Engineering topics
Publications and source records attributed to Rampe, E. B..
To obtain detailed mineralogy information, the Mars Science Laboratory rover Curiosity carries CheMin, the first X-ray diffraction (XRD) instrument used on a planet other than Earth. CheMin has provided the first in situ XRD analyses of full phase assemblages on another planet.
The Curiosity rover investigated the mineralogy of the Sheepbed mudstone member of the Yellowknife Bay formation in Gale crater. Data from the Chemistry and Mineralogy (CheMin) X-ray diffractometer (XRD) helped identify phyllosilicates in the two drilled samples, John Klein and Cumberland. These patterns showed peaks at low angles, consistent with (001) peaks in 2:1 swelling phyllosilicates [1]. Evolved gas analyses (EGA) by the Sample Analysis at Mars (SAM) instrument of these samples confirmed the presence of phyllosilicates through the release of H2O at high temperatures, consistent with dehydroxylation of octahedral OH in phyllosilicates [2]. CheMin data for the phyllosilicates at John Klein and Cumberland show that they are structurally similar in that their (02l) peaks are near 22.5 deg 2theta, suggesting both samples contain trioctahedral 2:1 phyllosilicates [1]. However, the positions of the (001) peaks differ: the phyllosilicate at John Klein has its (001) peak at 10 Angstroms, whereas the phyllosilicate at Cumberland has an (001) peak at 14 Angstroms. Such differences in (001) dspacings can be ascribed to the type of cation in the interlayer site [3]. For example, large monovalent cations (e.g., K(+)) have low hydration energies and readily lose their H2O of hydration, whereas small divalent cations (e.g., Mg(2+)) have high energies of hydration and retain H2O in the phyllosilicate interlayers [3,4]. The goal of this study is to determine whether differences in the interlayer cation composition can explain the CheMin data from John Klein and Cumberland and to use this knowledge to better understand phyllosilicate formation mechanisms.
The Sample Analysis at Mars (SAM) and Chemistry and Mineralogy (CheMin) instruments on the Mars Science Laboratory (MSL) analysed several subsamples of sample fines (<150 μm) from three sites in Yellowknife Bay, an aeolian bedform termed Rocknest (hereafter "RN") and two samples drilled from the Sheepbed mudstone at sites named John Klein ("JK") and Cumberland ("CB"). SAM's evolved gas analysis (EGA) mass spectrometry detected H2O, CO2, O2, H2, SO2, H2S, HCl, NO, OCS, CS2 and other trace gases. The identity of evolved gases and temperature (T) of evolution can support mineral detection by CheMin and place constraints on trace volatile-bearing phases present below the CheMin detection limit or difficult to characterize with XRD (e.g., X-ray amorphous phases). Here, we focus on potential constraints on phases that evolved SO2, H2S, OCS, and CS2 during thermal analysis.
A significant portion of the soil of the Rocknest dune is crystalline and is consistent with derivation from unweathered basalt. Minerals and their compositions are identified by X-ray diffraction (XRD) data from the CheMin instrument on MSL Curiosity. Basalt minerals in the soil include plagioclase, olivine, low- and high-calcium pyroxenes, magnetite, ilmenite, and quartz. The only minerals unlikely to have formed in an unaltered basalt are hematite and anhydrite. The mineral proportions and compositions of the Rocknest soil are nearly identical to those of the Adirondack-class basalts of Gusev Crater, Mars, inferred from their bulk composition as analyzed by the MER Spirit rover.
The CheMin instrument on the Mars Science Laboratory rover Curiosity performed X-ray diffraction analysis on Martian soil [1] at Rocknest in Gale Crater. In particular, crystalline phases from scoop 5 were identified and analyzed with the Rietveld method [2]. Refined unit-cell parameters are reported in Table 1. Comparing these unit-cell parameters with those in the literature provides an estimate of the chemical composition of the crystalline phases. For instance, Fig. 1 shows the Mg-content of Fa-Fo olivine as a function of the b unit-cell parameter using literature data. Our refined b parameter is indicated by the black triangle.
Numerous orbital and landed observations of the martian surface suggest a reasonably uniform martian soil composition, likely as a result of global aeolian mixing [1, 2]. Chemical data for martian soils are abundant [e.g., 2, 3], and phase information has been provided by lander thermal emission and Moessbauer spectroscopic measurements [3, 4, 5, 6]. However, until now no X-ray diffraction (XRD) data were available for martian soil nor has XRD ever been used on another body apart from Earth. XRD is generally considered the most definitive method for determining the crystalline phases in solid samples, and it is the method of choice for determining mineralogy. CheMin s first XRD analysis on Mars coincided with the 100th anniversary of the discovery of X-ray diffraction by von Laue. Curiosity delivered scooped samples of loose, unconsolidated material ("soil") acquired from an aeolian bedform at the Rocknest locality to instruments in the body of the rover (the laboratory). Imaging shows that the soil has a range of particle sizes, of 1-2 mm and smaller, presumably representing contributions from global, regional, and local sources.
The CheMin (Chemistry and Mineralogy) instrument on the Mars Science Laboratory rover Curiosity uses a CCD detector and a Co-anode X-ray tube source to acquire both mineralogy (from the pattern of Co diffraction) and chemical information (from energies of fluoresced X-rays). A key component of the CheMin instrument is the ability to move grains within sample cells during analysis, providing multiple, random grain orientations that disperse diffracted X-ray photons along Debye rings rather than producing discrete Laue spots. This movement is accomplished by piezoelectric vibration of the sample cells. A cryocooler is used to maintain the CCD at a temperature at about -50 C in order to obtain energy resolution better than 250 eV, allowing discrimination of diffracted Co K X-rays from Fe K and other fluorescent X-rays. A detailed description of CheMin is provided in [1]. The CheMin flight model (FM) is mounted within the body of Curiosity and has been operating on Mars since August 6, 2012. An essentially identical sister instrument, the CheMin demonstration model (DM), is operated in a Mars environment chamber at JPL.
X-ray diffraction (XRD) data collected of the Rocknest samples by the CheMin instrument on Mars Science Laboratory suggest the presence of poorly crystalline or amorphous materials [1], such as nanophase weathering products or volcanic and impact glasses. The identification of the type(s) of X-ray amorphous material at Rocknest is important because it can elucidate past aqueous weathering processes. The presence of volcanic and impact glasses would indicate that little chemical weathering has occurred because glass is highly susceptible to aqueous alteration. The presence of nanophase weathering products, such as allophane, nanophase iron-oxides, and/or palagonite, would indicate incipient chemical weathering. Furthermore, the types of weathering products present could help constrain pH conditions and identify which primary phases altered to form the weathering products. Quantitative analysis of phases from CheMin data is achieved through Reference Intensity Ratios (RIRs) and Rietveld refinement. The RIR of a mineral (or mineraloid) that relates the scattering power of that mineral (typically the most intense diffraction line) to the scattering power of a separate mineral standard such as corundum [2]. RIRs can be calculated from XRD patterns measured in the laboratory by mixing a mineral with a standard in known abundances and comparing diffraction line intensities of the mineral to the standard. X-ray amorphous phases (e.g., nanophase weathering products) have broad scattering signatures rather than sharp diffraction lines. Thus, RIRs of X-ray amorphous materials are calculated by comparing the area under one of these broad scattering signals with the area under a diffraction line in the standard. Here, we measured XRD patterns of nanophase weathering products (allophane, aluminosilicate gel, and ferrihydrite) mixed with a mineral standard (beryl) in the CheMinIV laboratory instrument and calculated their RIRs to help constrain the abundances of these phases in the Rocknest samples.
The Mars Science Laboratory rover Curiosity has been exploring Mars since August 5, 2012, conducting engineering and first-time activities with its mobility system, arm, sample acquisition and processing system (SA/SPaH-CHIMRA) and science instruments. Curiosity spent 54 sols at a location named "Rocknest," collecting and processing five scoops of loose, unconsolidated materials ("soil") acquired from an aeolian bedform (Fig. 1). The Chemistry and Mineralogy (CheMin) instrument analyzed portions of scoops 3, 4, and 5, to obtain the first quantitative mineralogical analysis of Mars soil, and to provide context for Sample Analysis at Mars (SAM) measurements of volatiles, isotopes and possible organic materials.
The mineralogy instrument CheMin onboard the MSL rover Curiosity analyzed by transmission XRD [1] the <150 microns size fraction of putative global basaltic martian soil from scoops 4 and 5 of the Rocknest aeolian bedform (sol 81-120). Here, we combine chemical (APXS) and mineralogical (Mossbauer; MB) results from the MER rovers with chemical (APXS) and mineralogical (CheMin) results from Curiosity to constrain the relative proportions of amorphous and crystalline components, the bulk chemical composition of those components, and the
The CheMin instrument on the Mars Science Laboratory (MSL) rover Curiosity is an X-ray diffraction (XRD) and X-ray fluorescence (XRF) instrument capable of providing the mineralogical and chemical compositions of rocks and soils on the surface of Mars. CheMin uses a microfocus X-ray tube with a Co target, transmission geometry, and an energy-discriminating X-ray sensitive CCD to produce simultaneous 2-D XRD patterns and energy-dispersive X-ray histograms from powdered samples. Piezoelectric vibration of the cell is used to randomize the sample to reduce preferred orientation effects. Instrument details are provided in [1, 2, 3]. Analyses of rock and soil samples by the Mars Exploration Rovers (MER) show nanophase ferric oxide (npOx) is a significant component of the Martian global soil [4] and is thought to be one of the major contributing phases that the Curiosity rover will encounter if a soil sample is analyzed in Gale Crater. Because of the nature of this material, npOx will likely contribute to an X-ray amorphous or short-order component of a XRD pattern measured by the CheMin instrument.
Orbital near-infrared (NIR) reflectance spectra of the martian surface from the OMEGA and CRISM instruments have identified a variety of phyllosilicates in Noachian terrains. The types of phyllosilicates present on Mars have important implications for the aqueous environments in which they formed, and, thus, for recognizing locales that may have been habitable. Current identifications of phyllosilicates from martian NIR data are based on the positions of spectral absorptions relative to laboratory data of well-characterized samples and from spectral ratios; however, some phyllosilicates can be difficult to distinguish from one another with these methods (i.e. illite vs. muscovite). Here we employ a multivariate statistical technique, principal component analysis (PCA), to differentiate between spectrally similar phyllosilicate minerals. PCA is commonly used in a variety of industries (pharmaceutical, agricultural, viticultural) to discriminate between samples. Previous work using PCA to analyze raw NIR reflectance data from mineral mixtures has shown that this is a viable technique for identifying mineral types, abundances, and particle sizes. Here, we evaluate PCA of second-derivative NIR reflectance data as a method for classifying phyllosilicates and test whether this method can be used to identify phyllosilicates on Mars.
We have collected laboratory thermal IR spectra of the mineraloid allophane and aluminosilicate gels. Using those spectra to model regional TES spectra, we suggest that several areas of Mars contain significant amounts of allophane-like weathering products. The presence of allophane on Mars indicates that 1) significant Al sources, such as feldspar or glass, were weathered; 2) weathering on Mars produced poorly-crystalline aluminosilicates, rather than easily identifiable crystalline minerals; and 3) some Martian weathering proceeded under moderate pH environments, suggesting acid weathering is not the only major alteration mechanism on Mars.
Allophane is an alteration product of volcanic glass and a clay mineral precursor that is commonly found in basaltic soils on Earth. It is a poorly-crystalline or amorphous, hydrous aluminosilicate with Si/Al ratios ranging from approx.0.5-1 [Wada, 1989]. Analyses of thermal infrared (TIR) spectra of the Martian surface from TES show high-silica phases at mid-to-high latitudes that have been proposed to be primary volcanic glass [Bandfield et al., 2000; Bandfield, 2002; Rogers and Christensen, 2007] or poorly-crystalline secondary silicates such as allophane or aluminous amorphous silica [Kraft et al., 2003; Michalski et al., 2006; Rogers and Christensen, 2007; Kraft, 2009]. Phase modeling of chemical data from the APXS on the Mars Exploration Rover Spirit suggest the presence of allophane in chemically weathered rocks [Ming et al., 2006]. The presence of allophane on Mars has not been previously tested with IR spectroscopy because allophane spectra have not been available. We synthesized allophanes and allophanic gels with a range of Si/Al ratios to measure TIR emission and VNIR reflectance spectra and to test for the presence of allophane in Martian soils. VNIR reflectance spectra of the synthetic allophane samples have broad absorptions near 1.4 m from OH stretching overtones and 1.9 m from a combination of stretching and bending vibrations in H2O. Samples have a broad absorption centered near 2.25 microns, from AlAlOH combination bending and stretching vibrations, that shifts position with Si/Al ratio. Amorphous silica (opaline silica or primary volcanic glass) has been identified in CRISM spectra of southern highland terrains based on the presence of 1.4, 1.9, and broad 2.25 m absorptions [Mustard et al., 2008]; however, these absorptions are also consistent with the presence of allophane. TIR emission spectra of the synthetic allophanes show two spectrally distinct types: Si-rich and Al-rich. Si-rich allophanes have two broad absorptions centered near 1080 and 430 cm-1 from Si(Al)-O stretching and Si(Al)-O bending vibrations, respectively, and Al-rich allophanes have three broad absorptions centered near 950, 540, and 430 cm-1. We used a spectral library commonly used to deconvolve TES spectra and four allophane spectra to model nine spectrally distinct regions on Mars [from Rogers et al., 2007]. Regions previously modeled with high-silica phases contain significant amounts of allophane (>10 vol.%) in our models. Our models of northern Acidalia, the type locality for surface type 2 materials, contain 40 vol.% Si-rich allophane. The presence of allophane in multiple surface regions of Mars indicates a more widespread occurrence of low-temperature aqueous alteration at moderate pH than has been previously recognized. The regional variations in modeled abundances and the types of allophane (Si- vs. Al-rich) suggest regional differences in Mars weathering processes.
Allophane is a poorly-crystalline, hydrous aluminosilicate with variable Si/Al ratios approx.0.5-1 and a metastable precursor of clay minerals. On Earth, it forms rapidly by aqueous alteration of volcanic glass under neutral to slightly acidic conditions [1]. Based on in situ chemical measurements and the identification of alteration phases [2-4], the Martian surface is interpreted to have been chemically weathered on local to regional scales. Chemical models of altered surfaces detected by the Mars Exploration Rover Spirit in Gusev crater suggest the presence of an allophane-like alteration product [3]. Thermal infrared (TIR) spectroscopy and spectral deconvolution models are primary tools for determining the mineralogy of the Martian surface [5]. Spectral models of data from the Thermal Emission Spectrometer (TES) indicate a global compositional dichotomy, where high latitudes tend to be enriched in a high-silica material [6,7], interpreted as high-silica, K-rich volcanic glass [6,8]. However, later interpretations proposed that the high-silica material may be an alteration product (such as amorphous silica, clay minerals, or allophane) and that high latitude surfaces are chemically weathered [9-11]. A TIR spectral library of pure minerals is available for the public [12], but it does not contain allophane spectra. The identification of allophane on the Martian surface would indicate high water activity at the time of its formation and would help constrain the aqueous alteration environment [13,14]. The addition of allophane to the spectral library is necessary to address the global compositional dichotomy. In this study, we characterize a synthetic allophane by IR spectroscopy, X-ray diffraction (XRD), and transmission electron microscopy (TEM) to create an IR emission spectrum of pure allophane for the Mars science community to use in Martian spectral models.
It has been suggested that allophane or related poorly crystalline aluminosilicates are present on Mars, and that they comprise the high-silica phase detected by the Thermal Emission Spectrometer (TES) in Surface Type 2 materials (Michalski et al., 2005). Using new laboratory spectra of allophanic materials, we (Rampe et al., this meeting) have detected allophane on the Martian surface via spectral modeling of TES data. We find that ST2 materials in the Northern Plains are consistent with a significant amount of high-silica allophane-like materials. In addition, we find that allophane may be present in some areas of ancient highlands (TES surface type 1), but spectra of those regions are more consistent with aluminous allophane. The presence of allophane and its chemical variability have important implications for chemical weathering and soil development on Mars. Allophane-like materials are amorphous or poorly crystalline hydrous aluminosilicates formed from chemical weathering of glasses, feldspars, and other silicates (cf. Parfitt, 2009). True allophane is a combination of SiO2, Al2O3 and H2O where Al:Si ranges from ~0.5-2. Aluminosilicate gels are amorphous and chemically similar to allophane but can have higher SiO2 contents. The presence of allophane indicates low-temperature chemical weathering and provides constraints on alteration conditions, limiting pH to circum-neutral (~4.5-8). Our model results indicate that weathering occurred in the relatively young northern plains of Mars. The high-silica allophane-like material present there implies little silica mobility through the soil column, which suggests that weathering involved small amounts of liquid water, consistent with our previous models of weathering in ice-rich soils (Kraft et al., 2007). The aluminous allophane indicated by our spectral models to be present in the highlands suggest that those regions experienced greater amounts of SiO2 leaching and weathering in those soils may have involved much larger amounts of water. The presence of allophane-like materials suggests that these weathering regimes were not influenced by the acidic weathering that appears to have affected other areas of Mars and has been proposed as a planetwide alteration process (Hurowitz and McLennan, 2007). Soil development in basaltic material (typically tephra) on Earth usually leads to formation of andosols. Although we do not suggest a one-to-one analogy between dark basaltic Martian soils and andosols, there may be important similarities, as andosols are typified by significant production of allophane as well as poorly crystalline Fe-hydroxides. The detection of allophane on Mars suggests a positive utility of an andosol model for Martian soils, particularly when coupled with the ubiquitous presence of Feoxide materials on Mars. An andosol model of soil formation is mineralogically consistent with palagonite models for the formation of Martian dust (cf. Banin et al., 1992; Morris et al., 2001), which suggests a possible genetic relationship of dust and bright soils to the broader soil layer of Mars.