Near-infrared reflectance spectra from bulk samples of the two Martian meteorites Zagami and Nakhla

Abstract— Zagami and Nakhla are achondrites and belong to the Shergotty-Nakhla-Chassigny (SNC) meteorite group. It is generally accepted that Mars is their parent body. Mineralogical and chemical analyses have revealed that the major mineral phases of these two meteorites are pyroxene, olivine, maskelynite, and plagioclase. In this work, near-infrared biconical reflectance measurements were performed on sawed surfaces of chips from Zagami and Nakhla. Spectra obtained with an analytical spot diameter on the order of the mineral grain size reflect the heterogeneous distribution of different mineral phases. The characteristic absorption bands of the pyroxenes are numerically evaluated in terms of the modified Gaussian model. Spectra with overlapping absorption features are resolved into the basic absorption bands. From these results, it can be estimated what kind of clinopyroxenes belong to the investigated mineral assemblages. As a result, the major clinopyroxene phase in Nakhla is Ca-rich augite, whereas in Zagami both Ca-rich and Ca-poor pyroxenes are present. By means of such a procedure, laboratory spectra of minerals become more informative and may help in discussing Martian remote sensing data in the near-infrared region.     

The basaltic shergottite Northwest Africa 856: Petrology and chemistry

Abstract— We report on the discovery of a new shergottite from South Morocco. This single stone weighing 320 g is referenced as Northwest Africa (NWA) 856 with Djel Ibone as a synonymous name. It is a fresh, fine‐grained basaltic rock consisting mainly of two pyroxenes (total ?68 vol%: 45% pigeonite, En_61‐16Wo_9–22Fs_26–68; 23% augite, En_46‐26Wo_34‐29Fs_21–43) and plagioclase converted to maskelynite (?23 vol%, Ab_43–57Or_1–5An_54‐36). Accessory minerals include merrillite, Cl‐apatite, pyrrhotite, ilmenite, ulvöspinel, silica (stishovite and glass), amorphous K‐feldspar and baddeleyite. Amorphous mixtures of maskelynite and silica occur most commonly as median layers inside maskelynite laths. In addition, melt pockets (?2 vol%) were recognized with relics of maskelynite, pyroxene and both dense silica glass and stishovite occurring as both grains and submicrometer needles. The compositions of the melt pockets are consistent with mixtures of maskelynite and pyroxenes with an average of ?50 vol% maskelynite. The meteorite is highly fractured at all scales. The bulk composition of NWA 856 has been measured for 44 elements. It is an Al‐poor ferroan basaltic rock which strongly resembles Shergotty and Zagami in its major and trace element composition. The nearly flat rare earth element (REE) pattern (La/Lu)_n = 0.9, is similar to that of Shergotty or Zagami and differs significantly from NWA 480, another Moroccan shergottite recently described. According to the U, Ba and Sr abundances, NWA 856 is not significantly weathered. The oxygen isotopes (δ18O = +5.03%, δ17O = +3.09%, and Δ17O = +0.47%) are in agreement with the martian origin of this meteorite. On the basis of grain size, pyroxene zoning and composition, abundance of silica inclusions associated with maskelynite, trace element abundances, REE pattern and oxygen isotopes, pairing with NWA 480 is excluded. The similarity with Shergotty and Zagami is striking. The only significant differences are a larger grain size, a greater abundance of silica and melt pockets, a slightly more restricted range of pyroxene compositions and the absence of significant mesostasis.     

The mid-infrared transmission spectra of Antarctic ureilites

Abstract— The mid-infrared (4000–450 cm^?1; 2.5–22.2 μm) transmission spectra of seven Antarctic ureilites and 10 Antarctic H-5 ordinary chondrites are presented. The ureilite spectra show a number of absorption bands, the strongest of which is a wide, complex feature centered near 1000 cm^?1 (10 μm) due to Si-O stretching vibrations in silicates. The profiles and positions of the substructure in this feature indicate that Mg-rich olivines and pyroxenes are the main silicates responsible. The relative abundances of these two minerals, as inferred from the spectra, show substantial variation from meteorite to meteorite, but generally indicate olivine is the most abundant (olivine:pyroxene = 60:40 to 95:5). Both the predominance of olivine and the variable olivine-to-pyroxene ratio are consistent with the known composition and heterogeneity of ureilites. The H-5 ordinary chondrites spanned a range of weathering classes and were used to provide a means of addressing the extent to which the ureilite spectra may have been altered by weathering processes. It was found that, while weathering of these meteorites produces some weak bands due to the formation of small amounts of carbonates and hydrates, the profile of the main silicate feature has been little affected by Antarctic exposure in the meteorites studied here. The mid-infrared ureilite spectra provide an additional means of testing potential asteroidal parent bodies for the ureilites. At present, the best candidates include the subset of S-type asteroids having low albedos and weak absorption features in the near infrared.     

Near-infrared reflectance spectroscopy of Ca-rich clinopyroxenes and prospects for remote spectral characterization of planetary surfaces

We present results of laboratory near-infrared reflectance studies of a set of calcic pyroxenes with comparable calcium contents (Wo_45-50) but variable iron content and oxidation states. This new dataset complements earlier published data (Cloutis and Gaffey, 1991, J. Geophys. Res. 96, 22809-28826, and references therein). In particular, our new spectra extend the scarce available spectral data on chemically analyzed Fe-rich high-Ca clinopyroxenes. We attempted to interpret the spectral behavior of our samples in terms of chemistry and coordination site occupancies. Tentatively, we conclude that Fe-rich calcic pyroxenes have very low contents of Fe²⁺ in the M2 sites and belong to the spectral type A lacking the 2-μm band. This may be due to high Ca and Mn contents in these pyroxenes. Fe-poor high-Ca pyroxenes are more spectrally variable. In general, they tend to belong to the spectral type B with two major bands near 1 and 2 μm, unless the samples have high Fe³⁺/Fe²⁺ ratios or are rich in Mn and Ca. Some of them (including unusual meteorite Angra dos Reis) are of type B despite very high Ca contents. We applied the Modified Gaussian Model (MGM) to characterize three major Fe²⁺ absorption bands in the 1-μm region of the spectra of Ca-rich pyroxenes. Only the band due to Fe²⁺ in the M1 coordination site near 1.15 μm may be potentially useful to estimate the Fe content in calcic pyroxenes on remotely-sensed surfaces of Solar System bodies. The spectral variability of basaltic meteorites (angrites) that are rich in calcic pyroxenes is also discussed. The presence of spectral type A calcic pyroxenes in these meteorites complicates unambiguous identification of olivine in asteroid spectra.     

Mineralogy of Antarctic basaltic shergottite Queen Alexandra Range 94201: Similarities to Elephant Moraine A79001 (Lithology B) martian meteorite

Abstract— Antarctic meteorite QUE 94201 is a new basaltic shergottite that is mainly composed of subequal amounts of maskelynite and pyroxenes (pigeonite and augite) plus abundant merrillite and accessory phases. It also contains impact melt. Complex zoning patterns in QUE 94201 pyroxenes revealed by elemental map analyses using an electron microprobe suggest a crystallization sequence from Mg-rich pigeonite (En₆₂Fss₃₀Wo_g) to extremely Fe-rich pigeonite (En₅Fs₈₁Wo₁₄) via {110} Mg-rich augite bands (En₄₄Fs₂₀Wo₃₆) in a single crystal. These textures, along with the abundant plagioclase (maskelynite), indicates single-stage rapid cooling (>5 °C/year) of this rock from a supercooled magma. Transition from Mg-rich augite to Fe-rich pigeonite reflects the onset of plagioclase crystallization. Enrichment of late-stage phases in QUE 94201 implies crystallization from an evolved magma and suggests a different parent magma composition from the other basaltic shergottites. Lithology B of EETA79001 basaltic shergottite contains pyroxenes that show complex zoning with augite bands similar to those in QUE 94201 pyroxene, which suggests similar one-stage rapid cooling. Lithology B of EETA79001 also resembles QUE 94201 in its coarse-grained texture of silicates and its high abundance of maskelynite, although QUE 94201 probably crystallized from a more fractionated magma. We also note that some Apollo lunar mare basalts (e.g., 12020 and 12021) have similar mineralogy and petrology to QUE 94201, especially in pyroxene zoning. All these basaltic rocks with complex pyroxene zoning suggest rapid metastable crystallization from supercooled magmas.     

Petrology and chemistry of the basaltic shergottite North West Africa 480

Abstract— North West Africa (NWA) 480 is a new martian meteorite of 28 g found in the Moroccan Sahara in November 2000. It consists mainly of large gray pyroxene crystals (the largest grains are up to 5 mm in length) and plagioclase converted to maskelynite. Excluding the melt pocket areas, modal analyses indicate the following mineral proportions: 72 vol% pyroxenes extensively zoned, 25% maskelynite, 1% phosphates (merrillite and chlorapatite), 1% opaque oxides (ilmenite, ulvöspinel and chromite) and sulfides, and 1% others such as silica and fayalite. The compositional trend of NWA 480 pyroxenes is similar to that of Queen Alexandra Range (QUE) 94201 but in NWA 480 the pyroxene cores are more Mg‐rich (En₇₇‐En₆₅). Maskelynites display a limited zoning (An_42–50Ab_54‐48Or_2–4). Our observations suggest that NWA 480 formed from a melt with a low nuclei density at a slow cooling rate. The texture was achieved via a single‐stage cooling where pyroxenes grew continuously. A similar model was previously proposed for QUE 94201 by McSween et al. (1996). NWA 480 is an Al‐poor ferroan basaltic rock and resembles Zagami or Shergotty for major elements and compatible trace element abundances. The bulk rock analysis for oxygen isotopes yields Δ¹⁷O = +0.42%, a value in agreement at the high margin, with those measured on other shergottites (Clayton and Mayeda, 1996; Romanek et al., 1998; Franchi et al., 1999). Its CI‐normalized rare earth element pattern is similar to those of peridotitic shergottites such as Allan Hills (ALH)A77005, suggesting that these shergottites shared a similar parent liquid, or at least the same mantle source.     

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.     

Noble gases in mineral separates from three shergottites: Shergotty,Zagami, and EETA79001

Abstract— This study provides a complete data set of all five noble gases for bulk samples and mineral separates from three Martian shergottites: Shergotty (bulk, pyroxene, maskelynite), Zagami (bulk, pyroxene, maskelynite), and Elephant Moraine (EET) A79001, lithology A (bulk, pyroxene). We also give a compilation of all noble gas and nitrogen studies performed on these meteorites. Our mean values for cosmic‐ray exposure ages from ³He, ²¹Ne, and ³⁸Ar are 2.48 Myr for Shergotty, 2.73 Myr for Zagami, and 0.65 Myr for EETA79001 lith. A. Serious loss of radiogenic ⁴He due to shock is observed. Cosmogenic neon results for bulk samples from 13 Martian meteorites (new data and literature data) are used in addition to the mineral separates of this study in a new approach to explore evidence of solar cosmic‐ray effects. While a contribution of this low‐energy irradiation is strongly indicated for all of the shergottites, spallation Ne in Chassigny, Allan Hills (ALH) 84001, and the nakhlites is fully explained by galactic cosmic‐ray spallation. Implanted Martian atmospheric gases are present in all mineral separates and the thermal release indicates a near‐surface siting. We derive an estimate for the ⁴⁰Ar/³⁶Ar ratio of the Martian interior component by subtracting from measured Ar in the (K‐poor) pyroxenes the (small) radiogenic component as well as the implanted atmospheric component as indicated from ¹²⁹Xe, * excesses. Unless compromised by the presence of additional components, a high ratio of ～2000 is indicated for Martian interior argon, similar to that in the Martian atmosphere. Since much lower ratios have been inferred for Chassigny and ALH 84001, the result may indicate spatial and/or temporal variations of ⁴⁰Ar/³⁶Ar in the Martian mantle.     

Mid‐infrared study of stones from the Sutter's Mill meteorite

The Sutter's Mill meteorite fell in northern California on April 22, 2012. Several fragments of the meteorite were recovered, some of them shortly after the fall, others several days later after a heavy rainstorm. In this work, we analyzed several samples of four fragments―SM2, SM12, SM20, and SM30―from the Sutter's Mill meteorite with two infrared (IR) microscopes operating in the 4000–650 cm^?1 (2.5–15.4 μm) range. Spectra show absorption features associated with minerals such as olivines, phyllosilicates, carbonates, and possibly pyroxenes, as well as organics. Spectra of specific minerals vary from one particle to another within a given stone, and even within a single particle, indicating a nonuniform mineral composition. Infrared features associated with aliphatic CH₂ and CH₃ groups associated with organics are also seen in several spectra. However, the presence of organics in the samples studied is not clear because these features overlap with carbonate overtone bands. Finally, other samples collected within days after the rainstorm show evidence for bacterial terrestrial contamination, which indicates how quickly meteorites can be contaminated on such small scales.     

Spectral reflectance properties of minerals exposed to simulated Mars surface conditions

A number of mineral species were exposed to martian surface conditions of atmospheric pressure and composition, temperature, and UV light regime, and their evolution was monitored using reflectance spectroscopy. The stabilities for different groups varied widely. Phyllosilicate spectra all showed measurable losses of interlayer H₂O, with some structural groups showing more rapid H₂O loss than others. Loss of OH from the phyllosilicates is not always accompanied by a change in metal-OH overtone absorption bands. OH-bearing sulfates, such as jarosite and alunite, show no measurable change in spectral properties, suggesting that they should be spectrally detectable on Mars on the basis of diagnostic absorption bands in the 0.4-2.5 μm region. Fe³⁺- and H₂O-bearing sulfates all showed changes in the appearance and/or reduction in depths of hydroxo-bridged Fe³⁺ absorption bands, particularly at 0.43 μm. The spectral changes were often accompanied by visible color changes, suggesting that subsurface sulfates exposed to the martian surface environment may undergo measurable changes in reflectance spectra and color over short periods of time (days to weeks). Organic-bearing geological materials showed no measurable change in CH related absorption bands, while carbonates and hydroxides also showed no systematic changes in spectral properties. The addition of ultraviolet irradiation did not seem to affect mineral stability or rate of spectral change, with one exception (hexahydrite). In some cases, spectral changes could be related to the formation of specific new phases. The data also suggest that hydrated minerals detected on Mars to date retain their diagnostic spectral properties that allow their unique identification.     

Optical constants of amorphous and crystalline H2O-ice in the near infrared from 1.1 to 2.6 μm

Using new laboratory spectra, we have calculated the real and imaginary parts of the index of refraction of amorphous and crystalline H₂O-ice from 20 to 150 K in the frequency range 9000-3800 cm⁻¹ (1.1-2.6 μm) at a spectral resolution of 1 cm⁻¹. These optical constants can be used to create model spectra for comparison to spectra from Solar System objects. We also analyzed the differences between the amorphous and crystalline H₂O-ice spectra, including weakening of bands and shifting of bands to shorter wavelength in amorphous H₂O-ice spectra. We have also observed two spectrally distinct phases of amorphous H₂O-ice.     

Exploration of faint absorption bands in the reflectance spectra of the asteroids by method of optimal smoothing: Vestoids

An optimization method of smoothing noisy spectra was developed to investigate faint absorption bands in the visual spectral region of reflectance spectra of asteroids and the compositional information derived from their analysis. The smoothing algorithm is called “optimal” because the algorithm determines the best running box size to separate weak absorption bands from the noise. The method is tested for its sensitivity to identifying false features in the smoothed spectrum, and its correctness of forecasting real absorption bands was tested with artificial spectra simulating asteroid reflectance spectra. After validating the method we optimally smoothed 22 vestoid spectra from SMASS1 [Xu, Sh., Binzel, R.P., Burbine, T.H., Bus, S.J., 1995. Icarus 115, 1-35]. We show that the resulting bands are not telluric features. Interpretation of the absorption bands in the asteroid spectra was based on the spectral properties of both terrestrial and meteorite pyroxenes. The bands located near 480, 505, 530, and 550 nm we assigned to spin-forbidden crystal field bands of ferrous iron, whereas the bands near 570, 600, and 650 nm are attributed to the crystal field bands of trivalent chromium and/or ferric iron in low-calcium pyroxenes on the asteroids' surface. While not measured by microprobe analysis, Fe³⁺ site occupancy can be measured with Mössbauer spectroscopy, and is seen in trace amounts in pyroxenes. We believe that trace amounts of Fe³⁺ on vestoid surfaces may be due to oxidation from impacts by icy bodies. If that is the case, they should be ubiquitous in the asteroid belt wherever pyroxene absorptions are found. Pyroxene composition of four asteroids of our set is determined from the band position of absorptions at 505 and 1000 nm, implying that there can be orthopyroxenes in all range of ferruginosity on the vestoid surfaces. For the present we cannot unambiguously interpret of the faint absorption bands that are seen in the spectra of 4005 Dyagilev, 4038 Kristina, 4147 Lennon, and 5143 Heracles. Probably there are other spectrally active materials along with pyroxenes on the surfaces of these asteroids.     

Martian xenon components in Shergotty mineral separates: Locations,sources, and trapping mechanisms

Abstract— Isotopic signatures and concentrations of xenon have been measured in Shergotty mineral separates by laser step heating. Martian atmosphere and ‘martian interior’ xenon are present, as is a spallation component. Martian atmospheric xenon is 5–10 times more concentrated in opaque minerals (magnetite, ilmenite, and pyrrhotite) and maskelynite than in pyroxenes, perhaps reflecting grain size variation. This is shown to be consistent with shock incorporation. A component consisting of solar xenon with a fission contribution, similar to components previously identified in martian meteorites and associated with the martian interior, is best defined in the pyroxene‐dominated separates. This component exhibits a consistent ¹²⁹Xe (¹²⁹Xe/¹³²Xe ?1.2) excess over solar/planetary (¹²⁹Xe/¹³²Xe ?1.04). We suggest that gas present in the melt, perhaps a mixture of interior xenon and martian atmosphere, was incorporated into the pyroxenes in Shergotty as the minerals crystallized.     

Assessing the spatial variability of the ~3 μm OH/H2O absorption feature in CM2 carbonaceous chondrites

H₂O and OH are readily detected in hydrated minerals in CM chondrites via reflectance spectroscopy due to their characteristic vibration absorptions at infrared wavelengths. Previous spectroscopic work on bulk powdered CM chondrites has shown that spectral parameters, like the wavelength position of the “3 μm absorption feature,” vary systematically with the extent to which the samples have been aqueously altered. However, it is yet unclear how these spectral features may vary across an intact meteorite chip when measured at spatial scales smaller than that of the individual components of the meteorite. Here, we explore the spatial variability of this spectral feature and others on intact CM2 chips which, unlike powders, retain their petrologic and textural characteristics. We also model the modal mineralogy of the bulk meteorite powders and correlate this with key spectral features, demonstrating that microscope Fourier transform infrared spectroscopic mapping provides a powerful, rapid, and non-destructive technique for assessing compositional diversity and variations in water–rock interactions in chondritic planetary materials. In all CM2 chondrites studied here, we find that variations in the position, shape, and strength of the 3 μm absorption feature reveal a single chondrite can exhibit as much spectral variation as the entire suite of CM2 chondrites. The observed variations in the position and shape of the 3 μm feature within individual CM2 chondrite chips suggest a range of alteration products (e.g., Mg-rich to Fe-rich phyllosilicates) are present and record sub-mm scale variations in the amount and/or chemistry of the altering fluids. The samples having experienced the most progressive aqueous alteration show the least amount of variability in features like the 3 μm absorption band minimum position, whereas the least altered samples exhibit the most variability. We also find that the bulk spectral signatures in the least altered samples appear to be biased toward the spectral signatures of clasts versus matrix. By extension, asteroid reflectance spectra exhibiting 3 μm absorption features consistent with those measured here may be interpreted in a similar framework in which the spectrum of what may appear to be the least altered asteroids represents an average that belies the true diversity of mineralogy and chemistry of the body.     

The lherzolitic shergottite Grove Mountains 99027: Rare earth element geochemistry

Abstract— We report here on an ion probe study of rare earth element (REE) geochemistry in the lherzolitic shergottite Grove Mountains (GRV) 99027. This meteorite shows almost identical mineralogy, petrology, and REE geochemistry to those of the lherzolitic shergottites Allan Hills (ALH) A77005, Lewis Cliff (LEW) 88516, and Yamato (Y‐) 793605. REE concentrations in olivine, pyroxenes, maskelynite, merrillite, and melt glass are basically comparable to previous data obtained from ALH A77005, LEW 88516, and Y‐793605. Olivine is the dominant phase in this meteorite. It is commonly enclosed by large (up to several mm) pigeonite oikocrysts. Non‐poikilitic areas consist of larger olivine grains (?mm), pigeonite, augite, and maskelynite. Minor merrillite (up to 150 μm in size) is widespread in non‐poikilitic regions, occurring interstitially between olivine and pyroxene grains. It is the main REE carrier in GRV 99027 and has relatively higher REEs (200–1000 × CI) than that of other lherzolitic shergottites. A REE budget calculation for GRV 99027 yields a whole rock REE pattern very similar to that of other lherzolites. It is characterized by the distinctive light REE depletion and a smooth increase from light REEs to heavy REEs. REE microdistributions in GRV 99027 strongly support the idea that all lherzolitic shergottites formed by identical igneous processes, probably from the same magma chamber on Mars. Despite many similarities in mineralogy, petrography, and trace element geochemistry, subtle differences exist between GRV 99027 and other lherzolitic shergottites. GRV 99027 has relatively uniform mineral compositions (both major elements and REEs), implying that it suffered a higher degree of sub‐solidus equilibration than the other three lherzolites. It is notable that GRV 99027 has experienced terrestrial weathering in the Antarctic environment, as its olivine and pyroxenes commonly display a light REE enrichment and a negative Ce anomaly. Caution needs to be taken in future chronological studies.     

Infrared diffuse reflectances (2.5–25 μm) of some meteorites

We measured emissionless infrared diffuse reflectances of some meteorites by using a Fourier transform infrared spectrophotometer to obtain additional information on identification of asteroidal surface materials. Although the spectral features of diffuse reflectances are apparently different from those of transmission spectra, the absorption bands of constituent minerals can be detected. C2 carbonaceous chondrite materials can be distinguished from C3 materials by the depth of their hydration bands around 3 and 6 μm. These hydration bands do not lose contrast by pulverization of the sample. Acid dissolution experiment shows that the 6.8-μm band in the spectra of the Murchison (C2) meteorite is probably due to carbonates. The enstatite meteorite examined (Norton County) shows absorption bands around 10 μm caused by pyroxene unlike the iron meteorite examined (Mundrabilla). Because these latter two meteorite types give similar spectra without strong absorption bands in the UV-Visible-near IR region, middle infrared spectra should be helpful in interpreting asteroidal surface materials when combined with the UV-Visible-near IR spectra.     

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.     

The Temperature-Dependent Spectrum of Methane Ice I between 0.7 and 5 μm and Opportunities for Near-Infrared Remote Thermometry

New infrared absorption coefficient spectra of pure methane ice I were measured at temperatures between 30 and 90 K, over wavelengths from 0.7 to 5 μm, along with spectra of methane ice II at 20 K and liquid methane at 93 K. The spectra were derived from transmission measurements through monocrystalline samples grown in a series of closed cells having interior dimensions ranging from 100 μm to 1 cm. The thicker samples permitted measurement of extremely weak absorption bands, with absorption coefficients as small as 0.003 cm⁻¹. We report 14 new absorption bands, which we tentatively assign to specific vibrational transitions. Two of the new bands are attributed to CH₃D. Measurements of the weaker CH₄ bands are particularly needed for interpreting spectral observations of Pluto and Triton, where a number of weak CH₄-ice absorption bands have been observed. The data presented in this paper complement studies of spectral transmission by thin films of methane ice, which are most suitable for measuring the stronger absorption bands. Temperature-dependent spectral features revealed by the new data offer the opportunity to determine CH₄-ice temperatures remotely, via near-infrared reflectance spectroscopy. This approach could prove particularly valuable for future spacecraft exploration of Pluto.     

Spectroscopy of synthetic Mg‐Fe pyroxenes I: Spin‐allowed and spin‐forbidden crystal field bands in the visible and near‐infrared

Abstract— Understanding the fundamental crystal chemical controls on visible and near‐infrared reflectance spectra of pyroxenes is critical to quantitatively assessing the mineral chemistry of pyroxenes viewed by remote sensing. This study focuses on the analysis of spectroscopic measurements of a comprehensive set of synthetic Mg‐Fe pyroxenes from the visible through the near‐infrared (0.3–2.6 μm) to address the constraints of crystal structure and Fe2+ content on spin‐forbidden and spin‐allowed crystal field absorptions in Ca‐free orthopyroxenes. The chemistry and oxidation state of the synthetic pyroxenes are characterized. Coordinated Mössbauer spectroscopy is used to determine site occupancy of Fe2+ in the M1 and M2 crystallographic sites. Properties of visible and near‐infrared absorption bands of the synthetic pyroxenes are quantified using the modified Gaussian model. The 1 and 2 μm spin‐allowed crystal field absorption bands move regularly with increasing iron content, defining a much tighter trend than observed previously. A spin‐allowed crystal field absorption band at 1.2 μm is explicitly verified, even at low total iron contents, indicating that some portion of Fe2+ resides in the M1 site. The 1.2 μm band intensifies and shifts to longer wavelengths with increasing iron content. At visible wavelengths, spin‐forbidden crystal field absorptions are observed in all iron‐bearing samples. The most prominent absorption near 506 nm, attributed to iron in the M2 site, shifts to slightly longer wavelengths with iron content. The purity and extent of this pyroxene series allows visible wavelength absorption bands to be directly assigned to specific transitions of Fe2+ in the M1 and M2 sites.     

A Martian PFS average spectrum: Comparison with ISO SWS

The evaluation of the planetary Fourier spectrometer performance at Mars is presented by comparing an average spectrum with the ISO spectrum published by Lellouch et al. [2000. Planet. Space Sci. 48, 1393.]. First, the average conditions of Mars atmosphere are compared, then the mixing ratios of the major gases are evaluated. Major and minor bands of CO₂ are compared, from the point of view of features characteristics and bands depth. The spectral resolution is also compared using several solar lines. The result indicates that PFS radiance is valid to better than 1% in the wavenumber range 1800-4200 cm⁻¹ for the average spectrum considered (1680 measurements). The PFS monochromatic transfer function generates an overshooting on the left-hand side of strong narrow lines (solar or atmospheric). The spectral resolution of PFS is of the order of 1.3 cm⁻¹ or better. A large number of narrow features to be identified are discovered.