ALBERT

Description: Sulfate minerals are important indicators for aqueous geochemical environments. The geology and mineralogy of Mars have been studied through the use of various remote-sensing techniques, including thermal (mid-infrared) emission and visible/near-infrared reflectance spectroscopies. Spectral analyses of spacecraft data (from orbital and landed missions) using these techniques have indicated the presence of sulfate minerals on Mars, including Fe-rich sulfates on the iron-rich planet. Each individual Fe-sulfate mineral can be used to constrain bulk chemistry and lends more information about the specific formational environment [e.g., Fe 2+ sulfates are typically more water soluble than Fe 3+ sulfates and their presence would imply a water-limited (and lower Eh) environment; Fe 3+ sulfates form over a range of hydration levels and indicate further oxidation (biological or abiological) and increased acidification]. To enable better interpretation of past and future terrestrial or planetary data sets, with respect to the Fe-sulfates, we present a comprehensive collection of mid-infrared thermal emission (2000 to 220 cm –1 ; 5–45 μm) and visible/near-infrared (0.35–5 μm) spectra of 21 different ferrous- and ferric-iron sulfate minerals. Mid-infrared vibrational modes (for SO 4 , OH, H 2 O) are assigned to each thermal emissivity spectrum, and the electronic excitation and transfer bands and vibrational OH, H 2 O, and SO 4 overtone and combination bands are assigned to the visible/near-infrared reflectance spectra. Presentation and characterization of these Fe-sulfate thermal emission and visible/near-infrared reflectance spectra will enable the specific chemical environments to be determined when individual Fe-sulfate minerals are identified.

Description: Although Fe-sulfate minerals occur only rarely on Earth as alteration products of sulfidic basalts or in hydrothermal systems, multiple lines of evidence point to the importance of Fe- (and other) sulfate minerals on the surface of Mars. One such martian data set comes from the MIMOS II Mössbauer spectrometers on the Mars Exploration Rovers, which acquired hundreds of spectra from the martian surface at two locations. Interpretation of those spectra has been limited by the lack of a comprehensive set of laboratory analog spectra of the broad range of naturally occurring sulfate minerals. Accordingly, this study reports Mössbauer data of 98 samples representing 47 different sulfate mineral species, all containing six- or higher-coordinated Fe. The resultant Mössbauer parameters are related to the local polyhedral environment around the Fe cation in each mineral to explain variations in spectral characteristics. Results show that the size of the coordination polyhedron is the best predictor of quadrupole splitting, which increases with both octahedral volume and mean bond length. Species within groups of structurally similar minerals are shown to have comparable spectral peaks that generally fall within small ranges. Although coordination polyhedron geometry is not necessarily unique to any particular mineral species or group, Mössbauer data can be used to help constrain mineral identifications from martian spectra. The number of mineral species is large, but the range of crystal structures and hyperfine parameters may be small, so that in many cases, individual minerals cannot be uniquely fingerprinted. Examples would include quenstedtite, coquimbite, kornelite, and lausenite, which have indistinguishable spectra, as do apjohnite, bilinite, dietrichite, and römerite. Overlap of Mössbauer parameters is a particular complication for identification of Fe 3+ -rich phases because the range of Mössbauer parameters for Fe 3+ in any coordination number is so small. Previous analyses of martian Mössbauer spectra reported the presence of jarosite ( Klingelhöfer et al. 2004 ; Morris et al. 2004 ) and an unspecific ferric sulfate ( Morris et al. 2008 ). New data presented here indicate that botryogen, metasideronatrite, and slavikite exhibit Mössbauer spectra similar to those attributed to jarosite at Meridiani Planum. Fibroferrite and rhomboclase have parameters similar to those observed at Arad Samra, and copiapite and parabutlerite could be present at Tyrone Mount Darwin and Berkner Island. Unique mineral identifications are generally not possible from Mössbauer data alone, particularly for paramagnetic phases, although combining Mössbauer results with other data sets enables a greater level of confidence in constraining mineralogy. This study provides a new expansive data set for future interpretation of iron sulfates on Mars.

Description: Phosphate minerals, while relatively rare, show a broad range of crystal structure types with linkages among PO 4 tetrahedra mimicking the hierarchy of polymerization of SiO 4 tetrahedra seen in silicate minerals. To augment previous Mössbauer studies of individual phosphate species and groups of species, this paper presents new Mössbauer data on 63 different phosphate samples, and integrates them with data on more than 37 phosphate species in 62 other studies from the literature. Variations in Mössbauer parameters of different sites in each mineral are then related to both the local polyhedral environment around the Fe cations and the overall structural characteristics of each species. The entire aggregated Mössbauer data set on phosphate minerals is juxtaposed against parameters obtained for spectra from the MIMOS spectrometers on Mars. This comparison demonstrates that signatures from many different phosphate or sulfate mineral species could also be contributing to Mars Mössbauer spectra. Results underscore the conclusion that unique mineral identifications are generally not possible from Mössbauer data alone, particularly for paramagnetic phases, although combining Mössbauer results with other data sets enables a greater level of confidence in constraining mineralogy. This study provides a wealth of new data on Fe-bearing phosphate minerals to bolster future analyses of Mössbauer spectra acquired on Mars.

Description: There is a strong case that asteroid 4 Vesta is the parent of the howardite, eucrite and diogenite (HED) meteorites. Models developed for the geological evolution of Vesta can satisfy the compositions of basaltic eucrites that dominate in the upper crust. The bulk compositional characteristics of diogenites - cumulate harzburgites and orthopyroxenites from the lower crust - do not fit into global magma ocean models that can describe the compositions of basaltic and cumulate eucrites. Recent more detailed formation models do make provision for a more complicated origin for diogenites, but this model has yet to be completely vetted. Compositional studies of bulk samples has led to the hypothesis that many diogenites were formed late by interaction of their parent melts with a eucritic crust, but those observations may alternatively be explained by subsolidus equilibration of trace elements between orthopyroxene and plagioclase and Ca-phosphate in the rocks. Differences in radiogenic Mg-26 content between diogenites and eucrites favors early formation of the former, not later formation. Understanding the origin of diogenites is crucial for understanding the petrologic evolution of Vesta. We have been doing coordinated studies of a suite of diogenites including petrologic investigations, bulk rock major and trace element studies, and in situ trace element analyses of orthopyroxene. Here we will focus on an especially unusual, and potentially key, diogenite, MIL 07001.

Description: The polymict breccias of the howardite, eucrite and diogenite (HED) clan of meteorites preserve records of regolith processes that occur on Vesta, their putative home world. These breccias -- howardites, polymict eucrites and polymict diogenites -- are impact-engendered mixtures of diogenites and eucrites. The compositions of polymict breccias can be used to constrain the lithologic diversity of the vestan crust and the excavation depths of these materials. We have done petrological and compositional studies of multiple samples of 5 polymict eucrites and 28 howardites to investigate these issues. Older analyses were done on samples of approx 0.5 gram mass by INAA; newer analyses on samples of approx 5 gram mass by XRF and ICP-MS. We estimate the percentage of eucritic material (POEM) of polymict breccias by comparing their Al and/or Ca contents to those of average basaltic eucrite and diogenite. Our samples have POEM ranging from 28 to 98; adding two polymict diogenites from extends the range to POEM 10. One hypothesis is that ancient, well-mixed vestan regolith has POEM approx 67 and has a higher content of admixed impactor material. Several of our howardites have POEM of 59-74 (Al and/or Ca contents +/- 10% of POEM 67); about a third have Ni contents 〉300 micro g/g suggesting they contain 〉2% chondritic material (CM and/or CR). These may be regolithic howardites. Only one (LEW 85313) contains Ne dominated by a solar wind (SW) component. PCA 02066 is dominated by impact-melt material of polymict parentage and petrologically appears to be a mature regolith breccia, yet it does not contain SW-Ne. GRO 95602 falls within the POEM window, contains SW-Ne], yet has a Ni content of 193 micro g/g. Its petrologic characteristics suggest it was formed from immature regolith (no polymict breccia clasts; no glass). Trace element characteristics of the polymict breccias demonstrate the dominance of main-group eucrites as the basaltic component. Mixing diagrams of Zr, Nb, Ba, Hf and Ta with Al show no evidence for a significant contribution from Stannern-trend eucrites. An exception is polymict eucrite LEW 86001 (POEM 92), which is dominated by Stannern-trend basaltic debris. Howardite LAP 04838 (POEM 84) has higher incompatible trace concentrations than other polymict breccias (excluding LEW 86001), and either contains a Stannern-trend basaltic component, or has a significant contributions from evolved eucrites like Nuevo Laredo.

Description: The occurrence of jarosite, other sulfates (e.g., Mg-and Ca-sulfates), and hematite along with silicic-lastic materials in outcrops of sedimentary materials at Meridiani Planum (MP) and detection of silica rich deposits in Gusev crater, Mars, are strong indicators of local acidic aqueous processes [1,2,3,4,5]. The formation of sediments at Meridiani Planum may have involved the evaporation of fluids derived from acid weathering of Martian basalts and subsequent diagenesis [6,7]. Also, our previous work on acid weathering of basaltic materials in a closed hydro-thermal system was focused on the mineralogy of the acid weathering products including the formation of jarosite and gray hematite spherules [8,9,10]. The object of this re-search is to extend our earlier qualitative work on acidic weathering of rocks to determine acidic dissolution rates of Mars analog basaltic materials at 80 C using a flow-thru reactor. We also characterized residual phases, including poorly crystalline or amorphous phases and precipitates, that remained after the treatments of olivine, siderite, and basalt which represent likely MP source rocks. This study is a stepping stone for a future simulation of the formation of MP rocks under a range of T and P.

Description: Sulfates have been identified on the martian surface during robotic surface exploration and by orbital remote sensing. Measurements at Meridiani Planum (MP) by the Alpha-Particle X-ray Spectrometer (APXS) and Mossbauer (MB) instruments on the Mars Exploration Rover Opportunity document the presence of a ubiquitous sulfate-rich outcrop (20-40% SO3) that has jarosite as an anhydrous Fe3+-sulfate [1- 3]. The presence of jarosite implies a highly acidic (pH 〈3) formation environment [4]. Jarosite and other sulfate minerals, including kieserite, gypsum, and alunite have also been identified in several locations in orbital remote sensing data from the MEx OMEGA and MRO CRISM instruments [e.g. 5-8]. Acid sulfate weathering of basaltic materials is an obvious pathway for formation of sulfate-bearing phases on Mars [e.g. 4, 9, 10]. In order to constrain acid-sulfate pathways on Mars, we are studying the mineralogical and chemical manifestations of acid-sulfate alteration of basaltic compositions in terrestrial environments. We have previously shown that acidsulfate alteration of tephra under hydrothermal conditions on the Puu Poliahu cone (summit region of Mauna Kea volcano, Hawaii) resulted in jarosite and alunite as sulfate-bearing alteration products [11-14]. Other, more soluble, sulfates may have formed, but were leached away by rain and melting snow. Acidsulfate processes on Puu Poliahu also formed hematite spherules similar (except in size) to the hematite spherules observed at MP as an alteration product [14]. Phyllosilicates, usually smectite }minor kaolinite are also present as alteration products [13]. We discuss here an occurrence of acid-sulfate alteration on Mauna Kea Volcano (Hawaii). We report VNIR spectra (0.35-2.5 microns ASD spectrometer), Mossbauer spectra (MER-like ESPI backscatter spectrometer), powder XRD (PANalytical), and major element chemical compositions (XRF with LOI and Fe redox) for comparison to similar data acquired or to be acquired by MRO-CRISM and MEx OMEGA, MERMB, MSL-CheMin, and MER and MSL APXS, respectively.