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The Windjana drill sample, a sandstone of the Dillinger member (Kimberley formation, Gale Crater, Mars), was analyzed by CheMin X-ray diffraction (XRD) in the MSL Curiosity rover. From Rietveld refinements of its XRD pattern, Windjana contains the following: sanidine (21% weight, ~Or95); augite (20%); magnetite (12%); pigeonite; olivine; plagioclase; amorphous and smectitic material (~25%); and percent levels of others including ilmenite, fluorapatite, and bassanite. From mass balance on the Alpha Proton X-ray Spectrometer (APXS) chemical analysis, the amorphous material is Fe rich with nearly no other cations-like ferrihydrite. The Windjana sample shows little alteration and was likely cemented by its magnetite and ferrihydrite. From ChemCam Laser-Induced Breakdown Spectrometer (LIBS) chemical analyses, Windjana is representative of the Dillinger and Mount Remarkable members of the Kimberley formation. LIBS data suggest that the Kimberley sediments include at least three chemical components. The most K-rich targets have 5.6% K2O, ~1.8 times that of Windjana, implying a sediment component with >40% sanidine, e.g., a trachyte. A second component is rich in mafic minerals, with little feldspar (like a shergottite). A third component is richer in plagioclase and in Na2O, and is likely to be basaltic. The K-rich sediment component is consistent with APXS and ChemCam observations of K-rich rocks elsewhere in Gale Crater. The source of this sediment component was likely volcanic. The presence of sediment from many igneous sources, in concert with Curiosity's identifications of other igneous materials (e.g., mugearite), implies that the northern rim of Gale Crater exposes a diverse igneous complex, at least as diverse as that found in similar-age terranes on Earth.

Diffraction effects from interstratified phyllosilicates have been studied extensively, and several computer programs such as NEWMOD© are available to facilitate interpretation of X-ray diffraction (XRD) profiles. However, accurate quantification of samples containing multiple interstratified phyllosilicate minerals is difficult due to the generally subjective nature of interpretations. More recent automated fitting interpretations require extensive computational effort, involving numerous calculations of profiles with different fitting-parameter values. Computational cost in time per calculation is the key factor influencing the overall efficiency of automated profile fitting. In general, the matrix methodology developed by Kakinoki and Komura is more efficient than the NEWMOD© architecture. A new matrix methodology was developed that reduces the number of matrix operations such as multiplication and addition, and these modifications improve calculation efficiency by up to a factor of three, with even greater improvement for small crystallite sizes (< 20 layers). A new computer program, ClayStrat, based on the modified matrix methodology, was developed to calculate one-dimensional XRD profiles from interstratified phyllosilicates along the Z direction. [ABSTRACT FROM AUTHOR]

Dolomite [CaMg(CO3)2] forms in numerous geological settings, usually as a diagenetic replacement of limestone, and is an important component of petroleum reservoir rocks, rocks hosting base metal deposits and fresh water aquifers. Dolomite is a rhombohedral carbonate with a structure consisting of an ordered arrangement of alternating layers of Ca2+ and Mg2+ cations interspersed with [ABSTRACT FROM AUTHOR]

The mineralogy of evaporites from the Lewis Cliff ice tongue (LCIT), Antarctica, and their mineral stabilities and transformation behaviours under different temperature and relative humidity (RH) conditions have been evaluated to elucidate formation mechanism(s). A variety of sodium (Na)-rich evaporite minerals were documented using RH-controlled powder X-ray diffraction (XRD) methods including Na-sulfates (mirabilite and thenardite), Na-carbonate/bicarbonates (nahcolite, occasional trona and natron) and Na-borates (qilianshanite and borax). Mirabilite begins to dehydrate to thenardite, and natron to trona and natrite when exposed to room temperature, even when maintained at RH values similar to those measured at the LCIT (50–70%). The boron-mineral qilianshanite was discovered for the first time in Antarctica within the evaporite mounds. The mirabilite-rich mounds are deduced to have formed via a freezing/sublimation process that occurred in glacial or subglacial bodies of water supplied by glacial tills containing microbially oxidized sulfate ions. The needle-like nahcolite crystals growing on the exteriors of the mounds suggest a dissolution/precipitation process involving atmospheric CO2 and water. The co-existence of nahcolite and boron-bearing minerals indicates the presence of a Na+-, HCO3-- and boron-bearing alkaline brine, which produces qilianshanite as a secondary mineral by reaction of nahcolite and borax in atmospheric CO2 and H2O. [ABSTRACT FROM PUBLISHER]

We present an X-ray diffraction and multi-nuclear (²H and 43Ca) NMR study of Ca-exchanged hectorite (a smectite clay) that provides important new insight into molecular behavior at the smectite-H2O interface. Variable-temperature 43Ca MAS NMR and controlled humidity XRD indicate that Ca2+ occurs as proximity-restricted outer-sphere hydration complexes between -120 and +25 °C in a two-layer hydrate and at T ≤ -50 °C in a 2:1 water/solid paste. Changes in the 43Ca NMR peak width and position with temperature are more consistent with diffusion-related processes than with dynamics involving metal-surface interactions such as site exchange. The ²H NMR signal between -50 and +25 °C for a two-layer hydrate of Ca-hectorite is similar to that of Na- and other alkali metal hectorites and represents 2H2O molecules experiencing anisotropic motion describable using the ²H C2/C3 jump model we proposed previously. ²H T1 relaxation results for Ca- and Na-hectorite are well fit with a fast-exchange limit, rotational diffusion model for ²H2O dynamics, yielding GHz-scale rotational reorientation rates compatible with the C3 component of the C2/C3 hopping model. The apparent activation energy for ²H2O rotational diffusion in the two-layer hydrate is greater for Ca-hectorite than Na-hectorite (25.1 vs. 21.1 kJ/mol), consistent with the greater affinity of Ca2+ for H2O. The results support the general principle that the dynamic mechanisms of proximity-restricted H2O are only weakly influenced by the cation in alkali metal and alkaline earth metal smectites and provide critical evidence that the NMR resonances of charge-balancing cations in smectites become increasingly influenced by diffusion-like dynamic processes at low temperatures as the charge density of the unhydrated cation increases. [ABSTRACT FROM AUTHOR]

Zeolites are low-density silicates with structures consisting of a negatively charged aluminosilicate framework that creates a system of uniform linked channels and cavities. Variable amounts of extraframework cations and H2O molecules occupy the channel system, and the H2O molecules are very responsive to changes in temperature, pressure and partial pressure of water (i.e. PH2O or relative humidity, RH). As the H2O molecules occupy much of the volume of the extraframework sites, a gain or loss of H2O molecules has a direct effect on the extraframework cations and an indirect effect on the framework. Temperature or RH-induced changes can result in both first- and second-order phase transitions, the latter resulting from continuous, minor changes in hydration state and cation position, and the former resulting from discrete changes in hydration state, which can cause similar shifts in cation position. Second-order transitions are typically reversible with no hysteresis, but first-order transitions exhibit considerable hysteresis. As H2O molecules are crucial in determining zeolite behavior, it is important that any study of thermal behavior involve control of not only temperature but also of relative humidity. Stabilization of a zeolite's hydrated phase to higher temperatures under higher RH conditions can cause some phase transitions to be missed, as is the case with natrolite. [ABSTRACT FROM AUTHOR]

The crystal structures of natrolite and its dehydrated high-temperature phases (α1- and α2-metanatrolite) have been determined from powder X-ray diffraction measurements as a function of temperature and partial pressure of water (PH2O) to characterize the phase transition behavior. The evolution of crystal structure as a function of temperature shows two different phase transitions, depending on the PH2O, with α1-metanatrolite occurring at elevated PH2O and α2-metanatrolite occurring at low PH2O. Our discovery of α2-metanatrolite implies the existence of more than one transition mechanism, which we correlate with the migration of Na+ ions and the rate of evolution of H2O molecules. The transition behavior is rationalized in terms of two cooperating mechanisms: (1) dehydration-induced processes, which determine the phase transition temperature; and (2) thermally induced processes, which determine how the framework and its extraframework cations are modified. [ABSTRACT FROM AUTHOR]

Presents information on a study which evaluated the response of the laumontite crystal structure to hydration/dehydration using Rietveld refinements with x-ray diffraction data collected. Crystal chemical background; Experimental setup; Rietveld refinements; Results and discussion.

FULLPAT is a quantitative X-ray diffraction methodology that merges the advantages of existing full-pattern fitting methods with the traditional reference intensity ratio (RIR) method. Like the Rietveld quantitative analysis method, it uses complete diffraction patterns, including the background. However, FULLPAT can explicitly analyze all phases in a sample, including partially ordered or amorphous phases such as glasses, clay minerals, or polymers. Addition of an internal standard to both library standards and unknown samples eliminates instrumental and matrix effects and allows unconstrained analyses to be conducted by direct fitting of library standard patterns to each phase in the sample. Standard patterns may include data for any solid material including glasses, and calculated patterns may also be used. A combination of standard patterns is fitted to observed patterns using least-squares minimization, thereby reducing user intervention and bias. FULLPAT has been coded into Microsoft EXCEL using standard spreadsheet functions. [ABSTRACT FROM AUTHOR]

Ferrian saponite from the eastern Santa Monica Mountain, near Griffith Park (Los Angeles, California), was investigated as a mineralogical analog to smectites discovered on Mars by the CheMin X-ray diffraction instrument onboard the Mars Science Laboratory (MSL) rover. The martian clay minerals occur in sediment of basaltic composition and have 02l diffraction bands peaking at 4.59 A, consistent with tri-octahedral smectites. The Griffith saponite occurs in basalts as pseudomorphs after olivine and mesostasis glass and as fillings of vesicles and cracks and has 02l diffraction bands at that same position. We obtained chemical compositions (by electron microprobe), X-ray diffraction patterns with a lab version of the CheMin instrument, Mössbauer spectra, and visible and near-IR reflectance (VNIR) spectra on several samples from that locality. The Griffith saponite is magnesian, Mg/(Mg+ΣFe) = 65-70%, lacks tetrahedral Fe3+ and octahedral Al3+, and has Fe3+ /ΣFe from 64 to 93%. Its chemical composition is consistent with a fully tri-octahedral smectite, but the abundance of Fe3+ gives a nominal excess charge of +1 to +2 per formula unit. The excess charge is likely compensated by substitution of O2- for OH-, causing distortion of octahedral sites as inferred from Mössbauer spectra. We hypothesize that the Griffith saponite was initially deposited with all its iron as Fe2+ and was oxidized later. X-ray diffraction shows a sharp 001 peak at 15 Å, 00l peaks, and a 02l diffraction band at the same position (4.59 A) and shape as those of the martian samples, indicating that the martian saponite is not fully oxidized. VNIR spectra of the Griffith saponite show distinct absorptions at 1.40, 1.90, 2.30-2.32, and 2.40 mu m, arising from H2+O and hydroxyl groups in various settings. The position of the ~2.31 μm spectral feature varies systematically with the redox state of the octahedrally coordinated Fe. This correlation may permit surface oxidation state to be inferred (in some cases) from VNIR spectra of Mars obtained from orbit, and, in any case, ferrian saponite is a viable assignment for spectral detections in the range 2.30-2.32 μm. [ABSTRACT FROM AUTHOR]

Abstract Shale reservoirs are characterized by low matrix permeability and therefore require effective models of geomechanical properties to optimize drilling and hydraulic fracturing strategies. Both initial rock composition and thermal maturity are potentially critical controls on geomechanical properties. We investigate the Upper Devonian Duvernay Formation, Western Canada Sedimentary Basin, a major shale gas target that spans a wide range in rock compositions and thermal maturity to identify relationships between these parameters and geomechanical properties. Core hardness measurements and dipole sonic and density log data were used to characterize the geomechanical properties. Major element chemical analysis, X-ray diffraction analysis and LECO combustion were used to determine mineralogy, bulk rock chemistry and total organic carbon (TOC) content and to distinguish biogenic from detrital silica. Scanning electron microscopy (SEM) images with complementary energy-dispersive spectroscopy (EDS) maps were obtained for representative samples to document the rock fabric and distribution of organic matter and minerals. Hardness and Al2O3 concentrations are strongly negatively correlated in all cores, regardless of thermal maturity, suggesting that clay minerals are the most significant factor controlling geomechanical properties. Biogenic silica is positively correlated to hardness. Detrital silica is negatively correlated to hardness, an artifact of the positive correlation between detrital clay minerals and detrital quartz. The positive correlations between CaO content and hardness in all cores suggest the brittle behavior of carbonate minerals. Increased thermal maturity from immature to oil window results in greater hardness for rocks of similar geochemical compositions. We propose that this results from: (1) enhanced mechanical compaction; (2) carbonate cementation; (3) increased stiffness of kerogen; and (4) partial conversion of kerogen into expelled hydrocarbons that reduces the load-bearing function of the organic matter. At maturities greater than oil window, thermal maturity does not exert a major control on the rock strength; thus, there are no significant changes in hardness between samples from oil window and dry gas window. Geomechanical properties can be related to mineralogy, which exerts a major impact on the geomechanical properties. Quartz cements sourced from biogenic silica rather than smectite-to-illite transition are the primary contributor to the rock strength in the Duvernay Formation. However, it is noteworthy that thermal maturity should also be considered as an important factor when predicting geomechanical properties from mineralogy. Highlights • Geomechanics in shales are controlled by both rock composition and subsequent diagenetic processes. • Clay minerals are the most significant factor controlling geomechanical properties. • Quartz cements sourced from biogenic silica considerably contribute to the rock strength. • Geomechanical variation can be related to position within a stratigraphic framework. [ABSTRACT FROM AUTHOR]

The use of non-recovery/heat-recovery cokemaking technology offers new possibilities for coke makers. The literature shows that most of the knowledge about the development of coke properties is based on work done on the traditional by-product cokemaking technology. This study investigates the nature and origin of the variation in coke strength after reaction (CSR) obtained in different regions of the heat-recovery oven chamber. Coke fingers collected from three different zones (bottom center, top center, and top right) of a commercial heat-recovery oven were studied. Coke fingers were collected intact and studied incrementally, starting from tar line to cauliflower end. Coke samples were investigated using the CSR test, gas adsorption techniques, optical microscopy, and X-ray diffraction analyses. The results show that the CSR trend in the bottom center region of the oven is unidirectional, increasing from tarline to cauliflower end, whilst a curving CSR trend is observed in coke collected from top center and top right regions of the oven. The highest CSR value was found in the bottom center region, a characteristic attributed to limited swelling, which inhibits porosity development in this region. It was found that, while the CSR trend along the coke finger is influenced by both the porous structure and carbon matrix, variations in CSR are better explained by porosity-related properties, particularly pores in the mesopore range (2–50 nm pore diameter). Swelling patterns in different zones of the oven appear to have a significant role in the determination of mesopore volume. For cokes with high surface area available for solution-loss, contrary to expectations, a weak relationship was found between CSR and carbon matrix development, as expressed by crystallite height and percentage of less-reactive carbon forms. [ABSTRACT FROM AUTHOR]

Abstract: Interlayered clays are common constituents of several soil orders. The presence of interlayering is indicated by modified thermal stability of soil vermiculites and smectites. In most studies the clays have been reported as Al-hydroxy-interlayered minerals. Despite the abundance of organic compounds in many soils, the potential existence of soil organo-clay intercalations has rarely been considered. In the present study three clay subfractions separated from the eluvial (E) horizon of one podzol from the Tatra Mts., Poland, were studied using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and elemental CHNS analysis, in the natural state and after being subjected to organic matter removal, free iron oxides removal, saturation with different cations, and heating at 330°C and 550°C. All fractions contain a “~14Å clay”. In the natural state the “~14Å clay” shows high thermal resistance, manifested by only a partial shift to 10Å after heating at 330°C. This behavior strongly suggests the presence of interlayering. Saturation with K+ shifted the ~14Å reflection to ~13–11Å, which suggests displacement of a charged species from the interlayer. Clay sample treatment with H2O2 and NaOCl reduced the stability of the interlayered phase because 330° C heat treatment shifted the ~14Å phase to ~10Å, which suggests that the interlayered phase might be organic. Furthermore, the 13–18% organic carbon content of the clays and near disappearance of infrared peaks at 2855cm−1, 2926cm−1, 1738cm−1, ~1600cm−1, and ~1400cm−1 after H2O2 or NaOCl treatment suggests that the clay interlayer phase is mostly organic. Both Al-hydroxy and organic interlayers can be evaluated using a combination of X-ray diffraction, elemental analysis, and infrared spectroscopy and should be considered as possible interlayer phases during the study of interlayered clays. [Copyright &y& Elsevier]