Formation Of Smectite Research Articles

Significance of the clay mineral distribution in fluvial sediments of the Neogene to Recent Himalayan Foreland Basin (west-central Nepal)

Clay mineral assemblages of the Neogene Himalayan foreland basin are studied to decipher their significance with respect to tectonic and climate processes. Fluvial deposits of the Siwalik Group (west-central Nepal), and sediment of the Ganga River drainage system were analysed for clay mineralogy. The observed clay mineral assemblages are mainly composed of illite (dominant), chlorite, smectite and kaolinite. Illite and chlorite are chiefly of detrital origin, derived from Himalayan sources. Kaolinite and smectite are authigenic, and mainly developed within pore space and as coating of detrital particles. With increasing burial, diagenetic processes affected the original clay mineral signature. Illitisation of smectite and kaolinite occurred below 2500 and 3500 m depth, respectively. Therefore, illite in the lower parts of the Siwalik Group consists of a mixture of inherited illite and illitised smectite and kaolinite, as suggested by illite crystallinity. Detrital grains that make up the framework of the Siwalik Group sandstones mainly consist of quartz, feldspar and lithic fragments, which are principally of sedimentary and metamorphic origin. Lithoclast content increases over time at the expense of quartz and K-feldspar in response to uplift and erosion of the Lesser Himalaya Series since about 11–10 Ma. Despite mainly felsic source rocks, dominantly physical erosion processes in the Himalayan belt, and high-energy fluvial depositional systems, smectite is abundant in the <7 Ma Siwalik Group deposits. Analyses of the Siwalik deposits and comparison with the clay mineralogy of the modern drainage system suggest that smectite preferentially formed in floodplains and intermontane valleys during early diagenesis because of downward percolating fluids rich in cations from weathering and soil development. In general, increasing seasonality and aridity linked to variability of the Asian monsoon from about 8 Ma enhanced clay mineral formation and development of authigenic smectite in paleo-plains on the southern side of the Himalaya.

Testing geochemical models of bentonite pore water evolution against laboratory experimental data

The determination of a bentonite pore water composition and understanding its evolution with time underpins many radioactive waste disposal issues, such as buffer erosion, canister corrosion, and radionuclide solubility, sorption, and diffusion, inter alia. Previous modelling approaches have tended to ignore clay dissolution–precipitation reactions, a consequence of which is that montmorillonite is theoretically preserved indefinitely in the repository system. Here, we investigate the applicability of an alternative clay pore fluid evolution model, that incorporates clay dissolution–precipitation reactions as an integral component and test it against well-characterised laboratory experimental data, where key geochemical parameters, Eh and pH, have been measured directly in compacted bentonite. Simulations have been conducted using different computer codes (Geochemist’s Workbench, PHREEQC, and QPAC) to test the applicability of this model. Thermodynamic data for the Gibb’s free energy of formation of MX-80 smectite used in the calculations were estimated using two different methods (‘Polymer’ and ‘Vieillard’ Models). Simulations of ‘end-point’ pH measurements in batch bentonite–water slurry experiments showed different pH values according to the complexity of the system studied. The most complete system investigated revealed pH values were a strong function of partial pressure of carbon dioxide, with pH increasing with decreasing PCO 2 (with log PCO 2 values ranging from −3.5 to −7.5 bars produced pH values ranging from 7.9 to 9.6). A second set of calculations investigated disequilibrium between clay and pore fluid in laboratory squeezing cell tests involving pure water (pH = 9.0) or a 1 M NaOH solution (pH = 12.1). Simulations carried out for 100 days (the same timescale as the experiments) showed that smectite remained far from equilibrium throughout, and that the lowering of pH due to smectite hydrolysis was trivial. However, extending the duration of the simulations to that required for clay–fluid equilibrium, necessitated timescales of 7 and 65 years for pure water and 1 M NaOH, respectively, but again produced relatively minor reduction in pH (in the order of 0.1–0.2 pH units). If the (equilibrium) precipitation of secondary minerals was included in the simulations, then not only was the clay–fluid equilibration period extended dramatically (from 7 to 360 years for pure water, and from 65 to 2600 years for 1 M NaOH), but concomitant changes in pH were significant, decreasing from 9.0 to 8.6 (pure water) and from 12.1 to 9.0 (1 M NaOH). Repetition of these latter calculations using an alternative method for Δ G f 0 smectite produced an increase in equilibration time for reaction with 1 M NaOH from 2600 to 5000 years, highlighting the potential effects of the uncertainty in thermodynamic data for smectite. A final set of calculations was carried out to investigate both the time- and space-dependent variations in pore fluid composition in laboratory in-diffusion experiments conducted for over 1200 days, initially with pure water and ‘spiked’ after 271 days with a Na–Ca–OH–Cl solution (pH = 11.7). Here, the sensitivity of the results to both variations in a number of parameters/conditions (porosity, reaction rate of secondary minerals, the degree of mixing of the external fluid reservoirs in the experiments, the effective diffusion coefficient) and the inclusion/exclusion of key processes (clay hydrolysis, secondary mineral precipitation, ion exchange, clay edge protonation–deprotonation reactions) was investigated. These calculations confirmed that smectite dissolution–precipitation reactions alone have an insignificant impact upon pH buffering over laboratory timescales and that the pH buffering observed is most likely controlled by clay protonation–deprotonation reactions, and kinetic secondary mineral (brucite + tobermorite) precipitation. Ion exchange reactions were found to have little effect on pH. Alternative data for the kinetic dissolution of smectite produced no observable differences, and the adoption of a reduced diffusion coefficient produced a poorer fit to experiment results. In conclusion, modelling predicts that the effects of smectite dissolution on the chemistry of bentonite pore waters would be essentially undetectable over experimental time scales, but when the model is combined with plausible constraints on the precipitation of secondary minerals, significant changes in solution chemistry and mineralogy are predicted to occur over time scales that are relevant to repository near-field evolution (hundreds to thousands of years). There are remaining fundamental uncertainties related to the variable chemistry of the smectite clays, the nature of porosity in highly compacted buffer materials, the reactive surface area of smectite, and the thermodynamic properties of these clay minerals.

Low-temperature alteration of basalts – the effects of temperature, acids and extent of reaction on mineralization and water chemistry

The weathering and low-temperature alteration of basaltic glass was studied by geochemical modelling in order to gain an insight into the effects of temperature, acid supply and extent of reaction on the secondary mineralogy and water chemistry. Basaltic glass was dissolved in dilute water at 10–150°C in a closed system and secondary minerals commonly observed in nature allowed to precipitate when saturated. The weathering of basalts in the presence of CO$_2$ was observed to go through three stages; initially simple insoluble Al and Fe hydroxides were formed. Upon progressive basaltic glass dissolution imogolite, allophane and/or kaolinite and Ca–Mg–Fe smectites predominated, decreasing the mobility of Al, Fe, Si, Ca and Mg whereas extensive weathering and alkaline pH values resulted in the formation of smectites, zeolites, calcite and SiO$_2$ minerals. Under low-temperature geothermal conditions and in strong H$_2$ SO$_4$ acid solutions (pH\&lt;4) amorphous silica, kaolinite, Al–Fe oxyhydroxides and sulphur-containing minerals were most important and most cations like Na, K, Ca and Mg were observed to be mobile. Under mildly acid conditions in CO$_2$ enriched waters (pH 5–7) kaolinite, chalcedony, Ca–Mg–Fe smectites and Mg–Fe–Ca carbonates predominated and Fe, Al and Si were found to be immobile, whereas Mg and Ca mobility depended on the mass of carbonate formed and water pH. Under alkaline conditions (pH\&gt;8) that resulted from a low acid supply and/or extensive basaltic glass dissolution chalcedony, celadonite, Ca–Mg–Fe smectites, zeolites and calcite were found to form, greatly reducing the mobility of most dissolved elements. The dominant factor determining the weathering and low-temperature alteration of basaltic glass and the associated elemental mobility is the pH of the water. In turn, the pH value is determined by the input and type of acid and their ionization constant and quantity of basaltic glass dissolution and secondary minerals formed that increases with the extent of the reaction and the temperature. The weathering mineralogy observed associated with basaltic glass in Iceland is typical of low to moderate degree of alteration under low (atmospheric) CO$_2$ conditions. The low-temperature regional geothermal alteration commonly observed in Iceland is also typical for low CO$_2$ alteration and the reaction order of celadonite and chalcedony, followed by mixed clays and chlorite and eventually zeolites and calcite, indicate increased water–rock interaction at pH&gt;8 with temperature being less important on the overall reaction path.

Hydrothermal Formation of Lath-Shaped Trioctahedral Smectite with High Crystallinity

Lath-shaped and highly crystalline trioctahedral smectites were synthesized under hydrothermal conditions. The quenched glasses with stoichiometrically dehydrated Na-smectite compositions were treated at (a) 500°C and 100 MPa for 1 and 11 days; and (b) 300°C and 100 MPa for 7 days. The crystallinity and particle size of products were dependent on the chemical composition of the starting glass, synthetic temperature and duration of hydrothermal treatment. The high structural ordering and large dimensions of the products were confirmed from the sharpness of XRD peaks; and hydration behavior under controlled relative humidity. Transmission electron microscopy was also performed for the characterization of the particle size of product. Particle sizes vary from ca. 10 nm to a few μm by changing the chemical compositions of the starting materials. The product with the highest structural ordering and largest dimension was obtained from Na0.33(Mg1.83Al0.67)Si4O11 glass treated at 500°C and 100 MPa for 1 day. The obtained results also confirmed the metastability and compositional dependency in the formation of highly crystalline trioctahedral smectite at hydrothermal conditions.

Reservoir characterization of Scollard-age fluvial sandstones, Alberta foredeep

A detailed laboratory study of 53 sandstone samples from 23 outcrops and 156 conventional core samples from the Maastrichtian-Paleocene Scollard-age fluvial strata in the Western Canada foredeep was undertaken to investigate the reservoir characteristics and to determine the effect of diagenesis on reservoir quality. The sandstones are predominantly litharenites and sublitharenites, which accumulated in a variety of fluvial environments. The porosity of the sandstones is both syn-depositional and diagenetic in origin. Laboratory analyses indicate that porosity in sandstones from outcrop samples with less than 5% calcite cement averages 14%, with a mean permeability of 16 mD. In contrast, sandstones with greater than 5% calcite cement average 7.9% porosity, with a mean permeability of 6.17 mD. The core porosity averages 17% with 41 mD permeability. Cementation coupled with compaction had an important effect in the destruction of porosity after sedimentation and burial. The reservoir quality of sandstones is also severely reduced where the pore-lining clays are abundant (>15%). The potential of a sandstone to serve as a reservoir for producible hydrocarbons is strongly related to the sandstone’s diagenetic history. Three diagenetic stages are identified: eodiagenesis before effective burial, mesodiagenesis during burial, and telodiagenesis during exposure after burial. Eodiagenesis resulted in mechanical compaction, calcite cementation, kaolinite and smectite formation, and dissolution of chemically unstable grains. Mesodiagenesis resulted in chemical compaction, precipitation of calcite cement, quartz overgrowths, and the formation of authigenic clays such as chlorite, dickite, and illite. Finally, telodiagenesis seems to have had less effect on reservoir properties, even though it resulted in the precipitation of some kaolinite and the partial dissolution of feldspar.

Kaolinite flocculation induced by smectite addition – A transmission X-ray microscopic study

The influence of smectite addition on kaolinite suspensions in water was investigated by transmission X-ray microscopy (TXM) and Scanning Electron Microscopy (SEM). Sedimentation test screening was also conducted. Micrographs were processed by the STatistic IMage Analysing (STIMAN) program and structural parameters were calculated. From the results of the sedimentation tests important influences of small smectite additions to about 3 wt.% on kaolinite suspension flocculation has been found. In order to determine the reason for this smectite impact on kaolinite suspension, macroscopic behaviour micro-structural examination using Transmission X-ray Microscope (TXM) and SEM has been undertaken. TXM & SEM micrographs of freeze-dried kaolinite–smectite suspensions with up to 20% smectite showed a high degree of orientation of the fabric made of highly oriented particles and greatest density when 3 wt.% of smectite was added to the 10 wt.% dense kaolinite suspension. In contrast, suspensions containing pure kaolinite do not show such platelet mutual orientation but homogenous network of randomly oriented kaolinite platelets. This suggests that in kaolinite–smectite suspensions, smectite forms highly oriented basic framework into which kaolinite platelets may bond in face to face preferential contacts strengthening structure and allowing them to show plastic behaviour which is cause of platelets orientation.

Mineralogy, Geochemistry, and Origin of Bentonite in Upper Cretaceous Pyroclastic Units of the Tirebolu Area, Giresun, Northeast Turkey

AbstractWidespread alteration in the Upper Cretaceous pyroclastic units of the Tirebolu (Giresun) area, NE Turkey, has resulted in significant occurrences of bentonite with economic potential. No detailed geological, mineralogical, or geochemical characterization of these occurrences has been carried out to date. The aim of this study was to describe the geological background, the mineralogical, chemical, and stable-isotope characteristics of the bentonite, and major aspects of their formation, e.g. type and source of low-temperature alteration, mass balance, chemical evolution of the smectites, and geochemistry of major and trace elements. The bentonite contains abundant smectite with occasional kaolinite and mordenite, volcanogenic feldspar, quartz, biotite, hornblende, glass shards, and pumice fragments, along with the diagenetic minerals, opal-CT, and, in some locations, calcite. X-ray diffraction patterns of the clay fractions exhibit characteristics of pure montmorillonite and beidellite-type smectite. Micromorphologically, the smectite exhibits a honeycomb texture, the kaolinite occurs in both vermiform and irregular platy forms, and the mordenite occurs in fibrous form. All of these minerals are edged with devitrified volcanic glass and resorbed feldspar. Chemically, the smectites are Ca-smectite. Geochemical data indicate that alteration of the pyroclastic units took place under suboxic and anoxic environmental conditions during bentonite formation. Field observations and mineralogical, geochemical, oxygen, and hydrogen isotopic data indicate that the alteration of feldspar and volcanic glass in the pyroclastics by mixed meteoric and sea water in a shallow marine environment under alkaline and acidic conditions, respectively, controlled by environmental Al, Ca, and Na concentrations, resulted in the formation of authigenic smectite, mordenite, and kaolinite. A large Ca content in the smectite originated from surrounding units, which resulted in high alkalinity; Mg originated from seawater.

Inheritance and formation of smectite in a texture contrast soil in the Pilliga State Forests, New South Wales

Smectite genesis is generally considered to require an alkaline environment, for in acid environments it is reportedly unstable. This study shows that smectite is forming in an acid, texture-contrast soil in the Pilliga State Forests in north-western New South Wales. Three modes of smectite genesis in the study soil are presented. The first mode involves direct inheritance from the underlying parent rock. The second and third modes involve precipitation of smectite from solution and its deposition from suspension, respectively. While the bulk of the smectite in the study soil is inherited from the transformation of labile primary minerals and rock fragments in the parent rock, restricted drainage coupled with a parent material capable of supplying the elemental constituents of smectite are also important factors in its genesis.

Low-Temperature Hydrothermal Alteration of Trachybasalt at Conical Seamount, Papua New Guinea: Formation of Smectite and Metastable Precursor Phases

AbstractThe conversion of volcanic glass to secondary alteration products is one of the most common mineralogical transformations during low-temperature hydrothermal alteration of submarine basalts. To better understand the mechanism and kinetics of this transformation, porphyritic and formerly glassy trachybasalt, recovered from Conical Seamount, Papua New Guinea, was studied in detail. Low-temperature interaction of trachybasalt with hydrothermal fluids at this submerged volcano occurred in response to the formation of submarine epithermal-style gold mineralization. Alteration of the coherent volcanic rocks is heterogeneous with pronounced differences in alteration intensity occurring between igneous minerals and the surrounding glassy groundmass. In comparison to the volcanic glass, the crystalline phases were less prone to hydrothermal alteration with the alteration susceptibility decreasing from clinopyroxene through biotite to feldspar. Low-temperature alteration of clinopyroxene resulted in the formation of abundant saponite-like smectite with no topotactic relationship being observed between the two phases. In contrast, the conversion of biotite to smectite involved structural inheritance as the orientation of common structural blocks was maintained during alteration. Transmission and analytical electron microscopy revealed that pervasive alteration of interstitial glass in the groundmass of the trachybasalt resulted in the formation of montmorillonite- and saponite-like smectite whereby smectite composition is strongly influenced by the glass chemistry. The occurrence of poorly crystalline domains with a 0.3 to 0.4 nm layer spacing in the altered interstitial glass suggests that the transformation of glass to smectite involved the formation of a transitional alteration product. Comparison with the results of previous studies highlights the fact that the glass-to-smectite transformation can proceed through more than one reaction pathway. Reaction style and reaction progress are controlled by kinetic factors such as the mode of fluid transport triggering alteration in the low-temperature hydrothermal environment. Alteration of the trachybasalt at Conical Seamount is inferred to have taken place at a comparably low fluid-rock ratio as the low permeability and the absence of primary fractures and joints restricted fluid circulation through the coherent volcanic rocks.

Continental and marine contributions to formation of mangrove sediments in an Eastern Amazonian mudplain: The case of the Marapanim Estuary

The coastline of the state of Pará in the Eastern Amazon is formed by submerged valleys occupied partially with mangroves, such as the estuary of the Marapanim River. The sediments of these mangroves are silty-clays, composed of quartz, kaolinite, illite, smectite, K-feldspar, pyrite, hematite, jarosite and halite with accessory zircon, estaurolite, tourmaline, rarely kyanite, rutile, ilmenite, sillimanite, andaluzite, topaz and anatase. Quartz, kaolinite, hematite and most accessories like zircon, estaurolite, tourmaline, rutile, kyanite, topaz, anatase and opaque minerals are inherited from the surrounding rocks (source area). The smectite, K-feldspar, pyrite, halite and jarosite are authigenic (neoformed). Halite and jarosite are currently and locally formed by intense evaporation. The sediments are formed mainly of SiO2, Al2O3 and Fe2O3, which indicates that they were subjected to intense chemical weathering, like the sediments of the Barreiras Formation. This is reinforced by the trace elements, with concentration of residual elements Zr, Cr, V, Nb, among others, while other trace elements are impoverished. The formation of K-feldspar, illite, smectite, halite and pyrite were linked to the environment of sedimentation of the mangrove, rich in organic matter and under the influence of sea water which contributed SO42-, Cl, Na+, K+, Ca2+, and Mg2+ for the formation of these minerals. In conclusion the inherited minerals, chemical composition and concentration of residual trace elements show the Barreiras Formation to be the main source of the land-derived sediments of the Marapanim mangroves.

The temporal evolution of pedogenic Fe–smectite to Fe–kaolin via interstratified kaolin–smectite in a moist tropical soil chronosequence

Fe-rich kaolins in soils of a terrace chronosequence in the moist tropics of Costa Rica are derived from the transformation of smectite via interstratified kaolin–smectite (K–S). The smectite is ferruginous smectite (10.1 ± 3.7% Fe 2O 3) that forms early during pedogenesis from basaltic–andesitic parent material and is the dominant mineral in < 5 ka soils. Interstratified K–S with 60–90% kaolin layers is the dominant mineral in 10 ka soils, while 125 ka soils contain a physical mixture of Fe–kaolin (6.0 ± 1.9% Fe 2O 3) and K–S with > 80% kaolin layers. K–S is indicated by X-ray diffraction (XRD) data that reveal asymmetric 001 peaks between 17.5 and 17.8 Å (ethylene glycol-solvated) and irrational 00 l peaks that exhibit Méring-like behaviour, and by transmission electron microscopy–analytical electron microscopy (TEM–AEM) data that document single crystals of K–S with compositions intermediate to those of end-member crystals of smectite and kaolin. Lattice fringe images from high resolution TEM (HRTEM) show lateral transitions from smectite layers to kaolin layers via a cell-preserved, layer-by-layer transformation mechanism, and changes in the compositions of tetrahedral and octahedral sheets, notably decreases in octahedral Fe and Mg and tetrahedral Al, indicate that the reaction is accompanied by localized dissolution of smectite 2:1 layers that proceeds laterally. Fourier transform infrared (FTIR) and XRD data indicate that kaolin layers are a mixture of kaolinite and halloysite, and differential thermal analysis–thermogravimetry (DTA–TG) combined with data from XRD and TEM–AEM indicate the development of Al-hydroxy-interlayers in K–S with time. The soil-forming factors that appear to control formation of K–S are (1) basaltic–andesitic parent that produces high concentrations of base cations and Si in young (< 5 ka) soils, and (2) moist tropical climate (3085 mm MAP, 27.3 °C MAT) with a short dry season that fosters formation of smectite in < 5 ka soils. By 125 ka, soils are dominated by Fe–kaolin and K–S, helping to constrain reaction rate. The relatively high cation exchange capacity (CEC) of the Fe-rich kaolins (18 ± 12 cmol c/kg) relative to many tropical kaolinites is attributed to small amounts of octahedral Mg and tetrahedral Al inherited from precursor ferruginous smectite layers. Accordingly, the origin (from smectite) and relatively high CEC of the K–S and Fe–kaolin has potentially important implications related to clay mineral reactions and elemental cycling in moist tropical soils.

Geochemical characteristics of the alteration of volcanic and volcaniclastic rocks in the Feres Basin, Thrace, NE Greece

AbstractThe Tertiary basin of Feres consists of sedimentary rocks, andesitic-rhyolitic volcanic rocks of K-rich calc-alkaline affinities, rocks with calc-alkaline and shoshonitic affinities and volcaniclastic fall and flow deposits. Volcanic and volcaniclastic rocks have variable concentrations of LIL elements (Ba, Sr, Rb, Th) and HFS elements (Zr, V) due to their mode of origin. The pyroclastic flows frequently show more or less intense devitrification, vapour-phase crystallization and, in some cases, evidence of fumarolic activity, as is indicated by the presence of scapolite. The volcanic and volcaniclastic rocks display various types of alteration including formation of zeolites (clinoptilolite, heulandite, mordenite, and laumontite) and smectite, as well as hydrothermal alteration (development of silicic, argillic, sericitic and propylitic zones) associated with polymetallic mineralization. The behaviour of chemical elements during alteration varies. Some are immobile and their distribution is controlled by the conditions prevailing during parent-rock formation and emplacement, but others, such as Ba and Sr, are mobile and selectively fractionate in zeolite extra-framework sites. The formation of zeolite from alteration of volcanic glass is accompanied by an increase in Mg and Al content, and a decrease in Si and Na content, whereas Ca is not affected by alteration. In certain pyroclastic flows, there is a significant difference in K-content between incipient glass and altered rock, due to K-feldspar formation during devitrification and vapour-phase crystallization.

The role of climate and vegetation in weathering and clay mineral formation in late Quaternary soils of the Swiss and Italian Alps

Interactions between climate and soil remain ambiguous, particularly when silicate weathering and clay mineral formation and transformation rates are considered in relation to global climate changes. Recent studies suggest that climate affects weathering rates much less than previously thought. Here we show that the climate in the central European Alps has a significant, but indirect, influence on the weathering of soils through vegetation. The pattern of element leaching and mineral transformations is not only due to precipitation and temperature. Element leaching was greatest in subalpine forests near the timberline; weathering is lessened at higher and lower altitudes. Vegetation, therefore, contributes significantly to weathering processes. The highest accumulation of organic matter was found in climatically cooler sites (subalpine range) where the production of organic ligands, which enhance weathering, is greatest. Patterns of smectite formation and distribution had strong similarities to that of the elemental losses of Fe and Al ( R = 0.69; P < 0.01) or base cations ( R = 0.58; P < 0.05). Higher precipitation rates and the production of organic chelating compounds in the soil promoted the appearance of smectites. The relationship between climate, element leaching (Fe, Al, Ca, Mg, K, Na), and smectite formation is strongly nonlinear and driven by the podzolisation process, which is more pronounced near the timberline because of the bioclimatic constellation. Climate warming will probably, in the future, lead to a decrease in SOM stocks in the subalpine to alpine range because of more favourable conditions for biodegradation that would also affect weathering processes.

Diagenesis in Okavango fan and adjacent dune deposits with implications for the record of palaeo-environmental change in Makgadikgadi–Okavango–Zambezi basin, northern Botswana

This work considers the spatial distribution and ages of western MOZ basin siliclastic sediments prior to providing insights into the diagenesis of degraded dune and alluvial fan sands. Previously published and new TL/OSL ages imply that extensive over-washing of dune sands took place at least 100 ka ago while ages on Okavango floodplains imply that the fan was formed ca. 40 ka and has since undergone periods of higher and lower flood regimes. Sediment analyses indicate that both dune and fan sands contain a diagenetic matrix of clay-enhanced amorphous silica (CEAS) which bonds weakly formed aggregates. The time of formation of diagenetic matrix products is inconclusive but may have been accelerated during or shortly after events dated using OSL/TL techniques. Hence earlier dune over-washing may have led to greater porewater of an acidic to near neutral nature which in turn promoted smectite formation and silicic acid precipitation > 100 000 years ago. The relatively abundant CEAS matrix in floodplain sands implies more recent semi-continuous flood events again of an acidic-near neutral nature leading to the formation of smectite. In this case the floodplain sediments are dated as having been deposited around 40 and 11 ka, when porewater content may have accelerated clay formation and silica dissolution. The dual nature of the CEAS in the islands reflects a changing environment from smectite-dominated flooding events to sepiolite-dominated desiccation events. Flooding may also correspond to TL/OSL ages over the past 40 000 years which contributed to accelerated CEAS formation. The sepiolite is associated with a Ca-rich matrix implying desiccation which may relate to drying events over the 40 000 year period or to riparian tree root pumping and selective salt accumulation. This work shows that sedimentation in incipient rifts is complex and rarely explained totally in terms of primary depositional events. The implications of different stages of sand diagenesis may be significant in enhancing palaeo-environmental interpretations in semi-arid fluvial environments.

Geochemical records of a bentonitic acid-tuff succession related to a transgressive systems tract — Indication of changes in the volcanic sedimentation rate

AbstractA detailed stratigraphic and facies reconstruction of a bentonitized acid-tuff succession, deposited within the transgressive systems tract of the Upper Miocene-Sarmatian Ser-3 eustatic cycle, at Sajóbábony, northern Hungary, was performed via petrographic, mineralogical and geochemical analyses. The purpose of the work was to analyze the degree of alteration of the volcanogenic sediments, as an indicator of the relative volcanic sedimentation rate. This may have an important role in indicating volcanic periods synchronous with sedimentation or reconstructing the volcanosedimentary paleoconditions. Sample pairs were collected from each bentonite and tuff layer, and, to facilitiate microstratigraphic relations, samples were collected every 10 cm within bentonite layers. Mineralogical analyses were performed by X-ray diffraction and geochemical analyses by inductively coupled plasma-mass spectroscopy.The CaO/K2O and Eu/La ratios correlate with each other and with a montmorillonite/X-ray-amorphous phase ratio, reflecting Ca and Eu incorporation associated with devitrification and smectite formation. In accordance with the current literature, these mineralogical and geochemical proxies can be related primarily to the weathering processes. Considering vertical distributions in a sequence-stratigraphic context, the Ca content and Eu/La values show that local peaks and Eu anomalies characteristic of acid tuffs show minima at flooding surfaces (FS). Within a bentonite layer, representing a single transgressive period, the repeated events of dust-tuff accumulations have been determined by K2O/CaO and La/Eu peaks, confirmed also by the Eu anomalies in the rare earth element (REE) patterns, thus leading to the conclusion that the level of alteration is closely correlated with the elimination of terrigenous input and a minimum in volcanic sedimentation rate allowing more intensive alteration of the deposited volcanic material. In the case of fine tuff beds, Eu anomalies on REE patterns reflect limited alteration at the bottom and more intensive alteration in the upper parts of the beds, reflecting the effect of infiltration of sea water into the pores.

Clay mineral formation during podzolization in an alpine environment of the Tatra Mountains, Poland

AbstractThe processes of clay mineral formation were studied in seven podzol profiles developed on granitic regoliths in the Polish part of the Tatra Mountains. The selected profiles have similar parent material and macroscopically represent different stages of soil development (from initial to advanced). Bulk soil material (&lt;2 mm fraction) and separated clay fractions (&lt;2 µm) were studied using a petrographic microscope, X-ray diffraction, Fourier transform infrared spectroscopy, and scanning electron microscopy-energy-dispersive spectrometry methods. The mineral compositions of the bulk soil samples are more or less the same (quartz, feldspars, mica and minor amounts of other phyllosilicates). The clay fractions are composed of mica and mixed-layer minerals which contain hydrated interlayers of vermiculitic and/or smectitic type, and kaolinite. Smaller amounts of chlorite, feldspars and quartz were also identified. Chlorite is present almost exclusively (except for one profile) in lower soil horizons (C, B/C, B). The amount of minerals with hydrated interlayers increases up the profiles. Kaolinite is present in all the samples except for the lowermost soil horizons (C) of two of the profiles. In some of the B horizons, the formation of hydroxy interlayers within hydrated interlayers is observed. The main processes of clay mineral formation recognized in the soils studied are: inheritance from the parent rocks; crystallization of kaolinite from soil solutions; the formation of dioctahedral vermiculite at the expense of inherited dioctahedral mica, and the formation of dioctahedral smectite at the expense of vermiculite. The recognized sequence of transformation is as follows: M → R0 M-V (12 Å or 14 Å) → R0 M-12 Å V → R1 M-12 Å V → 12 Å V → V-S → S. Observed formation of hydroxy interlayers seems to be pH dependent, starting when the pH ⩾ 4.4. The process of dissolution of primary silicates occurring simultaneously with the transformation is also documented.

Pedogenic formation of smectites in a vertisol developed from granitic rock from Kaélé (Cameroon, Central Africa)

AbstractSmectite formation in a vertisol developed from a granitic parent rock in the Kaélé region of Cameroon in a tropical, dry climate was studied by means of X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), chemical analyses, cation exchange capacity (CEC) and low temperature gas adsorption. The soil profile comprises three horizons (from base to top): (1) a saprolite, (2) an intermediate horizon, and (3) an upper dark grey horizon. In the saprolite, the progressive alteration of feldspars gave rise to the exclusive neoformation of beidellite exhibiting a typical honeycomb fabric. This process resulted in Al, Fe, Ca, Mg, Ti and Mn enrichment, a depletion of Si and Na and a significant negative Eu anomaly. In the upper horizons, beidellite evolves and is transformed into montmorillonite and kaolinite, probably through a series of smectite-kaolinite mixed layers. This transformation, from the saprolite to the upper horizons, causes the observed decrease in the CEC and the increase in specific surface area and mesoporosity of the clay. The REE patterns of the bulk soil and clay fraction display similar behaviour, indicating that the three horizons, and hence the clay minerals, have a common source in the underlying granite. Mass-balance calculations show that the intense weathering of the granite leads to a mass reduction of ~80–90%.

Quantifying Li isotope fractionation during smectite formation and implications for the Li cycle

Tri-octahedral Li–Mg smectites (hectorites) were synthesized at temperatures ranging from 25 to 250 °C, in the presence of solutions highly enriched in lithium. After removing all the exchangeable lithium from the synthesized clays, Li isotope fractionation (Δ 7Li clay-solution) was determined. This fractionation was linked to Li incorporation into the structural octahedral site, substituting for Mg 2+. As predicted, experimental Δ 7Li clay-solution inversely correlates with temperature, and ranges from −1.6‰ ± 1.3‰ at 250 °C to −10.0‰ ± 1.3‰ at 90 °C, and then stays relatively constant down to 25 °C. The relatively constant isotope fractionation factor below 90 °C may be due to high concentrations of edge octahedra in low crystallinity smectites. The isotopic fractionation factor ( α), for a given temperature, does not depend on the solution matrix, nor on the amount of structural Li incorporated into the clay. Empirical linear laws for α as a function of 1/ T (K) were inferred. Smectite Li contents and smectite-solution distribution coefficients ( D Li/Mg) increase with temperature, as expected for a substitution process. The fractions of dissolved Li incorporated into the smectite octahedral sites are small and do not depend on the duration of the experiment. In a seawater-like matrix solution, less Li is incorporated into the smectites, probably as a result of competition with dissolved Mg 2+ ions for incorporation into the octahedral sites. The high Li contents observed in marine smectites are therefore best explained either by a significant contribution from basalts, by adsorption processes, or by the influence of seawater chemical composition on distribution coefficients. We also calculate, using present-day estimates of hydrothermal water and river fluxes, that a steady-state ocean would require a relatively large global clay-water Li isotope fractionation (−12‰ to −21‰). This study demonstrates the ability of laboratory experiments to quantify the impact of secondary phases on the Li geochemical cycle and associated isotope fractionations.

Effect of exchangeable cations on the physicochemical properties of smectite

The effect of exchange cations (Mn+: Li+, Na+, K+, NH4+, Ca2+, Mg2+, Fe3+, and Al3+) and thermal treatment on the physicochemical properties of smectite was investigated. Before thermal treatment, unheated (25°C) Mn+-smectite showed increased d001 spacing upon glycol solvation; after heating at 300°C or above (400°C), d001 spacing upon glycol solvation of Al-, Fe-, Mg-, Li-smectite decreased and reached 10 A. However, an increase in d001 of Ca2+-, Na+-and NH4+-smectite upon glycol solvation indicated that d001 varied with the nature of exchangeable cation and the temperature of heating. The results generally suggested the following: d001 of homoionic smectite before and after heating at various temperatures depended upon the nature of exchangeable cation. The cation exchangeable capacities (CECs) and the BET surface areas (SBETs) were functions of the type of exchangeable cations, since SBETs drop off in the following order: Na+-smect > Ca2+-smect > Mg2+-smect > NH4+-smect > Li+-smect > K+-smect > Fe3+-smect > Al3+-smect. Finally, we have noted good progress in the exchangeable properties of synthesized clay in comparison with the Na homoionic smectite form, except for K homoionic clay, which have the lowest CECs, SBETs, and consequently, the lowest exchangeable properties.

Role of smectite in siliceous-sinter formation and microbial-texture preservation: Octopus Spring, Yellowstone National Park, Wyoming, USA

AbstractA siliceous sinter collected from Octopus Spring in Yellowstone National Park, USA contains an occluded volcanic rock fragment that has undergone alteration. The sinter piece beyond the fragment is mostly dominated by opal-A with trace amounts of bacterial cells, calcite and detrital quartz. Within the altered rock region, the mineral assemblage is dominated by dioctahedral smectite and quartz with trace amounts of pseudobrookite, ilmenite, rutile and hematite. Onset of opal-CT formation was only found in the outer spicular region of the sinter, which is unexpected given that this outer part represents newest growth. A reaction mechanism is proposed whereby the alteration of feldspar to smectitic clay locally produces excess silica, and alkali metal, and raises pH. As the clay mineral forms, it sequesters ions from pore fluids thereby inhibiting the opal-A phase change to more ordered opal-CT. Ions such as Mg are known to promote the opal-A to opal-CT reaction. Smectite formation therefore may assist microbial-texture preservation processes as excess silica produced increases the rate at which primary opal-A is formed. The altered zone also retains the greatest amount of fixed C and fixed N (operationally defined as C and N retained upon combustion at 450°C). The fixed N probably represents ammonium trapped in the exchangeable interlayer site of the smectite. This fixed N may serve as a potential biological signature of microbial activity in ancient rocks formed in similar environments.