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Evidence for low-grade metamorphism, hydrothermal alteration, and diagenesis on Mars from phyllosilicate mineral assemblages

The enhanced spatial and spectral resolution provided by the Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) on the Mars Reconnaissance Orbiter (MRO) has led to the discovery of numerous hydrated silicate minerals on Mars, particularly in the ancient, cratered crust comprising the southern highlands. Phases recently identified using visible/near-infrared spectra include: smectite, chlorite, prehnite, high-charge phyllosilicates (illite or muscovite), the zeolite analcime, opaline silica, and serpentine. Some mineral assemblages represent the products of aqueous alteration at elevated temperatures. Geologic occurrences of these mineral assemblages are described using examples from west of the Isidis basin near the Nili Fossae and with reference to differences in implied temperature, fluid composition, and starting materials during alteration. The alteration minerals are not distributed homogeneously. Rather, certain craters host distinctive alteration assemblages: (1) prehnite-chlorite-silica, (2) analcime-silica-Fe,Mg-smectite-chlorite, (3) chlorite-illite (muscovite), and (4) serpentine, which furthermore has been found in bedrock units. These assemblages contrast with the prevalence of solely Fe,Mg-smectites in most phyllosilicate-bearing terrains on Mars, and they represent materials altered at depth then exposed by cratering. Of the minerals found to date, prehnite provides the clearest evidence for subsurface, hydrothermal/metamorphic alteration, as it forms only under highly restricted conditions ( T = 200–400ºC). Multiple mechanisms exist for forming the other individual minerals; however, the most likely formation mechanisms for the characteristic mineralogic assemblages observed are, for (1) and (2), low-grade metamorphism or hydrothermal (<400ºC) circulation of fluids in basalt; for (3), transformation of trioctahedral smectites to chlorite and dioctahedral smectites to illite during diagenesis; and for (4), low-grade metamorphism or hydrothermal (<400ºC) circulation of fluids in ultramafic rocks. Evidence for high-grade metamorphism at elevated pressures or temperatures >400ºC has not been found.

Clays and Clay Minerals

Measurement of illite particle thickness using a direct Fourier transform of small-angle X-ray scattering data

It has been suggested that interstratified illite-smectite (I-S) minerals are composed of aggregates of fundamental particles. Many attempts have been made to measure the thickness of such fundamental particles, but each of the methods used suffers from its own limitations and uncertainties. Small-angle X-ray scattering (SAXS) can be used to measure the thickness of particles that scatter X-rays coherently. We used SAXS to study suspensions of Na-rectorite and other illites with varying proportions of smectite. The scattering intensity ( I ) was recorded as a function of the scattering vector, q = (4 /) sin(/2), where  is the X-ray wavelength and  is the scattering angle. The experimental data were treated with a direct Fourier transform to obtain the pair distance distribution function (PDDF) that was then used to determine the thickness of illite particles. The Guinier and Porod extrapolations were used to obtain the scattering intensity beyond the experimental q , and the effects of such extrapolations on the PDDF were examined. The thickness of independent rectorite particles (used as a reference mineral) is 18.3 Å. The SAXS results are compared with those obtained by X-ray diffraction peak broadening methods. It was found that the power-law exponent (α) obtained by fitting the data in the region of q = 0.1-0.6 nm -1 to the power law ( I = I 0 q -α ) is a linear function of illite particle thickness. Therefore, illite particle thickness could be predicted by the linear relationship as long as the thickness is within the limit where α <4.0.

Clays and Clay Minerals

Surface area of vermiculite with nitrogen and carbon dioxide as adsorbates

Surface-area studies were made on several homoionic vermiculites with both nitrogen and carbon dioxide as adsorbates. These studies show that only very slight penetration occurs between individual vermiculite platelets. This is in contrast to an earlier investigation of montmorillonite where it was found that the degree of penetration between layers is quite high, particularly for carbon dioxide, and is governed by the size and charge of the interlayer cation. The inability of these adsorbates to penetrate substantially between vermiculite platelets is due primarily to this mineral's high surface-charge density. The extent of penetration of nitrogen and carbon dioxide at the edges of vermiculite platelets, though slight, is influenced by the coordinated water retained within the sample at a given degassing temperature. Forces between layers are weakened with increasing water content, which permits slightly greater penetration by adsorbate gases. Thus, the surface area of vermiculite, as determined by gas adsorption, is larger than the calculated external surface area based upon particle size and shape considerations. In addition, "extra" surface is provided by the lifting and scrolling of terminal platelets. These morphological features are shown in scanning electron micrographs of a naturally occuring vermiculite.

Clays and Clay Minerals

The formation of illite from nontronite by mesophilic and thermophilic bacterial reaction

The formation of illite through the smectite-to-illite (S-I) reaction is considered to be one of the most important mineral reactions occurring during diagenesis. In biologically catalyzed systems, however, this transformation has been suggested to be rapid and to bypass the high temperature and long time requirements. To understand the factors that promote the S-I reaction, the present study focused on the effects of pH, temperature, solution chemistry, and aging on the S-I reaction in microbially mediated systems. Fe(III)-reduction experiments were performed in both growth and non-growth media with two types of bacteria: mesophilic ( Shewanella putrefaciens CN32) and thermophilic ( Thermus scotoductus SA-01). Reductive dissolution of NAu-2 was observed and the formation of illite in treatment with thermophilic SA-01 was indicated by X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). A basic pH (8.4) and high temperature (65°C) were the most favorable conditions for the formation of illite. A long incubation time was also found to enhance the formation of illite. K-nontronite (non-permanent fixation of K) was also detected and differentiated from the discrete illite in the XRD profiles. These results collectively suggested that the formation of illite associated with the biologically catalyzed smectite-to-illite reaction pathway may bypass the prolonged time and high temperature required for the S-I reaction in the absence of microbial activity.

Clays and Clay Minerals

XRD measurement of mean thickness, thickness distribution and strain for illite and illite-smectite crystallites by the Bertaut-Warren-Averbach technique

A modified version of the Bertaut-Warren-Averbach (BWA) technique (Bertaut 1949, 1950; Warren and Averbach 1950) has been developed to measure coherent scattering domain (CSD) sizes and strains in minerals by analysis of X-ray diffraction (XRD) data. This method is used to measure CSD thickness distributions for calculated and experimental XRD patterns of illites and illite-smectites (I-S). The method almost exactly recovers CSD thickness distributions for calculated illite XRD patterns. Natural I-S samples contain swelling layers that lead to nonperiodic structures in the c * direction and to XRD peaks that are broadened and made asymmetric by mixed layering. Therefore, these peaks cannot be analyzed by the BWA method. These difficulties are overcome by K-saturation and heating prior to X-ray analysis in order to form 10-Å periodic structures. BWA analysis yields the thickness distribution of mixed-layer crystals (coherently diffracting stacks of fundamental illite particles). For most I-S samples, CSD thickness distributions can be approximated by lognormal functions. Mixed-layer crystal mean thickness and expandability then can be used to calculate fundamental illite particle mean thickness. Analyses of the dehydrated, K-saturated samples indicate that basal XRD reflections are broadened by symmetrical strain that may be related to local variations in smectite interlayers caused by dehydration, and that the standard deviation of the strain increases regularly with expandability. The 001 and 002 reflections are affected only slightly by this strain and therefore are suited for CSD thickness analysis. Mean mixed-layer crystal thicknesses for dehydrated I-S measured by the BWA method are very close to those measured by an integral peak width method.

Clays and Clay Minerals

The Curiosity Rover’s exploration of Glen Torridon, Gale crater, Mars: An overview of the campaign and scientific results

The Mars Science Laboratory rover, Curiosity , explored the clay mineral-bearing Glen Torridon region for one martian year between January 2019 and January 2021, including a short campaign onto the Greenheugh pediment. The Glen Torridon campaign sought to characterize the geology of the area, seek evidence of habitable environments, and document the onset of a potentially global climatic transition during the Hesperian era. Curiosity roved 5 km in total throughout Glen Torridon, from the Vera Rubin ridge to the northern margin of the Greenheugh pediment. Curiosity acquired samples from 11 drill holes during this campaign and conducted the first martian thermochemolytic-based organics detection experiment with the Sample Analysis at Mars instrument suite. The lowest elevations within Glen Torridon represent a continuation of lacustrine Murray formation deposits, but overlying widespread cross bedded sandstones indicate an interval of more energetic fluvial environments and prompted the definition of a new stratigraphic formation in the Mount Sharp group called the Carolyn Shoemaker formation. Glen Torridon hosts abundant phyllosilicates yet remains compositionally and mineralogically comparable to the rest of the Mount Sharp group. Glen Torridon samples have a great diversity and abundance of sulfur-bearing organic molecules, which are consistent with the presence of ancient refractory organic matter. The Glen Torridon region experienced heterogeneous diagenesis, with the most striking alteration occurring just below the Siccar Point unconformity at the Greenheugh pediment. Results from the pediment campaign show that the capping sandstone formed within the Stimson Hesperian aeolian sand sea that experienced seasonal variations in wind direction.

JGR Planets

Physicochemical properties and bioreactivity of sub-10 µm geogenic particles: Comparison of volcanic ash and desert dust

Exposure to ambient particulate matter (PM) with an aerodynamic diameter of <10 μm (PM 10 ) is a well-established health hazard. There is increasing evidence that geogenic (Earth-derived) particles can induce adverse biological effects upon inhalation, though there is high variability in particle bioreactivity that is associated with particle source and physicochemical properties. In this study, we investigated physicochemical properties and biological reactivity of volcanic ash from the April 2021 eruption of La Soufrière volcano, St. Vincent, and two desert dust samples: a standardized test dust from Arizona and an aeolian Gobi Desert dust sampled in China. We determined particle size, morphology, mineralogy, surface texture and chemistry in sub-10 μm material to investigate associations between particle physicochemical properties and observed bioreactivity. We assessed cellular responses (cytotoxic and pro-inflammatory effects) to acute particle exposures (24 hr) in monocultures at the air-liquid interface using two types of cells of the human airways: BEAS-2B bronchial epithelial cells and A549 alveolar type II epithelial cells. In acellular assays, we also assessed particle oxidative potential and the presence of microorganisms. The results showed that volcanic ash and desert dust exhibit intrinsically different particle morphology, surface textures and chemistry, and variable mineralogical content. We found that Gobi Desert dust is more bioreactive than freshly erupted volcanic ash and Arizona test dust, which is possibly linked to the presence of microorganisms (bacteria) and/or nanoscale elongated silicate minerals (potentially clay such as illite or vermiculite) on particle surfaces.

GeoHealth

Beyond the Kubler index

The value of peak width at half-height for the illite 001 XRD reflection is known as the Kubler index or the illite ‘crystallinity’ index. This measurement, which has been related to the degree of metamorphism of very low-grade, pelitic rocks, is a function of at least two crystal-chemical factors: (1) illite X-ray scattering domain size; and (2) illite structural distortions (especially swelling). Reynolds' NEWMOD computer program is used to construct a grid with which these two contributions to illite peak width can be determined independently from measurements of the 001 peak width at half-height and the Środoń intensity ratio. This method yields more information about changes undergone by illite during metamorphism than application of the Kubler index method alone.

Clay Minerals

Synthesis of illite-smectite from smectite at Earth surface temperatures and high pH

It is well known that illite-smectite can form from smectite at elevated temperatures in natural and experimental systems. However, the conversion of smectite to illite-smectite is also found in some natural systems that have never been heated. The present experiments show that illite layers can form from smectite by chemical reaction at 35° and 60°C at high solution pH. The rate of this reaction is accelerated by wetting and drying.

Clay Minerals

Lithium and potassium absorption, dehydroxylation temperature, and structural water content of aluminous smectites

X-ray analysis of Li + - and K + -saturated samples, differential thermal analysis (DTA), thermal gravimetric analysis (TGA), and chemical analysis of 83 samples enable a distinction to be made between Wyoming, Tatatilla, Otay, Chambers, and non-ideal types of montmorillonite, and between ideal and non-ideal types of beidellite. The Greene-Kelly Li + -test differentiates between the montmorillonites and beidellites. Re-expansion with ethylene glycol after K + -saturation and heating at 300°C depends upon total net layer charge and not upon location of the charge. Wyoming-type montmorillonites characteristically have low net layer charge and re-expand to 17 Å . whereas most other montmorillonites and beidellites have a higher net layer charge and re-expand to less than 17 Å . Major differences in dehydroxylation temperatures cannot be related consistently to the amount of Al 3 + -for-Si 4 + substitution, nor to the amount of Mg, Fe, type of interlayer cations, or particle size. The major factor controlling temperature of dehydroxylation seems to be the amount of structural (OH). Of 19 samples analyzed by TGA, montmorillonites and the one ideal beidellite that give dehydroxylation endotherms on their DTA curves between 650° and 760°C all contain nearly the ideal amount of 4(OH) per unit cell, but the non-ideal montmorillonites and beidellites that give dehydroxylation peaks between 550° and 600°C do not. Non-ideal beidellites contain more than the ideal amount of structural (OH) and non-ideal montmorillonites seem to contain less, although the low temperature of dehydroxylation of the latter could also be due to other structural defects. Change in X-ray diffraction intensity of the 001 reflection during dehydroxylation suggests that the extra (OH) of beidellite occurs at the apex of SiO 4 or AlO 4 tetrahedrons with the H + of the (OH) - polarized toward vacant cation sites in the octahedral sheet.

Clays and Clay Minerals

Mixed-layer kaolinite-montmorillonite from the Yucatan Peninsula, Mexico

Clay beds 1–2 m thick and interbedded with marine limestones probably of early Eocene age are composed of nearly pure mixed-layer kaolinite-montmorillonite. Particle size studies, electron micrographs, X-ray diffraction studies, chemical analyses, cation exchange experiments, DTA, and TGA indicate that clays from three different localities contain roughly equal proportions of randomly interlayered kaolinite and montmorillonite layers. The montmorillonite structural formulas average K 0·2 Na 0·2 Ca 0·2 Mg 0·2 (Al 2·5 Fe 1·0 3+ Mg 0·5 )(Al 0·75 Si 7.25 )O 20+ (OH) 4− , with a deficiency of structural (OH) in either the montmorillonite or kaolinite layers. Nonexchangeable K + indicates that a few layers are mica-like. Crystals are mostly round plates 1/10 to 1/20 µ across. The feature most diagnostic of the mixed-layer character is an X-ray reflection near 8 Å after heating at 300°C. The clays are inferred to have developed by weathering of volcanic ash and subsequent erosion and deposition in protected nearshore basins.

Clays and Clay Minerals

Surface charge density dependency on Al2O3 content in imogolite

An analysis of the available literature data indicates that the cation exchange capacity and surface charge density of imogolite decrease systematically as the mole % of Al 2 O 3 (i.e. 100 Al 2 O 3 /SIO 2 + Al 2 O 3 ) increases. This behavior is analogous to that of synthetic aluminosilicates. In contrast, no relation is apparent between the cation exchange capacity and mole % Al 2 O 3 for allophane. This difference is rather striking and although both are amorphic, i.e. show minimal specific X-ray diffraction effects, imogolite is somewhat more crystalline than allophane (Russell et al., 1969)

Clays and Clay Minerals

Imogolite and allophane formed in saprolite of basalt on Maui, Hawaii

Inorganic gel and allophane collected from basaltic saprolite on Maul, Hawaii, and studied by Patterson in I964 were reexamined. The main constituent of the gel is imogolite, and gibbsite and allophane are the minor constituents. Electron and X-ray diffraction patterns, DTA curve, and an infrared spectrum of the gel are characteristic of imogolite. The allophane is virtually noncrystalline to X-rays but contains a small amount of imogolite in relatively short threads. High-resolution electron micrographs indicate differences in structural organization between allophane and imogolite and suggest crystallization of imogolite from allophane. The occurrence of imogolite as a weathering product has been reported in many localities from pyroclastic materials but not from massive rocks. Probably the exceptionally high rainfall, excellent subsurface permeability of the weathered material, and the low pH and high organic content of the leaching solution provide favorable conditions for formation of imogolite from basalt on Maul.

Hawaii

Interlamellar adsorption of carbon dioxide by smectites

The adsorption of CO 2 at low temperature (∼ −70°C) on thin films of homoionic smectites was studied by X-ray diffraction and by i.r. absorption. An increase in the d 001 spacings of these clay films upon adsorption of CO 2 was observed. In addition, a dichroic effect was readily discernible by comparing the i.r. spectra at two different orientations of the smectite films; i.e. with the film normal and tilted 35° with respect to the i.r. beam. The CO 2 stretching vibration at 2350 cm −1 was used for the i.r. study. These observations conclusively show that CO 2 intercalates the smectite structure rather than being adsorbed only in pores between clay tactoids—the limiting process proposed by other investigators. Adsorption isotherm data from earlier surface area studies are re-examined here through application of the Dubinin equation. Again, intercalation is demonstrated by convergence of the plotted experimental data for smectites containing large monovalent interlayer cations toward a pore volume that is near the calculated theoretical value for a monolayer of intercalated CO 2 . Scanning electron photomicrographs of Li- and Cs- smectites provide additional evidence that aggregation differences are not responsible for the large observed difference in BET surface areas obtained for these smectites with CO 2 as the adsorbate. At low magnification, visual differences in macro-aggregates are apparent, but at high magnification no significant differences are observed in the micro-structure of individual aggregates where the major amount of gas adsorption really occurs.

Clays and Clay Minerals

Woolly erionite from the Reese River zeolite deposit, Lander County, Nevada, and its relationship to other erionites

Woolly erionite from the Reese River deposit, Nevada, is identical in appearance to that at the type locality, near Durkee, Oregon. Both of these erionites differ in appearance from all other erionite reported in the past 20 years from diverse rocks throughout the world which are described as prismatic or acicular in habit. The non-woolly erionites are especially common as microscopic crystals in diagenetically altered vitroclastic lacustrine deposits of Cenozoic age. The Reese River woolly erionite fills joints in gray to brownish-gray lacustrine mudstone of probably Pliocene age, in a zone about 1 m thick beneath a conspicuous gray vitric tuff. Compact masses of long, curly, woolly erionite fibers are in the plane of the joint and locally are associated with opal. Indices of refraction are ω = 1.468 and ε = 1.472; hexagonal unit-cell parameters are a = 13.186(2) Å, c = 15.055(1) Å, and V = 2267.1(0.9) Å 3 . A chemical analysis of woolly erionite yields a unit-cell composition of: Na 1.01 K 2.84 Mg 0.3 Ca 1.69 Al 8.18 Si 27.84 O 72 · 28.51H 2 O.

Clays and Clay Minerals

Hydrothermal reactivity of saponite

Saponite crystallizes from amorphous gel having an ideal saponite composition within 7 days at all experimental temperatures between 300° and 550°C at 1 kbar pressure. Reactions subsequent to this initial crystallization vary in type and degree, depending on the temperature of reaction and the type of interlayer cation. Above 450°C the intitially crystallized K-saponite dissolves, and talc and phlogopite nucleate and grow as discrete phases. At 450°C the initial K-saponite reacts to form talc and phlogopite layers, but the reaction proceeds via intracrystalline layer transformations rather than via dissolution and precipitation, producing a mixture of fully ordered, interstratified talc/saponite and fully ordered saponite/ phlogopite. The K-saponite shows subtle signs of reaction at 400°C after 200 days: this temperature is at least 150°C lower than experimental reaction temperatures previously reported for saponites. No reactions beyond the initial crystallization of saponite were observed below 400°C. K-saponite reacts more rapidly than either Na-saponite or Ca-saponite above 400°C and the Na-saponite and Ca-saponite produce no mica iayers during their transformation to mixed-layer clays. Interstratified talc/saponite formed in the Na-saponite system, and the Ca-saponite system produced both talc/saponite and chlorite/saponite.

Clays and Clay Minerals

Talc in the suspended matter of the northwestern Atlantic

Knowledge of the distribution, concentration, and composition of suspended particulate matter in seawater is important to the understanding of sedimentation processes on the Continental Shelf. Because the surfaces of both organic and inorganic particles have high affinities for pollutants, such as certain trace metals, chlorinated hydrocarbons, and petroleum (Bothner et al., 1981a), suspended matter plays a major role in the transport and fate of pollutants introduced into shelf and coastal waters. Although the composition of bottom sediments on the shelf off the northeastern United States is reasonably well known, the mineralogical composition and distribution of inorganic suspended matter is less well studied.

Northwestern Atlantic