Ultraviolet spectral reflectance properties of common planetary minerals

Ultraviolet spectral reflectance properties (200-400 nm) of a large number of minerals known or presumed to exist on the surfaces of Mars, the Moon, and asteroids, and in many meteorites, were investigated. Ultraviolet reflectance spectra (200-400 nm) of these minerals range from slightly blue-sloped (reflectance decreasing toward longer wavelengths) to strongly red-sloped (reflectance increasing toward longer wavelengths). Most exhibit one or two absorption features that are attributable to FeO charge transfers involving Fe³⁺ or Fe²⁺. The UV region is a very sensitive indicator of the presence of even trace amounts (<0.01 wt%) of Fe³⁺ and Fe²⁺. The major Fe³⁺O absorption band occurs at shorter wavelengths (∼210-230 nm), and is more intense than the major Fe²⁺O absorption band (∼250-270 nm). Ti-bearing minerals, such as ilmenite, rutile and anatase exhibit UV absorption bands attributable to Ti⁴⁺O charge transfers. While the positions of metal-O charge transfer bands sometimes differ for different minerals, the variation is often not diagnostic enough to permit unique mineral identification. However, iron oxides and oxyhydroxides can generally be distinguished from Fe-bearing silicates in the 200-400 nm region on the basis of absorption band positions. Within a given mineral group (e.g., low-calcium pyroxene, olivine, plagioclase feldspar), changes in Fe²⁺ or Fe³⁺ abundance do not appear to result in a measurable change in absorption band minima positions. Absorption band positions can vary as a function of grain size, however, and this variation is likely due to band saturation effects. The intensity of metal-O charge transfers means that some minerals will exhibit saturated UV absorption bands even for fine-grained (<45 μm) powders. In cases where absorption bands are not saturated (e.g., Fe²⁺O bands in some plagioclase feldspars and pyroxenes), changes in Fe²⁺ content do not appear to cause variations in band position. In other minerals (e.g., olivine), changes in band positions are correlated with compositional and/or grain size variations, but this is likely due to increasing band saturation rather than compositional variations. Overall, we find that the UV spectral region is sensitive to different mineral properties than longer wavelength regions, and thus offers the potential to provide complementary capabilities and unique opportunities for planetary remote sensing.     

Detection and discrimination of sulfate minerals using reflectance spectroscopy

A suite of sulfate minerals were characterized spectrally, compositionally, and structurally in order to develop spectral reflectance-compositional-structural relations for this group of minerals. Sulfates exhibit diverse spectral properties, and absorption-band assignments have been developed for the 0.3-26 μm range. Sulfate absorption features can be related to the presence of transition elements, OH, H₂O, and SO₄ groups. The number, wavelength position, and intensity of these bands are a function of both composition and structure. Cation substitutions can affect the wavelength positions of all major absorption bands. Hydroxo-bridged Fe³⁺ results in absorption bands in the 0.43, 0.5, and 0.9 μm regions, while the presence of Fe²⁺ results in absorption features in the 0.9-1.2 μm interval. Fundamental SO bending and stretching vibration absorption bands occur in the 8-10, 13-18, and 19-24 μm regions (1000-1250, 550-770, and 420-530 cm⁻¹). The most intense combinations and overtones of these fundamentals are found in the 4-5 μm (2000-2500 cm⁻¹) region. Absorption features seen in the 1.7-1.85 μm interval are attributable to HOH/OH bending and translation/rotation combinations, while bands in the 2.1-2.7 μm regions can be attributed to H₂O- and OH-combinations as well as overtones of SO bending fundamentals. OH- and H₂O-bearing sulfate spectra are fundamentally different from each other at wavelengths below ∼6 μm. Changes in H₂O/OH content can shift SO band positions due to change in bond lengths and structural rearrangement. Differences in absorption band wavelength positions enable discrimination of all the sulfate minerals used in this study in a number of wavelength intervals. Of the major absorption band regions, the 4-5 μm region seems best for identifying and discriminating sulfates in the presence of other major rock-forming minerals.     

Stability field and phase transition pathways of hydrous ferric sulfates in the temperature range 50 °C to 5 °C: Implication for martian ferric sulfates

We report the results from a systematic laboratory investigation on the fundamental properties of hydrous ferric sulfates. The study involves 150 experiments with duration of over 4 years on the stability field and phase transition pathways under Mars relevant environmental conditions for five ferric sulfates: ferricopiapite [Fe_4.67(SO₄)₆(OH)₂·20H₂O], kornelite [Fe₂(SO₄)₃·7H₂O], a crystalline and an amorphous pentahydrated ferric sulfate [Fe₂(SO₄)₃·5H₂O], and rhomboclase [FeH(SO₄)₂·4H₂O]. During the processes of phase transitions, we observed the phenomena that reflect fundamental properties of these species and the occurrence of other common hydrous ferric sulfates, e.g. paracoquimbite [Fe₂(SO₄)₃·9H₂O]. Based on the results of this set of experiments, we have drown the boundaries of deliquescence zone of five hydrous ferric sulfates and estimated the regions of their stability field in temperature (T) – relative humidity (RH) space. Furthermore, we selected the experimental parameters for a next step investigation, which is to determine the location of the phase boundary between two solid ferric sulfates, kornelite [Fe₂(SO₄)₃·7H₂O] and pentahydrated ferric sulfate [Fe₂(SO₄)₃·5H₂O]. The experimental observations in ferricopiapite dehydration processes were used to interpret the observed spectral change of Fe-sulfate-rich subsurface soils on Mars after their exposure by the Spirit rover to current martian atmospheric conditions.     

Search for sulfates on the surface of Ceres

The formation of hydrated salts is an expected consequence of aqueous alteration of Main Belt objects, particularly for large, volatile‐rich protoplanets like Ceres. Sulfates, present on water‐bearing planetary bodies (e.g., Earth, Mars, and carbonaceous chondrite parent bodies) across the inner solar system, may contribute to Ceres’ UV and IR spectral signature along with phyllosilicates and carbonates. We investigate the presence and stability of hydrated sulfates under Ceres’ cryogenic, low‐pressure environment and the consequent spectral effects, using UV–Vis–IR reflectance spectroscopy. H₂O loss begins instantaneously with vacuum exposure, measured by the attenuation of spectral water absorption bands, and a phase transition from crystalline to amorphous is observed for MgSO₄·6H₂O by X‐ray powder diffraction. Long‐term (>40 h), continuous exposure of MgSO₄·nH₂O (n = 0, 6, 7) to low pressure (10^?3–10^?6 Torr) causes material decomposition and strong UV absorption below 0.5 μm. Our measurements suggest that MgSO₄·6H₂O grains (45–83 μm) dehydrate to 2% of the original 1.9 μm water band area over ~0.3 Ma at 200 K on Ceres and after ~42 Ma for 147 K. These rates, inferred from an Avrami dehydration model, preclude MgSO₄·6H₂O as a component of Ceres’ surface, although anhydrous and minimally hydrated sulfates may be present. A comparison between Ceres emissivity spectra and laboratory reflectance measurements over the infrared range (5–17 μm) suggests sulfates cannot be excluded from Ceres’ mineralogy.     

Spectroscopy of Loose and Cemented Sulfate-Bearing Soils: Implications for Duricrust on Mars

The goal of this work is to determine the spectroscopic properties of sulfate in martian soil analogs over the wavelength range 0.3 to 25 μm (which is relevant to existing and planned remotely sensed data sets for Mars). Sulfate is an abundant component of martian soil (up to 9% SO₃ by weight) and apparently exists as a particulate in the soil but also as a cement. Although previous studies have addressed the spectroscopic identity of sulfates on Mars, none have used laboratory mixtures of materials with sulfates at the abundances measured by landed spacecraft, nor have any works considered the effect of salt-cementation on spectral properties of soil materials. For this work we created mixtures of a palagonitic soil (JSC Mars-1) and sulfates (MgSO₄ and CaSO₄·2H₂O). The effects of cementation were determined and separated from the effects of packing and hydration by measuring the samples as loose powders, packed powders, cemented materials, and disaggregated materials. The results show that the presence of particulate sulfate is best observed in the 4-5 μm region. Soils cemented with sulfate exhibit a pronounced restrahlen band between 8 and 9 μm as well as well-defined absorptions in the 4-5 μm region. Cementation effects are distinct from packing effects and disaggregation of cemented samples rapidly diminishes the strength of the restrahlen bands. The results of this study show that sulfate in loose materials is more detectable in the near infrared (4-5 μm) than in the thermal infrared (8-9 μm). However, cemented materials are easily distinguished from loose mixtures in the thermal infrared because of the high values of their absorption coefficient in this region. Together these results suggest that both wavelength regions are important for determining the spatial extent and physical form of sulfates on the surface of Mars.     

Spectral properties of simulated impact glasses produced from martian soil analogue JSC Mars-1

To simulate the formation of impact glasses on Mars, an analogue of martian bright soil (altered volcanic soil JSC Mars-1) was melted at relevant oxygen fugacities using a pulsed laser and a resistance furnace. Reduction of Fe³⁺ to Fe²⁺ and in some cases formation of nanophase Fe⁰ in the glasses were documented by Mössbauer spectroscopy and TEM studies. Reflectance spectra for several size fractions of the JSC Mars-1 sample and the glasses were acquired between 0.3 and 25 μm. The glasses produced from the JSC Mars-1 soil show significant spectral variability depending on the method of production and the cooling rate. In general, they are dark and less red in the visible compared to the original JSC Mars-1 soil. Their spectra do not have absorption bands due to bound water and structural OH, have positive spectral slopes in the near-infrared range, and show two broad bands centered near 1.05 and 1.9 μm, typical of glasses rich in ferrous iron. The latter bands and low albedo partly mimic the spectral properties of martian dark regions, and may easily be confused with mafic materials containing olivine and low-Ca pyroxene. Due to their disordered structures and vesicular textures, the glasses show relatively weak absorption features from the visible to the thermal infrared. These weak absorption bands may be masked by the stronger bands of mafic minerals. Positive near-infrared spectral slopes typical of fresh iron-bearing impact or volcanic glasses may be masked either by oxide/dust coatings or by aerosols in the Mars' atmosphere. As a result, impact glasses may be present on the surface of Mars in significant quantities that have been either misidentified as other phases or masked by phases with stronger infrared features. Spectrometers with sufficient spatial resolution and wavelength coverage may detect impact glasses at certain locations, e.g., in the vicinity of fresh impact craters. Such dark materials are usually interpreted as accumulations of mafic volcanic sand, but the possibility of an impact melt origin of such materials also should be considered. In addition, our data suggest that high contents of feldspars or zeolites are not necessary to produce the transparency feature at 12.1 μm typical of martian dust spectra.     

Spectral unmixing for mineral identification in pancam images of soils in Gusev crater, Mars

The objective of this work is to propose an automated unmixing technique for the analysis of 11-channel Mars Exploration Rover Panoramic Camera (MER/Pancam) spectra. Our approach is to provide a screening tool for identifying unique/distinct reflectance spectra. We demonstrate the utility of this unmixing technique in a study of the mineralogy of the bright salty soils exposed by the rover wheels in images of Gusev crater regions known as Paso Robles (Sols 400,426), Arad (Sol 721), and Tyrone (Sol 790). The unmixing algorithm is based on a novel derivation of the Nonnegative Matrix Factorization technique and includes added features that preclude the adverse effects of low abundance materials that would otherwise skew the unmixing. In order to create a full 11-channel spectrum out of the left and right eye stereo pairs, we also developed a new registration procedure that includes rectification and disparity calculation of the images. We identified two classes of endmember spectra for the bright soils imaged on Sols 426 and 790. One of these endmember classes is also observed for soils imaged on Sols 400 and 721 and has a unique spectral shape that is distinct from most iron oxide, sulfate and silicate spectra and differs from typical martian surface spectra. Instead, its unique spectral character resembles the spectral shape of the ferric sulfate minerals fibroferrite (Fe³⁺(SO₄)(OH) · 5H₂O) and ferricopiapite and the phosphate mineral ferristrunzite . The other endmember class is less consistent with specific minerals and is likely a mixture of altered volcanic material and some bright salts. Further analyses of data from Sols 400 and 790 using an anomaly detection algorithm as a tool for detecting low abundance materials additionally suggests the identification of the sulfate mineral paracoquimbite (Fe₂(SO₄)₃ · 9H₂O). This spectral study of Pancam images of the bright S- and P-enriched soils of Gusev crater identifies specific ferric sulfate and ferric phosphate minerals that are consistent with the unique spectral properties observed here in the 0.4-1 μm range.     

Modelling of atmospheric dust extinction and surface reflectance of Mars applying a radiative transfer simulation in the 2.0 and 2.7 μm CO2 bands

Infrared radiation spectra of Mars which can be measured by an orbiting Planetary Fourier Spectrometer (PFS) have been simulated in the spectral region from 1 to 50 μm. The radiative transfer simulation technique considers absorption, emission and multiple scattering by molecular (CO₂, H₂O, CO) and particulate (palagonite) species. It is shown that the contribution from atmospheric dust extinction and surface reflectance can be separated in the region of the CO₂ bands at 2.0 and 2.7 μm. Quantitative results of simultaneous surface pressure, reflectance and aerosol optical depth retrievals are discussed.     

Loss of water from Mars:: Implications for the oxidation of the soil

The evolution of the martian atmosphere with regard to its H₂O inventory is influenced by thermal loss processes of H, H₂, nonthermal atmospheric loss processes of H⁺, H₂⁺, O, O⁺, CO₂, and O₂⁺ into space, as well as by chemical weathering of the surface soil. The evolution of thermal and nonthermal escape processes depend on the history of the intensity of the solar XUV radiation and the solar wind density. Thus, we use actual data from the observation of solar proxies with different ages from the Sun in Time program for reconstructing the Sun's radiation and particle environment from the present to 3.5 Gyr ago. The correlation between mass loss and X-ray surface flux of solar proxies follows a power law relationship, which indicates a solar wind density up to 1000 times higher at the beginning of the Sun's main sequence lifetime. For the study of various atmospheric escape processes we used a gas dynamic test particle model for the estimation of the pick up ion loss rates and considered pick up ion sputtering, as well as dissociative recombination. The loss of H₂O from Mars over the last 3.5 Gyr was estimated to be equivalent to a global martian H₂O ocean with a depth of about 12 m, which is smaller than the values reported by previous studies. If ion momentum transport, a process studied in detail by Mars Express is significant on Mars, the water loss may be enhanced by a factor of about 2. In our investigation we found that the sum of thermal and nonthermal atmospheric loss rates of H and all nonthermal escape processes of O to space are not compatible with a ratio of 2:1, and is currently close to about 20:1. Escape to space cannot therefore be the only sink for oxygen on Mars. Our results suggest that the missing oxygen (needed for the validation of the 2:1 ratio between H and O) can be explained by the incorporation into the martian surface by chemical weathering processes since the onset of intense oxidation about 2 Gyr ago. Based on the evolution of the atmosphere-surface-interaction on Mars, an overall global surface sink of about 2×10⁴² oxygen particles in the regolith can be expected. Because of the intense oxidation of inorganic matter, this process may have led to the formation of considerable amounts of sulfates and ferric oxides on Mars. To model this effect we consider several factors: (1) the amount of incorporated oxygen, (2) the inorganic composition of the martian soil and (3) meteoritic gardening. We show that the oxygen incorporation has also implications for the oxidant extinction depth, which is an important parameter to determine required sampling depths on Mars aimed at finding putative organic material. We found that the oxidant extinction depth is expected to lie in a range between 2 and 5 m for global mean values.     

Spectral evidence for zeolite in the dust on Mars

Spectral features observed in Mars Global Surveyor Thermal Emission Spectrometer data (∼1670-220 cm⁻¹) of martian surface dust provide clues to its mineralogy. An emissivity peak at ∼1630 cm⁻¹ is consistent with the presence of an H₂O-bearing mineral. This spectral feature can be mapped globally and shows a distribution related to the classical bright regions on Mars that are known to be dust covered. An important spectral feature at ∼830 cm⁻¹ present in a newly derived average spectrum of surface dust likely is a transparency feature arising from the fine particulate nature of the dust. Its shape and location are consistent with plagioclase feldspars and also zeolites, which essentially are the hydrous form of feldspar. The generally favored visible/near-infrared spectral analog for martian dust, JSC Mars-1 altered tephra, does not display the ∼830 cm⁻¹ feature. Zeolites commonly form from the interaction of low temperature aqueous fluids and volcanic glass in a variety of geologic settings. The combination of spectral features that are consistent with zeolites and the likelihood that Mars has (or had) geologic conditions necessary to produce them makes a strong case for recognizing zeolite minerals as likely components of the martian regolith.     

Oxygen and carbon isotope ratios in the martian atmosphere

Oxygen and carbon isotope ratios in the martian CO₂ are key values to study evolution of volatiles on Mars. The major problems in spectroscopic determinations of these ratios on Mars are uncertainties associated with: (1) equivalent widths of the observed absorption lines, (2) line strengths in spectroscopic databases, and (3) thermal structure of the martian atmosphere during the observation. We have made special efforts to reduce all these uncertainties. We observed Mars using the Fourier Transform Spectrometer at the Canada–France–Hawaii Telescope. While the oxygen and carbon isotope ratios on Mars were byproducts in the previous observations, our observation was specifically aimed at these isotope ratios. We covered a range of 6022 to 6308 cm⁻¹ with the highest resolving power of ν/δν=3.5×10⁵ and a signal-to-noise ratio of 180 in the middle of the spectrum. The chosen spectral range involves 475 lines of the main isotope, 184 lines of ¹³CO₂, 181 lines of CO¹⁸O, and 119 lines of CO¹⁷O. (Lines with strengths exceeding 10⁻²⁷ cm at 218 K are considered here.) Due to the high spectral resolution, most of the lines are not blended. Uncertainties of retrieved isotope abundances are in inverse proportion to resolving power, signal-to-noise ratio, and square root of the number of lines. Laboratory studies of the CO₂ isotope spectra in the range of our observation achieved an accuracy of 1% in the line strengths. Detailed observations of temperature profiles using MGS/TES and data on temperature variations with local time from two GCMs are used to simulate each absorption line at various heights in each part of the instrument field of view and then sum up the results. Thermal radiation of Mars' surface and atmosphere is negligible in the chosen spectral range, and this reduces errors associated with uncertainties in the thermal structure on Mars. Using a combination of all these factors, the highest accuracy has been achieved in measuring the CO₂ isotope ratios: ¹³C/¹²C = 0.978 ± 0.020 and ¹⁸O/¹⁶O = 1.018 ± 0.018 times the terrestrial standards. Heavy isotopes in the atmosphere are enriched by nonthermal escape and sputtering, and depleted by fractionation with solid-phase reservoirs. The retrieved ratios show that isotope fractionation between CO₂ and oxygen and carbon reservoirs in the solid phase is almost balanced by nonthermal escape and sputtering of O and C from Mars.     

Detection of methane in the martian atmosphere: evidence for life?

Using the Fourier Transform Spectrometer at the Canada-France-Hawaii Telescope, we observed a spectrum of Mars at the P-branch of the strongest CH₄ band at 3.3 μm with resolving power of 180,000 for the apodized spectrum. Summing up the spectral intervals at the expected positions of the 15 strongest Doppler-shifted martian lines, we detected the absorption by martian methane at a 3.7 sigma level which is exactly centered in the summed spectrum. The observed CH₄ mixing ratio is 10±3 ppb. Total photochemical loss of CH₄ in the martian atmosphere is equal to , the CH₄ lifetime is 340 years and methane should be uniformly mixed in the atmosphere. Heterogeneous loss of atmospheric methane is probably negligible, while the sink of CH₄ during its diffusion through the regolith may be significant. There are no processes of CH₄ formation in the atmosphere, so the photochemical loss must therefore be balanced by abiogenic and biogenic sources. Outgassing from Mars is weak, the latest volcanism is at least 10 million years old, and thermal emission imaging from the Mars Odyssey orbiter does not reveal any hot spots on Mars. Hydrothermal systems can hardly be warmer than the room temperature at which production of methane is very low in terrestrial waters. Therefore a significant production of hydrothermal and magmatic methane is not very likely on Mars. The calculated average production of CH₄ by cometary impacts is 2% of the methane loss. Production of methane by meteorites and interplanetary dust does not exceed 4% of the methane loss. Methane cannot originate from an extinct biosphere, as in the case of “natural gas” on Earth, given the exceedingly low limits on organic matter set by the Viking landers and the dry recent history which has been extremely hostile to the macroscopic life needed to generate the gas. Therefore, methanogenesis by living subterranean organisms is a plausible explanation for this discovery. Our estimates of the biomass and its production using the measured CH₄ abundance show that the martian biota may be extremely scarce and Mars may be generally sterile except for some oases.     

Spectral characterization of weathering products of elemental iron in a Martian atmosphere: Implications for Mars hyperspectral studies

Visible and near-infrared spectroscopic properties have been measured on elemental iron experimentally weathered in simulated Martian atmosphere and correlated to mineralogical compositions determined by X-ray diffraction. Two main features are observed in the reflectance spectra, corresponding to two deep bands located at 0.9 and 3.1 μm, respectively the iron band and the hydration band. In early weathering stages both Fe²⁺ and Fe³⁺ bands are identified. In addition, whereas the water band position does not change with time, the Fe²⁺ band disappears, and the Fe³⁺ band shifts towards longer wavelength (from 0.88 to 0.92 μm) because of transition from Fe²⁺ phases (siderite) to Fe³⁺ phases (ferrihydrite and goethite). Apart from these spectral signatures, other bands more specific of each phase are not clearly evidenced, especially for siderite. This is due to relatively low abundance of siderite (<20 wt%), but also to the very small grain size of secondary phase as well as surface coatings of iron (oxy)hydroxides. Therefore, our results suggest that carbonates, even if not detected, could be present in the form of very small grains in the surface of Mars.     

Water sorption on martian regolith analogs: Thermodynamics and near-infrared reflectance spectroscopy

The near-infrared reflectance spectra of the martian surface present strong absorption features attributed to hydration water present in the regolith. In order to characterize the relationships between this water and atmospheric vapor and decipher the physical state of water molecules in martian regolith analogs, we designed and built an experimental setup to measure near-IR reflectance spectra under martian atmospheric conditions. Six samples were studied that cover part of the diversity of Mars surface mineralogy: a hydrated ferric oxide (ferrihydrite), two igneous samples (volcanic tuff, and dunite sand), and three potential water rich soil materials (Mg-sulfate, smectite powder and a palagonitic soil, the JSC Mars-1 regolith stimulant). Sorption and desorption isotherms were measured at 243 K for water vapor pressure varying from 10⁻⁵ to ∼0.3 mbar (relative humidity: 10⁻⁴ to 75%). These measurements reveal a large diversity of behavior among the sample suite in terms of absolute amount of water adsorbed, shape of the isotherm and hysteresis between the adsorption and desorption branches. Simultaneous in situ spectroscopic observations permit a detailed analysis of the spectral signature of adsorbed water and also point to clear differences between the samples. Ferric (oxy)hydroxides like ferrihydrite or other phases present in palagonitic soils are very strong water adsorbent and may play an important role in the current martian water cycle by allowing large exchange of water between dust-covered regions and atmosphere at diurnal and seasonal scales.     

Trace ferric ion in lunar and meteoritic titanaugites

Evidence for presence of Fe³⁺ in lunar rocks is furnished by heating them in air to 200-225°C for two hours. This causes a large decrease in the same charge transfer bands attributed to Fe³⁺ that can be enhanced by heating the same rocks in air at 500°C. This data is interpreted as evidence that the Fe³⁺ was not in equilibrium in the melt but was produced by cosmic radiation subsequent to the rock formation. The decrease of the Fe³⁺ charge-transfer bands is accompanied by decrease in intensity of spin-allowed Fe²⁺ bands attributed toM ₁ sites in the pyroxene in rock 12018. This decrease in the Fe²⁺ bands is attributed to decrease in the Fe²⁺ Fe³⁺ charge-transfer intensification of these Fe²⁺ spin-allowed transitions when radiation-produced Fe³⁺ is partially-reduced by the low-temperature heating.The reaction of Fe³⁺ on heating to 200-225°C is probably Fe³⁺ + Ti³⁺ Fe²⁺ + Ti⁴⁺.This is the reverse of the reaction caused by cosmic ray bombardment of the rock on the lunar surface. Possible tetrahedrally coordinated Fe³⁺ is present in the meteoritic and lunar augites as suggested by comparison of their spectra to that of terrestrial augite high in Fe³⁺. This would have been present in the original melt and is distinct from radiation produced Fe³⁺ in theM-sites.The polarized absorption spectra of single crystal pigeonite and augite from rock 12021 before heating, and augite from 12018 after heating are compared to that of meteoritic titanaugite in the Angra dos Reis meteorite and terrestrial titanaugite from Maui, Hawaii. The absorption spectrum of meteoritic hypersthene (Tatahouine) is also included for comparison to the pigeonite.     

Near‐infrared spectra of clinopyroxenes: Effects of calcium content and crystal structure

Abstract– Pyroxenes are among the most common minerals in the solar system and are ideally suited for remote geochemical analysis because of the sensitivity of their distinctive spectra to mineral composition. Fe²⁺ is responsible for the dominant pyroxene absorptions in the visible and near‐infrared, but substitutions of other cations such as Ca²⁺ change the crystal structure and site geometries and thus the crystal field splitting energies of the Fe cations. To define spectral systematics resulting from major pyroxene cations (Ca²⁺, Mg²⁺, and Fe²⁺), we focus on a suite of pyroxenes synthesized with only Ca²⁺, Mg²⁺, and Fe²⁺ in the two octahedral sites, specifically examining the effect of Ca²⁺ on pyroxene absorption bands. The modified Gaussian model is used to deconvolve pyroxene spectra into component bands that can then be linked directly to crystal field absorptions. In orthopyroxenes and low‐Ca clinopyroxenes, Ca²⁺‐content has a strong and predictable effect on the positions of the absorption bands. At a threshold of Wo₃₀, the crystal field environment stagnates and the M2 bands cease to change significantly as more Ca²⁺ is added. At Wo₅₀, when most of the M2 sites are filled by Ca²⁺, band positions do not change drastically, although the presence and strengths of the 1 and 2 μm bands are affected by even trace amounts of Fe²⁺ in the M2 site. It is thus apparent that next‐nearest neighbors and the distortions they impose on the pyroxene lattice affect the electronic states around the Fe²⁺ cations and control absorption band properties.     

Hydrogen peroxide on Mars: evidence for spatial and seasonal variations

Hydrogen peroxide (H₂O₂) has been suggested as a possible oxidizer of the martian surface. Photochemical models predict a mean column density in the range of 10¹⁵-10¹⁶ cm⁻². However, a stringent upper limit of the H₂O₂ abundance on Mars (9×10¹⁴ cm⁻²) was derived in February 2001 from ground-based infrared spectroscopy, at a time corresponding to a maximum water vapor abundance in the northern summer (30 pr. μm, Ls=112°). Here we report the detection of H₂O₂ on Mars in June 2003, and its mapping over the martian disk using the same technique, during the southern spring (Ls=206°) when the global water vapor abundance was ∼10 pr. μm. The spatial distribution of H₂O₂ shows a maximum in the morning around the sub-solar latitude. The mean H₂O₂ column density (6×10¹⁵ cm⁻²) is significantly greater than our previous upper limit, pointing to seasonal variations. Our new result is globally consistent with the predictions of photochemical models, and also with submillimeter ground-based measurements obtained in September 2003 (Ls=254°), averaged over the martian disk (Clancy et al., 2004, Icarus 168, 116-121).     

Spectral detectability of Ca- and Mg-sulfates in Martian bright soils in the 4–5 μm wavelength range

Chemical analyses of soil samples performed at different landing sites on Mars suggest the presence of sulfate minerals. These minerals are also thought to be present in the globally mixed Martian bright soils covering large areas of the planet. However, remote soil spectra have so far provided only tentative identification of sulfates regarding mineral types and abundances. This paper concentrates on the detectability of four Ca- and Mg-sulfates (anhydrite, gypsum, kieserite, hexahydrite) in the 4–5 μm range of Martian remote soil spectra. This spectral range is important for sulfate detection as most fine-grained sulfates exhibit significant absorption bands between 4 and 5 μm, independent of the texture of the host soils (e.g., loose powdered or cemented soils). Furthermore, this is the spectral range for which the Planetary Fourier Spectrometer (PFS) and Observatoire pour la Minéralogie, l’Eau, les Glaces, et l’Activité (OMEGA) instruments onboard ESA/Mars Express mission provide high spectral and spatial resolution data. Laboratory near- and mid-IR reflectance spectra of the pure sulfates and their mixtures with a terrestrial Martian soil analog were acquired. The results show that even the smallest amount of admixed sulfate (∼5 wt%) generates significant absorption features in the portion of the 4–5 μm range not covered by the saturated Martian atmospheric CO₂ absorption band between 4.2 and 4.4 μm. Model calculations of the influence of emitted surface radiation on the detectability of sulfate features show that the depth of the features decreases strongly with increasing surface temperature of an observed area resulting in the fact that all sulfates are spectrally hidden at surface temperatures around 270 K even at ∼14 or ∼25 wt% sulfate content in the soils. Sulfates become increasingly detectable depending on the sulfate content if the surface temperature is below 260 K. The outcome of this work helps to constrain the conditions needed for remote detection of sulfates within Martian bright soils in the 4–5 μm range.     

Material composition assessment and discovering sublimation activity on asteroids 145 Adeona, 704 Interamnia, 779 Nina,and 1474 Beira

Spectrophotometric observations of 145 Adeona, 704 Interamnia, 779 Nina, and 1474 Beira—asteroids of close primitive types—allowed us to detect similar mineralogical absorption bands in their reflectance spectra centered in the range 0.35 to 0.92 μm; the bands are at 0.38, 0.44, and 0.67–0.71 μm. On the same asteroids, the spectral signs of simultaneous sublimation activity were found for the first time. Namely, there are maxima at ～0.35–0.60 μm in the reflectance spectra of Adeona, Interamnia, and Nina and at ～0.55–075 μm in the spectra of Beira. We connect this activity with small heliocentric distances of the asteroids and, consequently, with a high insolation at their surfaces. Examination of the samples of probable analogues allowed us to identify Fe³⁺ and Fe²⁺ in the material of these asteroids through the mentioned absorption bands. For analogues, we took powdered samples of carbonaceous chondrites Orgueil (CI), Mighei (CM2), Murchison (CM2), and Boriskino (CM2), as well as hydrosilicates of the serpentine group. Laboratory spectral reflectance study of the samples of low-iron Mg serpentines (<2 wt % FeO) showed that the equivalent width of the absorption band centered at 0.44–0.46 μm strongly correlates with the content of Fe³⁺ in octahedral and tetrahedral coordinations. Our conclusion is that this absorption band can be used as a qualitative indicator of Fe³⁺ in the surface matter of asteroids and other solid celestial bodies. The comparison of the listed analog samples and the asteroids by parameters of the spectral features suggests that the silicate component of the asteroids' surface material is a mixture of hydrated and oxidized compounds, including oxides and hydroxides of bivalent and trivalent iron and carbonaceous-chondritic material. At the same time, the sublimation activity of Adeona, Interamnia, Nina, and Beira at high surface temperatures points to a substantial content of water ice in their material. This contradicts the previously existing notions on the C-type and similar asteroids as bodies containing water only in the bound state. Moreover, since the sublimation process simultaneously occurs in four primitive-type bodies at small heliocentric distances, we may suppose that this phenomenon is common for the main-belt asteroids.     

Minimum estimates of the amount and timing of gases released into the martian atmosphere from volcanic eruptions

Volcanism has been a major process during most of the geologic history of Mars. Based on data collected from terrestrial basaltic eruptions, we assume that the volatile content of martian lavas was typically ∼0.5 wt.% water, ∼0.7 wt.% carbon dioxide, ∼0.14 wt.% sulfur dioxide, and contained several other important volatile constituents. From the geologic record of volcanism on Mars we find that during the late Noachian and through the Amazonian volcanic degassing contributed ∼0.8 bar to the martian atmosphere. Because most of the outgassing consisted of greenhouse gases (i.e., CO₂ and SO₂) warmer surface temperatures resulting from volcanic eruptions may have been possible. Our estimates suggest that ∼1.1 × 10²¹ g (∼8 ± 1 m m⁻²) of juvenile water were released by volcanism; slightly more than half the amount contained in the north polar cap and atmosphere. Estimates for released CO₂ (1.6 × 10²¹ g) suggests that a large reservoir of carbon dioxide is adsorbed in the martian regolith or alternatively ∼300 cm cm⁻² of carbonates may have formed, although these materials would not occur readily in the presence of excess SO₂. Up to ∼120 cm cm⁻² (2.2 × 10²⁰ g) of acid rain (H₂SO₄) may have precipitated onto the martian surface as the result of SO₂ degassing. The hydrogen flux resulting from volcanic outgassing may help explain the martian atmospheric D/H ratio. The amount of outgassed nitrogen (∼1.3 mbar) may also be capable of explaining the martian atmospheric ¹⁵N/¹⁴N ratio. Minor gas constituents (HF, HCl, and H₂S) could have formed hydroxyl salts on the surface resulting in the physical weathering of geologic materials. The amount of hydrogen fluoride emitted (1.82 × 10¹⁸ g) could be capable of dissolving a global layer of quartz sand ∼5 mm thick, possibly explaining why this mineral has not been positively identified in spectral observations. The estimates of volcanic outgassing presented here will be useful in understanding how the martian atmosphere evolved over time.