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Structural charge site influence on the interlayer hydration of expandable three-sheet clay minerals

Previous investigations have demonstrated the influences of interlayer cation composition, relative humidity, temperature, and magnitude of interlayer surface charge on the interlayer hydration of montmorillonites and vermiculites. It has been suggested that the sites of layer charge deficiencies may also have an influence upon the amount of hydration that can take place in the interlayers of expandable clay minerals. If the interlayer cation-to-layer bonds are considered as ideally electrostatic, the magnitude of the forces resisting expansion may be expressed as a form of Coulomb's law. If this effect is significant, expandable structures in which the charge-deficiency sites are predominantly in the tetrahedral sheet should have less pronounced swelling properties than should structures possessing charge deficiencies located primarily in the octahedral sheet. Three samples that differed in location of layer charge sites were selected for study. An important selection criterion was a non-correlation between tetrahedral charge sites and high surface-charge density, and between octahedral charge sites and low surface-charge density. The effects of differences in interlayer cation composition were eliminated by saturating portions of each sample with the same cations. Equilibrium (001) d values at controlled constant humidities were used as a measure of the relative degree of interlayer hydration. Although no correlation could be made between the degree of interlayer hydration and total surface-charge density, the investigation does not eliminate total surface-charge density as being significant to the swelling properties of three-sheet clay-mineral structures. The results do indicate a correlation between more intense expandability and predominance of charge deficiencies in the octahedral sheet. Conversely, less intense swelling behavior is associated with predominantly tetrahedral charge deficiencies.

Clays and Clay Minerals

Analysis of mixed-layer clay mineral structures

Among the enormously abundant natural occurrences of clay minerals, many examples are encountered in which no single specific crystallization scheme extends through a single ultimate grain. The characterization of such assemblages becomes an analysis of the distribution of matter within such grains, rather than the simple identification of mineral species. It having become established that the particular coordination complex typified by mica is a common component of many natural subcrystalline assemblages, the opportunity is afforded to analyze scattering from random associations of these complexes with other structural units. Successful analyses have been made of mixed hydration states of montmorillonite, of montmorillonite with mica, of vermiculite with mica, and of montmorillonite with chlorite, all of which are variants of the mica complex, and of halloysite with hydrated halloysite.

Conference Paper

Scanning electron microscopy of clays and clay minerals

The scanning electron microscope (SEM) proves to be ideally suited for studying the configuration, texture, and fabric of clay samples. Growth mechanics of crystalline units—interpenetration and interlocking of crystallites, crystal habits, twinning, helical growth, and topotaxis—also are uniquely revealed by the SEM. Authigenic kaolins make up the bulk of the examples because their larger crystallite size, better crystallinity, and open texture make them more suited to examination by the SEM than most other clay mineral types.

Clays and Clay Minerals

Stratigraphic and climatic implications of clay mineral changes around the Paleocene/Eocene boundary of the northeastern US margin

Kaolinite usually is present in relatively small amounts in most upper Paleocene and lower Eocene neritic deposits of the northern US Atlantic Coastal Plain. However, there is a short period (less than 200,000 k.y.) in the latest Paleocene (upper part of calcareous nannoplankton Zone NP 9) when kaolinite-dominated clay mineral suites replaced the usual illite/smectite-dominated suites. During this time of global biotic and lithologic changes, kaolinite increased from less than 5% of the clay mineral suite to peak proportions of 50-60% of the suite and then returned to less than 5% in uppermost Paleocene/lowermost Eocene strata. This kaolinite pulse is present at numerous localities from southern Virginia to New Jersey. These sites represent both inner and middle neritic depositional environments and reflect input from several river drainage systems. Thus, it is inferred that kaolinite-rich source areas were widespread in the northeastern US during the latest Paleocene. Erosion of these source areas contributed the kaolinite that was transported and widely dispersed into shelf environments of the Salisbury embayment. The kaolinite increase, which occurred during a time of relatively high sea level, probably is the result of intensified weathering due to increased temperature and precipitation. The southern extent of the kaolinite pulse is uncertain in that uppermost Paleocene beds have not been identified in the southern Atlantic Coastal Plain. The late Paleocene kaolinite pulse that consists of an increase to peak kaolinite levels followed by a decrease can be used for detailed correlation between more upbasin and more downbasin sections in the Salisbury embayment. Correlations show that more upbasin Paleocene/Eocene boundary sections are erosionally truncated. They have varying portions of the kaolinite increase and, if present at all, discontinuous portions of the subsequent kaolinite decrease. As these truncated sections are disconformably overlain by lower Eocene strata, rapid erosional removal of large parts of the most kaolinite-rich P/E boundary clay deposits occurred by early Eocene time. Erosion of the kaolinite-rich P/E boundary beds was enhanced during times of sea-level fall when kaolinite-rich sediments were redeposited to produce kaolinite spikes in basal beds of lower and middle Eocene sequences that have little or no kaolinite elsewhere in the sequence. In contrast, more downbasin sites document only the upper, decreasing part of the kaolinite pulse. The absence of strata documenting the earlier kaolinite increase is attributed to slow sedimentation (condensed interval) as a result of a significant sea level rise that ponded most sediments in shallower waters, combined with the probable subsequent erosional removal of these thin downbasin deposits by oceanic currents.

Sedimentary Geology

The distribution of clay minerals and their impact on diagenesis in Glen Torridon, Gale crater, Mars

Glen Torridon (GT) is a recessive-trough feature on the northwestern slope of “Mt. Sharp” in Gale crater, Mars with the highest Fe-/Mg-phyllosilicates abundances detected by the Curiosity rover to date. Understanding the origin of these clay minerals and their relationship with diagenetic processes is critical for reconstructing the nature and habitability of past surface and subsurface environments in Gale crater. We aim to constrain the distribution and extent of diagenesis using compositional and morphological trends observed by visible-to-near infrared reflectance spectra in GT from Mastcam and ChemCam, supported by high-resolution images from the Mars Hand Lens Imager. Spectral features consistent with nontronite and fine-grained red hematite are ubiquitous throughout lower GT, and are strongest where diagenetic features are limited, suggesting that both were formed early, before burial. Diagenetic features increase in both abundance and diversity farther up-section, and we observe morphologic evidence for multiple episodes of diagenesis, with the edge of a diagenetic front partially preserved in the middle stratigraphic member, Knockfarril Hill. Near the contact between GT and the overlying Greenheugh pediment capping unit, we observe a lack of clay minerals with signatures consistent instead with coarse-grained gray hematite, likely formed through late-diagenetic alteration. We hypothesize that the sandstone-dominant Stimson formation acted as a conduit for diagenetic fluid flow into the area and that the clay-rich impermeable GT slowed the flow of those fluids, leading to enhanced alteration surrounding the clay-rich portions of GT, including within the nearby Vera Rubin ridge.

JGR Planets

Hydrogen and oxygen isotope exchange reactions between clay minerals and water

The extent of hydrogen and oxygen isotope exchange between clay minerals and water has been measured in the temperature range 100–350° for bomb runs of up to almost 2 years. Hydrogen isotope exchange between water and the clays was demonstrable at 100°. Exchange rates were 3–5 times greater for montmorillonite than for kaolinite or illite and this is attributed to the presence of interlayer water in the montmorillonite structure. Negligible oxygen isotope exchange occurred at these low temperatures. The great disparity in D and O 18 exchange rates observed in every experiment demonstrates that hydrogen isotope exchange occurred by a mechanism of proton exchange independent of the slower process of O 18 exchange. At 350° kaolinite reacted to form pyrophyllite and diaspore. This was accompanied by essentially complete D exchange but minor O 18 exchange and implies that intact structural units in the pyrophyllite were inherited from the kaolinite precursor.

Geochimica et Cosmochimica Acta

Clay mineral content of continental shelf and river sediments, southern California

This report contains data on the clay mineral content of 250 shelf surface-sediment samples from the California Continental Borderland (Tables 1, 2; Figures 1-7), 79 samples with depth in cores from Santa Monica Bay (Table 3; see Table 1 for surface sediment data for those same cores and for core locations), 24 suspended and 13 bottom sediment samples from rivers draining Southern California (Table 4), and six rock samples or composite rock samples from the Palos Verdes Headland (Table 4). This report is designed as the data repository and these data are discussed in a paper by Hein et al. (2001).

California

A recommended procedure for the preparation of oriented clay-mineral specimens for X-ray diffraction analysis; modifications to Drever's filter-membrane peel technique

Extremely well-oriented clay mineral mounts for X-ray diffraction analysis can be prepared quickly and without introducing segregation using the filter-membrane peel technique. Mounting problems encountered with smectite-rich samples can be resolved by using minimal sample and partial air-drying of the clay film before transfer to a glass slide. Samples containing small quantities of clay can produce useful oriented specimens if Teflon masks having more restrictive areas are inserted above the membrane filter during clay deposition. War]page and thermal shock of glass slides can be controlled by using a flat, porous, ceramic plate as a holding surface during heat treatments.

Open-File Report

Tetraphenylborate-assisted extraction of K and Ar from micaceous clay minerals: A promising method for the geochronology of diagenetic illite

Tetraphenylborate (TPB)-assisted exchange of Na + for structural K was explored to establish the extent to which K and radiogenic Ar were removed from mixed-layer illite-smectite (Ilt-Sme) and detrital muscovite in various clay fractions (<1, 1–2 and 2–5 µm) of three Illinois Basin palaeosols and of Ilt-Sme from a K-bentonite (<2 µm) clay. The K–Ar age value of the treated Ilt-Sme was virtually the same as that of the untreated material regardless of TPB exchange duration in the K-bentonite. Interlayer K is extracted quickly but not completely from fine illitic material. Interlayer K is extracted more slowly but more completely from coarser clay-sized muscovite based on changes in X-ray diffraction traces, K contents and K–Ar age values of the palaeosol size fractions upon TPB treatment. One hour of TPB treatment revealed that (1) detrital Ilt-Sme was predominant over diagenetic Ilt-Sme in one palaeosol and (2) relatively more of the K in R0 Ilt-Sme is resistant to TPB treatment than in illite-rich, ordered Ilt-Sme, which indicates that the single illite layers hold K + against TPB exchange in the fine Ilt-Sme. The age values of all palaeosol size fractions treated for several weeks converged into a narrow range (mean value 247 ± 5 Myr), consistent with the remaining K and Ar being predominantly in illitic interlayers of diagenetic origin. TPB treatment is a promising technique to isolate diagenetic (or pedogenic) illite in clay fractions containing detrital components for K–Ar age determinations.

Clay Minerals

Origin of two clay-mineral facies of the Potomac Group (Cretaceous) in the Middle Atlantic States

Sedimentary clay that crops out in the coastal plains of New Jersey, Delaware, the part of Maryland north and east of Washington, B.C., and the northeast half of Washington, D.C., in the nonmarine Cretaceous Potomac Group is predominantly kaolinite and illite. In contrast, in part of southeastern Maryland, the southwest half of Washington, D.C., and most of eastern Virginia, Potomac Group clay is predominantly montmorillonite. Kaolinite and illite were probably derived by intense acid weathering of metamorphic and granitic rocks to the west during the Cretaceous and were deposited in a well-drained basin. Montmorillonite was most likely produced by deep weathering of a mainly granitic source. Poor drainage and alkaline surface- and ground-water conditions probably accompanied the production, transportation, deposition, and burial of the montmorillonite. Kaolinization of the montmorillonite is taking place now at the surface in northern Virginia.

Delaware, Maryland, New Jersey, Pennsylvania, Virg

Adsorption of bacteriophages on clay minerals

The ability to predict the fate of microorganisms in soil is dependent on an understanding of the process of their sorption on soil and subsurface materials. Presently, we have focused on studying the thermodynamics of sorption of bacteriophages (T-2, MS-2, and φX-174) on clays (hectorite, saponite, kaolinite, and clay fraction of samples collected from a landfill site). The thermodynamic study not only determines the feasibility of the process but also provides information on the relative magnitudes of the different forces under a particular set of conditions. The total free energy of interaction during sorption of bacteriophages on clays (Δ G ) has been assumed to be the summation of Δ G H (Δ G due to hydrophobic interactions) and Δ G EL (Δ G due to electrostatic interactions). The magnitude of Δ G H was determined from the different interfacial tensions (γ) present in the system, while Δ G EL was calculated from ζ-potentials of the colloidal particles. Calculated results show that surface hydrophobicities of the selected sorbents and sorbates dictate sorption. Among the selected bacteriophages, maximum sorption was observed with T-2, while hectorite has the maximum sorption capacity. Experimental results obtained from the batch adsorption studies also corroborated those obtained from the theoretical study.

Environmental Science & Technology

Geochemical studies of clay minerals III. The determination of free silica and free alumina in montmorillonites

Determination of free silica by the method proposed made possible the derivation of logical formulas for several specimens of montmorillonites for which the formulas could not be derived from the analyses alone. Other montmorillonites, for which logical formulas could be derived from their analyses, were found to contain small amounts of free silica or free alumina. Others were found to contain neither free silica nor free alumina. The method consists of the following steps: (1) digestion of 1 g of the specimen with 0.5 N NaOH solution in a covered platinum crucible or dish on a steam bath for 4 hrs, stirring the mixture at 30-min intervals, (2) filtration of the undissolved material, followed by washing several times with 1% NaOH solution, (3) neutralization of the filtrate with HCl, addition of 5 ml HCl in excess and determination of SiO and Al 2 O 3 in the usual way and (4) calculation of the amount of free SiO 2 or free Al 2 O 3 if any and the amount of attack of the clay structure by the treatment from the ratio of SiO 2 to Al 2 O 3 dissolved and the ratio of SiO 2 to Al 2 O 3 obtained on analysis. Tests with 5% Na 2 CO 3 solution, the reagent formerly used for the solution of free SiO 2 in rocks and minerals, showed that solution of opal by this reagent is always fractional, never complete, no matter how small the amount present or how long the period of treatment. Re-treatment of the sample results in 90–95% solution if 10 mg or less of opal is present, but for larger amounts of opal the percentage dissolved decreases as the amount present increases. On the other hand, 75 ml of 0.5 N NaOH completely dissolves as much as 400 mg of opal in 4 hrs digestion in a covered platinum crucible or dish, on a steam bath. However, a weaker solution or a shorter period of digestion does not effect complete solution. The same amount (75 ml) of 0.5 N NaOH also dissolves 90 mg of cristobalite and 57 mg of quartz having a grain size of less than 2 microns. Use of NaOH also permits determination of the amount of alumina dissolved, and estimation of the extent to which the clay structure was attacked by the treatment.

Geochimica et Cosmochimica Acta

Relationship of clay-mineral diagenesis to temperature, age, and hydrocarbon generation&ndash;an example from the Anadarko Basin, Oklahoma

Randomly interstratified illite/smectite (I/S) is present in Springeran and Morrowan rocks (Late Mississippian and Early Pennsylvanian) of the Anadarko basin, Oklahoma, at present-day depths <2,750 m, but disappears at depths of 2,750-3,050 m. Only ordered I/S is found in samples below 3,050 m. The work reported here relates the diagenesis of I/S to burial history and oil generation in the Anadarko basin and tests the dependence of the smectite-to-illite reaction on temperature and time. Published temperature models of clay diagenesis suggest that, for Tertiary and Cretaceous rocks, the transition from randomly interstratified I/S to ordered I/S occurs at 100-110°C. Burial reconstructions for the Anadarko basin indicate that maximum temperatures of 100-110°C correspond to present-day burial depths between 2,700 and 3,100 m. These independently calculated depths for the 100-110°C isotherm match the depths at which randomly interstratified I/S is observed to disappear in Morrowan-Springeran rocks. Thus, random I/S disappears at the same temperature in rocks that differ in age by some 300 m.y. Although the extent of the smectite-to-illite reaction is controlled by kinetics, and effects of time are apparent in laboratory experiments and short-lived geologic systems, the results of this study suggest that time plays a secondary role in long-term diagenetic settings.

Oklahoma

Leaching of clay minerals in a limestone environment

Water saturated with CO 2 at about 25°C was percolated through mixed beds of limestone or marble fragments and montmorillonite, “illite” and kaolinite in polyethylene tubes for six and fortyfive complete runs. The leachates were analysed for SiO 2 , A1 2 O 3 and Fe 2 O 3 , but only SiO 2 was found. The minerals lost SiO 2 in this order: montmorillonite > kaolinite > “illite”. The differential removal of SiO 2 during the short period of these experiments suggests a mechanism for the accumulation of bauxite deposits associated with limestones.

Geochimica et Cosmochimica Acta

Brine-driven destruction of clay minerals in Gale crater, Mars

Mars’ sedimentary rock record preserves information on geological (and potential astrobiological) processes that occurred on the planet billions of years ago. The Curiosity rover is exploring the lower reaches of Mount Sharp, in Gale crater on Mars. A traverse from Vera Rubin ridge to Glen Torridon has allowed Curiosity to examine a lateral transect of rock strata laid down in a martian lake ~3.5 billion years ago. We report spatial differences in the mineralogy of time-equivalent sedimentary rocks <400 meters apart. These differences indicate localized infiltration of silica-poor brines, generated during deposition of overlying magnesium sulfate–bearing strata. We propose that destabilization of silicate minerals driven by silica-poor brines (rarely observed on Earth) was widespread on ancient Mars, because sulfate deposits are globally distributed.

Science