resulted in the formation of nanometer minerals with large specific surface area and excellent property of physics and chemistry in smec-tite-palygorskite mixing clay. The results from TEM investigation are important for understanding properties of palygorskite clay and application.

Experimental study of the transformation of smectite at 80 and 300°C in the presence of Fe oxides

The alteration and transformation behaviour of montmorillonite (Wyoming bentonite) was studied experimentally to simulate the mineralogical and chemical reaction of clays in contact with steel in a nuclear waste repository. Batch experiments were conducted at 80 and 300°C, in low-salinity solutions (NaCI, CaCl 2 ) and in the presence or otherwise of magnetite and hematite, over a period of 9 months. The mineralogical and chemical evolution of the clays was studied by XRD, SEM, transmission Mossbauer spectroscopy and EDS-TEM. Experimental solutions were characterized by ICP-AES and ICP-MS. The main results are that no significant change in the crystal chemistry of the montmorillonite occurred at 80°C, while at 300°C, the presence of Fe oxides leads to a partial replacement of montmorillonite by high-charge trioctahedral Fe 2+ -rich smectite (saponite-like) together with the fonnation of feldspars, quartz and zeolites.

Experimental study of the transformation of smectite at 80 and 300°C in the presence of Fe oxides

Experimental study of the transformation of smectite at 80 and 300°C in the presence of Fe oxides

Comparison of smectite- and illite-rich gouge frictional properties: application to the updip limit of the seismogenic zone along subduction megathrusts

Along plate boundary subduction thrusts, the transformation of smectite to illite within fault gouge at temperatures of ∼150°C is one of the key mineralogical changes thought to control the updip limit of seismicity. If correct, this hypothesis requires illite-rich gouges to exhibit frictionally unstable (velocity-weakening) behavior. Here, we report on laboratory experiments designed to investigate the frictional behavior of natural and synthetic clay-rich gouges. We sheared 5-mm-thick layers of commercially obtained pure Ca-smectite, a suite of smectite–quartz mixtures, and natural illite shale (grain size ranging from 2 to 500 μm) in the double-direct shear geometry to shear strains of ∼7–30 at room humidity and temperature. XRD analyses show that the illite shale contains dominantly clay minerals and quartz; within the clay-sized fraction (<2 μm), the dominant mineral is illite. Thus, we consider this shale as an appropriate analog for fine-grained sediments incoming to subduction zones, within which smectite has been transformed to illite. We observe a coefficient of friction (μ) of 0.42–0.68 for the illite shale, consistent with previous work. Over a range of normal stresses from 5 to 150 MPa and sliding velocities from 0.1 to 200 μm/s, this material exhibits only velocity-strengthening behavior, opposite to the widely expected, potentially unstable velocity-weakening behavior of illite. Smectite sheared under identical conditions exhibits low friction (μ=0.15–0.32) and a transition from velocity weakening at low normal stress to velocity strengthening at higher normal stress (>40 MPa). Our data, specifically the velocity-strengthening behavior of illite shale under a wide range of conditions, do not support the hypothesis that the smectite–illite transition is responsible for the seismic–aseismic transition in subduction zones. We suggest that other depth- and temperature-dependent processes, such as cementation, consolidation, and slip localization with increased shearing, may play an important role in changing the frictional properties of subduction zone faults, and that these processes, in addition to clay mineralogy, should be the focus of future investigation.

Palygorskite genesis through silicate transformation in Tunisian continental Eocene deposits

AbstractThe mineralogical and geochemical characteristics of Eocene continental sediments in south central Tunisia (Chebket Bouloufa and Jebel Hamri) and in north central Tunisia (Jebel Lessouda and Jebel Rhéouis), which contain considerable amounts of palygorskite, were studied. The clay fraction of the sediments also comprises illite, kaolinite, Mg smectite and Al smectite, together with carbonates (calcite and/or dolomite), quartz, gypsum and feldspars, all of which are present in extremely variable proportions.The textural characteristics of the samples containing most palygorskite, as well as the chemical composition of the fibres and the contents of certain trace and rare earth elements suggest that the genesis of this fibrous clay is intimately linked to the diagenetic transformation of illite, mixedlayered minerals and/or Al smectite, as has also been observed in contemporaneous deposits in Morocco.

Palygorskite genesis through silicate transformation in Tunisian continental Eocene deposits

The mineralogical and geochemical characteristics of Eocene continental sediments in south central Tunisia (Chebket Bouloufa and Jebel Hamri) and in north central Tunisia (Jebel Lessouda and Jebel Rhéouis), which contain considerable amounts of palygorskite, were studied. The clay fraction of the sediments also comprises illite, kaolinite, Mg smectite and Al smectite, together with carbonates (calcite and/or dolomite), quartz, gypsum and feldspars, all of which are present in extremely variable proportions.The textural characteristics of the samples containing most palygorskite, as well as the chemical composition of the fibres and the contents of certain trace and rare earth elements suggest that the genesis of this fibrous clay is intimately linked to the diagenetic transformation of illite, mixedlayered minerals and/or Al smectite, as has also been observed in contemporaneous deposits in Morocco.

Salinity variation of formation water and diagenesis reaction in abnormal pressure environments

An understanding to the chemistry of formation waters in sedimentary basins is important for many geological processes, such as the fluid-rock interaction, the migrating paths of fluid and the entrapment mechanisms of hydrocarbon. This paper deals with the salinity variation of formation water and diagenesis reaction in the abnormally pressured system. The Shiwu depression of the Songliao basin and the Yinggehai basin are selected for case studies. The studies indicate that there is a distinct difference in the chemistry of subsurface water between hydropressured and abnormally pressured systems. The Shiwu depression of the Songliao basin is composed of terrigeneous clastics in fluvial-lacustrine environments, which contain brackish water with salinity ranging from less than 1000 mg/L to 12000 mg/L. Water composition varies with depth and hydrochemical regions. In the underpressured strata deposited during the rifting period, the formation water is characterized by CaCl2 type water with high salinity. NaHCO3-dominanted water with lower salinity occurs at the hydropressured strata deposited during the post-rifting period. In this halite-free basin, brackish water may be attributed to the condensation of meteoric water and water-rock interaction. In the deeply buried underpressured water, a predominated diagenesis reaction resulting in enrichment of Ca and Cl and reduction of Na may be related to the albitization of plagioclase following the basinal fluid line (BFL). The Yinggehai basin constitutes clastic deposits in nearshore, neritic, shelf environments and contains brackish and saline water with salinity ranging from less than 15000 mg/L to 50000 mg/L. Pore water in these marine deposits must have originated from seawater. In the overpressured system, however, the formation water has much lower salinity and ion concentrations (except bicarbonate and carbonate) than normal seawater. The low salinity indicates that interstitial connate seawater is diluted by the water released from the transformation of smectite to illite. High bicarbonate and carbonate concentrations may contribute to mineral dehydration and kerogen-cracking reactions. Furthermore, low salinity water also occurs near and above the top of the geopressured zone in the diapiric structures, which may indicate that pore water with normal seawater salinity has been mixed by fresher saline water from deeper portions of the overpressured stratigraphic section.

Effets thermique et hydrothermal de la coulée de basalte triasico-liasique sur les argiles du bassin d'Argana (Maroc)

Thermal and hydrothermal effects of Triassic-Liassic basalt flow deposition on clays (Agana Basin, Morocco). Thermal and hydrothermal effects of Triassic-Liassic basalt flow deposition on sedimentary series of the Argana Basin are responsible for major modifications in detrital clays, until 20 m in depth. It expressed by transformation of detrital smectite to corrensite and moreover to chlorite, and by increasing illite crystallinity. On the 2 m of sediments located immediately under the flow, magnesium-rich hydrothermal fluids have caused precipitation of new mineral phases. To cite this article: L. Daoudi, J.-L. Pot de Vin, C. R. Geoscience 334 (2002) 463-468.  2002 Academie des sciences / Editions

Palaeomagnetic dating of widespread remagnetization on the southeastern border of the French Massif Central and implications for fluid flow and Mississippi Valley-type mineralization

Palaeomagnetic dating techniques have been applied to determine the age of fluid migration that produced the Mississippi Valley-type (MVT) Pb–Zn–Ba–F deposits in the Cévennes region of southern France. 15 sampling sites in two gently deformed areas around the Largentière and Croix-de-Pallières mines on the Cévennes border were selected for palaeomagnetic study. They yielded a very well-defined direction of remagnetization corresponding to an Early-Middle Eocene age. This remagnetization cannot be related to the formation of magnetite as a result of the transformation of smectite to illite because the latter has been well dated as a Mesozoic event. The magnetic overprint in this area is related to a chemical phenomenon during fluid migration. The age of remagnetization corresponds to a major uplift in the Pyrénées mountains, located to the south of the Cévennes. This implies that fluid migration occurred from the south to the north as a result of hydraulic head established in the Pyrénées orogenic belt during orogenesis and suggests that the MVT deposits in the Cévennes region formed from a gravity-driven fluid system as described by Garven & Freeze (1984a, b).

Lithium isotopic compositions of pore fluids and sediments in the Costa Rica subduction zone: implications for fluid processes and sediment contribution to the arc volcanoes

Pore fluid and sediment Li concentrations and isotopic ratios provide important insights on the hydrology, sediment contribution to the arc volcanoes and fluid–sediment reactions at the dominantly non-accretionary Costa Rica subduction zone. Ocean Drilling Program Site 1039 in the trench axis provides a reference section of 400 m of the incoming sediments, and Site 1040, situated arcward from the trench, consists of a deformed sedimentary wedge and apron sediments, the décollement, and the partially dewatered underthrust sediment section. At the reference site, pore fluids show important isotopic variations (δ 6Li=−21.7 to −37.8‰), reflecting the interplay of in situ alteration of volcanic material and ion exchange with clay minerals. In the basal section, a reversal of Li concentration and δ 6Li toward seawater values is observed, providing supporting evidence for a lateral seawater flow system in the upper oceanic basement underlying this sediment section. At Site 1040, pore fluid of the lower deformed wedge sediments and within the décollement is enriched in Li and the isotopic compositions are relatively light, suggesting infiltration of a deep-seated fluid. The δ 6Li value of −22‰ of this Li-enriched fluid (261 μM), when compared with the δ 6Li value of the subducted sediment section (−11‰), suggests that the deep source fluid originates from mineral fluid dehydration and transformation reactions at temperatures of 100 to 150°C, consistent with the temperature range of the up-dip seismogenic zone and of transformation of smectite to illite. The distribution of Li and its isotopes in the underthrust section are similar to those at the reference site, indicating near complete subduction of the incoming sediments and that early dewatering of the underthrust sediments occurs predominantly by lateral flow into the ocean. The hemipelagic clay-rich sediment section of the subducting plate carries most of the Li into this subduction zone, and the pelagic diatomaceous and nannofossil calcareous oozes contain little Li. The Li isotopes of both the clay-rich hemipelagic sediments and of the pelagic oozes are, however, similar, with δ 6Li values of −9 to −12‰. The observations that (1) the δ 6Li values of the underthrust sediments are distinctly lower than that of the mantle, and (2) the lavas of the Costa Rican volcanoes are enriched in Li and 7Li, provide an approximation of the contribution of the subducted sediments to the arc volcanoes. A first order mass balance calculation suggests that approximately half of the Li flux delivered by subducted sediments and altered oceanic crust into the Middle American Trench is recycled to the Costa Rican arc and at most a quarter of sedimentary Li is returned into the ocean through thrust faults, primarily the décollement thrust.

Palaeozoic clay mineral sedimentation and diagenesis in the Dinant and Avesnes Basins (Belgium, France): relationships with Variscan tectonism

Abstract Clay mineral investigations have been performed on more than 500 limestones and shales sampled in Lower Devonian (Emsian) to Lower Carboniferous (Namurian) outcrops in the Dinant and Avesnes Basins (Ardenne Massif, NW Europe). Clay mineral data have been placed in the palaeoenvironmental and structural histories documented by previous lithological, stratigraphical, palaeontological, diagenetic and tectonic contexts. The clay associations are dominated by illite and chlorite derived partly from the erosion of land masses surrounding the marine domain. The geothermal gradient estimated from correlation with conodont colour alteration index ranges between 40 and 70°C/km. A diachronous northwards migration of the diagenesis/metamorphism interface links to uplift caused by Late Carboniferous compressional folding and overthrusting. Associated clay minerals include smectite, locally preserved from diagenetic changes mainly by early pore closure, that reflect lagoonal or quiet offshore marine conditions. Smectite and subordinate kaolinite abundances decrease upwards during the Devonian in three successive intervals suggesting alternations of sub-arid to drier climates. The local occurrence of corrensite (ordered chlorite–smectite mixed-layer) is attributed to the moderate diagenetic transformation of pre-existing smectite

Mixed Layering of Illite-Smectite: Results from High-Resolution Transmission Electron Microscopy and Lattice-Energy Calculations

AbstractMixed layering of illite-smectite was studied both experimentally, by using high-resolution transmission electron microscopy (HRTEM) and analytical electron microscopy (AEM), and theoretically, by using lattice-energy calculations.Samples from a hydrothermal origin show the transformation of smectite to illite with different ordering types in the illite-smectite layer sequences. Ordering ranges from complete disordered (Reichweite, R = 0 type) in the less transformed samples to increased local order, with IS and IIS sequences (R = 1 and R = 2, respectively; I = illite, S = smectite) in more illitized samples.Lattice-energy calculations are used to determine the structure of the illite-smectite sequence, which corresponds to the minimum energy. The unit layers are: O0.5TI′TO0.5 (O, T, and I′, respectively, denote the octahedral and tetrahedral sheets, and the interlayer. The 0.5 signifies half of the octahedral cations.) For example, the arrangements of the perfectly ordered … ISIS … and … IISIIS … sequences are respectively … OM(TI′T)IOM(TI′T)S … and … OM(TI′T)IOI(TI′T)1OM(TI′T)S … (the subscripts I, S, and M, respectively, refer to compositions of illite, smectite, and midway between at 0.5). Such arrangements produce a polar model for TOT layers, which display a TIOMTS structure in the case of IS adjacent layers. Furthermore, the lattice energies of … ISIS … and … IISIIS … are found to be nearly equal to the corresponding sums of the lattice energies of illite and smectite. This result indicates that interstratified illite-smectite and the two-phase assemblage of illite + smectite have similar stabilities.On the basis of the above model, the solid-state transformation of one smectite layer to one illite layer, which produces mixed-layer sequences, involves the transformation of an O0.5TI′TO0.5 unit of smectite into the same corresponding unit of illite.

Pedogenic Formation of Kaolinite-Smectite Mixed Layers in a Soil Toposequence Developed from Basaltic Parent Material in Sardinia (Italy)

AbstractFormation of kaolinite-smectite (K-S) mixed layers in a soil toposequence developed from basaltic parent material was examined. The soil formed in a temperate climate with alternating dry and wet seasons in Sardinia (Italy). Chemical composition and charge characteristics of the smectite component in the K-S mixed layers were analyzed to help determine a mechanism for formation. Soils were sampled at the top, intermediate, and base of a steep (35%) slope. As indicated by X-ray diffraction data, the fine clay fraction (&gt;0.1 μm) in the soils is dominated by K-S with a decreasing proportion of kaolinite from the top (70%) to the base (30%). Rapid internal drainage induced by the slope is probably the major factor responsible for the formation of K-S. Chemical composition and charge characteristics of the smectite component in the K-S were analyzed by X-ray diffraction (intercalation with alkylammonium ions), cation exchanged capacity (CEC) and surface area measurements, and infrared spectroscopy. Results indicate that the smectite component is nearly identical over the soil toposequence. The smectite component is the same with respect to charge magnitude and chemical composition, independent of the proportion of kaolinite and smectite components. This suggests the pedogenic formation of K-S by transformation of smectite through dissolution of some smectite layers and subsequent crystallization of kaolinite between the layers of the remaining smectite crystallites.

Potassium sources and illitization in Texas Gulf Coast shale diagenesis

ABSTRACT The aim of this paper is to identify the controls on the rates of illitization in Texas Gulf Coast shales under diagenetic conditions. Two different mineral transformations are considered: the transformation of smectite to (nearly) illite and the precipitation of discrete illite, i.e., the formation of pure illite. Analyses of potassium feldspar and kaolinite abundance, in addition to K2O, Al2O3, and TiO2 contents, in shales from three wells are used to supplement published data in order to identify the mineral reactions responsible for the smectite-to-illite transformation in shales involving illite/smectite (I/S) mineral series. These data indicate that the first stage of the smectite-to-illite reaction in shales (R = 0 structures, ca. 0- 50% illite content) is controlled by the presence of feldspar and hence also by the dissolution kinetics of feldspar. The empirically derived activation energy for the first I/S transformation in shales is similar to that for K-feldspar dissolution. Kaolinite is not involved in this transformation in the shales investigated. The second stage of the reaction sequence (R = 1 structures, ca. 50- 100% illite content) occurs after potassium feldspar has largely or completely disappeared from the shale system. This indicates that the feldspar no longer controls the second stage of the smectite-to-illite transformation, and suggests another, external, source of potassium for the reaction in the shales. This assumption is supported by the relative increase of potassium content of the shales, at least in two of the three studied wells. Kaolinite does not seem to be involved either in this second stage of the I/S reaction sequence. The formation of discrete illite crystallites in shales is independent of the I/S transformation reactions and takes place only after a very significant period of time has elapsed. The slow rate of this reaction reflects the low activity of potassium in solutions that are in equilibrium with shale, in comparison with sandstones, where a rapid precipitation of pure illite can in some cases be observed. It is suggested that the different reactions in the smectite-to-illite transformation necessitate different sources of potassium either from within or outside an argillaceous whole-rock system. These different sources of potassium give rise to different rates for the I/S conversion reaction and the formation of illite.

Randomly Interstratified Kaolinite-Smectite from Galicia (NW Spain): A New Procedure for Determination

AbstractA new protocol was developed to examine an assemblage of kaolinite-smectite in a buried horizon of a paleosol developed on gabbro parent material. The new extraction procedure appears suitable for removing kaolinite and for ascertaining the nature of the smectite interstratified with kaolinite. Smectite was identified by X-ray diffraction (XRD) and infrared (IR) patterns, cation exchange capacity (CEC) and chemical analyses.The results obtained provide for increased understanding of the process of transformation of smectite into kaolinite.

Water–rock interaction and hydrothermal mineral equilibria in the Tendaho geothermal system

The Tendaho geothermal system occurs within a NW–SE-trending rift basin filled with Quaternary volcanics (mainly basalts) and fluvio-lacustrine sediments. Three deep (TD-1, TD-2 and TD-3) and one shallow (TD-4) geothermal wells have been drilled. The waters of productive wells TD-1, TD-2 and TD-4 are typical Na–Cl geothermal waters with reservoir temperature ranging between 220 and 270°C. Chemical analysis of core samples (altered basalts) shows increased Ca, Fe, Mg, Al content (owing to the dissolution of plagioclase and femics and the precipitation of wairakite, laumontite, epidote, garnet, calcite and clay minerals) and decreased Na, K, Si and Ti (owing mostly to the dissolution of glass matrix). Petrographic study of cuttings and core samples shows: (1) evidence of an early stage of calcite, zeolite (wairakite or laumontite) and quartz crystallization, while calcite underwent different stages of dissolution/precipitation, possibly due to abrupt changes in pH and CO 2 partial pressure; (2) that epidote, garnet, prehnite, pyroxene and amphibole crystallization occurred after wairakite or laumontite. Chlorite is the main layered silicate in the basaltic rocks in wells TD-1 and TD-2, temperatures beyond the stability of smectite and chlorite/smectite (C/S) interlayers must have been reached. The smectites and C/S interlayers in association with chlorite in well TD-3 indicate that this well has had a more complex thermal history, with variable temperatures. The smectites occur at temperatures above 120°C, which is considered to be the threshold for the transformation of smectite to illite. No evidence of disequilibrium conditions of smectites has been found at reservoir temperatures currently present at Tendaho. Fluid inclusion data indicate heating in the well TD-1, and thermal conditions similar to the ones measured in the deepest part of well TD-2, while the uppermost part of this latter has undergone cooling. Intense cooling has affected well TD-3, drilled far from the upflow zone of the field, probably in an area characterized by self-sealing, cooling and very low permeability.

Transformation Mechanisms and Interstratification in Conversion of Smectite to Kaolinite: An HRTEM Study

AbstractThe transformation of smectite into kaolinite and kaolinite-smectite interstratification were studied in samples belonging to the Argiles Plastiques formation of the Paris basin, by high-resolution transmission electron microscopy (HRTEM). Two original smectite phases, 1) beidellite with 1-nm-thick layers, and 2) beidellite-montmorillonite with 1.25-nm-thick layers, are progressively transformed into kaolinite-smectite mixed-layer minerals, and into kaolinite. As the percentage of kaolinite layers increases in the interlayered minerals, the kaolinite-smectite layer sequences, initially disordered, become locally more ordered, with the presence of KS and KKS units repeated 2 to 4 times (K = kaolinite layer, S = smectite layer). Two solid-state mechanisms seem to be responsible for the formation of kaolinite: 1) the transformation of 1 smectite layer into 1 kaolinite layer, denoted S → K, by stripping of a tetrahedral sheet and the adjacent interlayer region; 2) the intercalation of 1 kaolinite layer into smectite, denoted 0 (zero)→K. Structural and chemical incidences of these mechanisms are discussed.

Electron microscopic study of the illite–smectite transformation in the bentonites from Cerro del Aguila (Toledo, Spain)

AbstractA mineralogical and microstructural study of bentonites from 'Cerro del Aguila' located in the Tagus Basin (Toledo, Spain) was carried out using XRD, SEM and TEM observations and chemical data obtained by TEM-EDX. The bentonites are mainly composed of trioctahedral smectite with a unit-cell formula (Si3.76Al0.24)(Al0.44Fe3+0.26Mg1.81)Ca0.05K0.19O10(OH)2 and small amounts of illite. The relationships between illite and smectite particles observed by SEM and TEM allowed the study of the weathering process of illite to form smectite through possible intermediate stages. The transformation begins as an exfoliation normal to the stacking direction and develops by opening of the interlayer spacing, the replacement of K+ by hydrated interlayer cations and slight reorganization of the 2:1 layer structure. The so-called solid-state transformation process then proceeds by further dissolution and the formation of a colloidal phase acting as raw material in the growth of new phyllosilicates such as smectite.

Lithological control on the occurrence of chlorite in the diagenetic Wealden complex of the Bilbao anticlinorium (Basco-Cantabrian Basin, Northern Spain)

AbstractSandstones and shales from the southern flank of the Bilbao anticline in the Gordexola and Orozko valleys, northwestern Spain, have been subjected to a detailed sedimentological, mineralogical and geochemical study. They are composed of proximal frontdeltaic sandbars interbedded with silty-clayey sediments and correspond to a prograding sequence of a deltaic system. The clay mineral assemblages of doublets of sandstones and shales are composed mainly of illite, chlorite and illite-smectite mixed-layers R3 (ISII). The clay diagenesis consists of the transformation of smectite and I-S mixed-layers to illite, the precipitation of Fe-rich chlorite in the pore spaces, and the alteration of micas to chlorite. According to petrographic, mineralogical and geochemical analyses, chlorite is more abundant in sandstones than in shales in both the &lt;2 µm and coarser fractions. The relative abundance of chlorite increases in the sandstones located at the top of coarsening upward sandbars. Furthermore, chlorite formation occurs preferentially in the coarser grained sansdstones previously cemented by ankerite. The geochemical and petrological investigations suggest that chlorite formed during burial diagenesis in a relatively closed system.

An oxygen isotope study of illite and calcite in three Appalachian Paleozoic vertic Paleosols

ABSTRACT The oxygen isotope compositions of pedogenic calcite and illite in three Paleozoic vertic red bed paleosols record a complex history of pedogenic and diagenetic processes. The paleosols are preserved in the upper Mississippian (Chesterian) Mauch Chunk (Pennsylvania), Hinton (West Virginia), and Pennington (Tennessee) Formations in the Appalachian Basin and were buried to 7-8 km (230-260°C), 3-4 km (100-145°C), and 1.5-3 km (70-100°C), respectively. The submicron-size clay fractions of the paleosols are presently composed of R3-ordered illite/smectite (I/S), inferred from K-Ar dates and soil morphology to have been authigenically produced by the reaction of smectite to illite. Oxygen isotope fractionations, calculated pore-fluid compositions, and K-Ar dates were used to constrain the conditions and timing of I/S and pedogenic calcite (re)crystallization in each of the paleosols. The data were interpreted in light of three possible end-member environments for formation and recrystallization: (1) the pedogenic environment; (2) the burial diagenetic environment; and (3) a burial environment dominated by hot, tectonically driven fluid. The 18O values of pedogenic calcite and authigenic I/S in vertic red bed paleosols generally reflect recrystallization and exchange during burial diagenesis and are thus not suitable for interpretation of paleoenvironment or paleoclimate. The involvement of orogenic fluids during burial cannot be ruled out, but it is not required by any of the paleosols. In the coastal-margin Pennington Formation paleosol, I/S formation may have been initiated in the pedogenic environment in response to cyclical wetting and drying of the soil clay matrix. Continued smectite transformation and coarsening and ordering of I/S during a long period of shallow burial led to its isotopic reequilibration with pore fluids at slightly elevated temperature, but oxygen isotope compositions of pedogenic calcite in the paleosol are preserved.