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Ureilites are ultramafic achondrite meteorites that likely represent a large parent body. Large olivine and pyroxene grains display a high degree of textural equilibrium, forming “triple-junction” contacts at their grain boundaries. However, ureilites also have primitive characteristics, for example high siderophile and carbon content, high noble gas content, and unequilibrated olivine and pyroxene compositions. So far, the origin of ureilites and their parent body are still debated as it is difficult to explain the observation of textural equilibrium juxtaposed with such primitive properties. Conventionally, ureilites are considered to be mantle residues from within an unknown, large rocky body. Because feldspar is completely depleted from most ureilite samples, it has been thought that the parent body accreted early and experienced extensive igneous differentiation processes, with primary heating attributed to short-lived 26Al decay in the early solar system. Here we report on polymict ureilite breccia Elephant Moraine 87720. We found that the sample has several unusually magnesian-rich olivine clasts with mg# (Mg/(Mg+Fe)) up to 98.7 and calcium-poor pyroxene with Wo as low as to 1.0. Moreover, we discovered two coarse-grained aluminous spinel grains with over 56.4-58.7 wt% Al2O3 and 11.3-11.8wt% Cr2O3, in contact with olivine and pyroxene grains. These aluminous spinel clasts are unique among ureilite samples. To determine the provenance of the spinel grains and other clasts (e.g., high magnesian olivine and low calcium pyroxene) in this sample, we conducted in situ oxygen 3-isotope analyses by Secondary Ion Mass Spectrometry SIMS (IMS 1280), University of Wisconsin-Madison. SIMS mineral data plot along the slope ~1 line in the oxygen 3-isotope diagram, similar to those of bulk ureilites (Greenwood et al., 2017, Chemie der Erde 77, 1-43) including ureilitic samples found in Almahata Sitta, with the same range of ∆17O (from –2.3‰ to –0.2‰). These grains follow the Fe-loss/addition trend defined by a molar plot of Fe/Mn versus molar Fe/Mg, showing a near constant and chondritic Mn/Mg ratio, falling in among common ureilitic compositions. We conclude that the origin of these clasts, including the aluminous spinel, is primarily ureilitic, but they extend the δ18O measurement for ureilites up to 9.7 ‰. We hypothesize a magmatic origin for these clasts that they were formed under low-oxygen fugacity, in a high Al/Si ratio hot melt, favouring the crystallization of Al-spinel instead of a Cr-rich endmember. The clasts in this EET 87720 specimen may possibly represent a new type of high Al, low Ca, low Cr lithic material within the ureilite parent body. Finally, we calculated a possible crystallization temperature of 1379 K using spinel-olivine equilibrium crystallization (Roeder et al 1979, Contrib. Min. Petrol. 6, 325-334). Our estimate corresponds well with the theoretical model proposed by Goodrich et al. (2004, Chemie der Erde 64, 283-327) that the UPB was hot, with a temperature above 1100 °C (1373 K). Our results are consistent with other petrological evidence and olivine-pigeonite-melt thermometry (Singletary and Grove, 2003, Met. Planet. Sci. 38, 95-108) which constrain smelting temperatures within the ureilite parent body.

The impact melt‐bearing breccias at the Ries impact structure, Germany, host degassing pipes: vertical structures that are inferred to represent conduits along which gases and fluids escaped to the surface, consistent with hydrothermal activity that occurs soon after an impact event. Although the presence of degassing pipes has been recognized within the well‐preserved and long‐studied ejecta deposits at the Ries, a detailed mineralogical study of their alteration mineralogy, as an avenue to elucidate their origins, has not been conducted to date. Through the application of high‐resolution in situ reflectance imaging spectroscopy and X‐ray diffraction, this study shows for the first time that the degassing pipe interiors and associated alteration are comprised of hydrated and hydroxylated silicates (i.e., Fe/Mg smectitic clay minerals with chloritic or other hydroxy‐interlayered material) as secondary hydrothermal mineral phases. This study spatially extends the known effects of impact hydrothermal activity into the ejecta deposits, beyond the crater rim. It has been suggested that the degassing pipes at the Ries are analogous to crater‐related pit clusters observed in impact melt‐bearing deposits on Mars, Ceres, and Vesta. The results of this work may inform on the presence of crustal volatiles and their interaction during the impact process on rocky bodies throughout the solar system. The Mars 2020 Perseverance rover may have the opportunity to investigate impact‐related features in situ; if so, this work suggests that such investigations may provide key information on the origin and formation of clay minerals on Mars as well as hold exciting implications for future Mars exploration.

Niobium and tantalum, rare metals and high field strength elements (HFSEs) that are essential to modern technologies, are concentrated among others in lithium-cesium-tantalum (LCT) pegmatites and rare metal granites. The most important hosts for Nb-Ta in these types of deposits are the columbite group minerals (columbite-tantalite), but at some ore deposits significant Ta is also contained in wodginite, microlite, and tapiolite. Previous solubility experiments of HFSE minerals have been limited to high temperatures because of the slow diffusivities of HFSEs in granitic melts. An experiment protocol is described herein that allows HFSE mineral solubilities to be determined at lower temperatures, more in line with the estimated solidus temperatures of LCT pegmatites and rare metal granites. This is achieved through the interaction of a melt that is enriched in high field strength elements (e.g., P and Nb or Ta) with a fluid enriched in a fluid-mobile element (FME, e.g., Mn). A starting glass enriched in a slow diffusing HFSE was synthesized, and HFSE mineral saturation is obtained via the diffusion of a FME into the melt via interaction with a fluid. This interaction can occur at much lower temperatures in reasonable experimental durations than for experiments that require diffusion of niobium and tantalum. The solubility product of columbite-(Mn) from the fluid-melt interaction experiment in a highly fluxed granitic melt at 700 °C is the same as those from dissolution and crystallization (reversal) experiments at the same P-T conditions. Thus, both methods produce reliable measurements of mineral solubility, and the differences in the metal concentrations in the quenched melts indicates that the solubility of columbite-(Mn) follows Henry's Law. Results show that columbite-(Mn) saturation can be reached at geologically reasonable concentrations of niobium in melts and manganese in hydrothermal fluids. This experimental protocol also allows the investigation of HFSE mineral crystallization by fluid-melt interactions in rare-metal pegmatites. Magmatic origins for columbite group minerals are well constrained, but hydrothermal Nb-Ta mineralization has also been proposed for pegmatite-hosted deposits such as Tanco, Greenbushes, and granite-hosted deposits such as Cínovec/Zinnwald, Dajishan, and Yichun. This study shows that columbite-(Mn), lithiophilite, and a Ca-Ta oxide mineral (that is likely microlite) crystallized from experiments in fluid-melt systems at temperatures as low as 650 °C at 200 MPa. It is important to note that HFSE minerals that crystallize from fluid-melt interactions texturally occur as euhedral crystals as phenocrysts in glass, i.e., are purely magmatic textures. Therefore, crystallization of HFSE minerals from fluid-melt interactions in rare metal granites and pegmatite deposits may be more widespread than previously recognized. This is significant because the formation of these deposits may require magmatic-hydrothermal interaction to explain the textures present in deposits worldwide, rather than always being the result of a single melt or fluid phase.

Knowing the amount and timing of water incorporation into the Moon has fundamental implications for our understanding of how the Earth–Moon system formed. Water has been detected in lunar samples but its abundance, distribution and origin are debated. To address these issues, we report water concentrations and hydrogen isotope ratios obtained by secondary ion mass spectrometry (SIMS) of plagioclase from ferroan anorthosites (FANs), the only available lithology thought to have crystallized directly from the lunar magma ocean (LMO). The measured water contents are consistent with previous results by Fourier transform infrared spectroscopy (FTIR). Combined with literature data, δD values of lunar igneous materials least-degassed at the time of their crystallization range from −280 to +310‰, the latter value being that of FAN 60015 corrected for cosmic ray exposure. We interpret these results as hydrogen isotopes being fractionated during degassing of molecular hydrogen (H_2) in the LMO, starting with the magmatic δD value of primordial water at the beginning of LMO being about −280‰, evolving to about +310‰ at the time of anorthite crystallization, i.e. during the formation of the primary lunar crust. The degassing of hydrogen in the LMO is consistent with those of other volatile elements. The wide range of δD values observed in lunar igneous rocks could be due to either various degrees of mixing of the different mantle end members, or from a range of mantle sources that were degassed to different degrees during magma evolution. Degassing of the LMO is a viable mechanism that resulted in a heterogeneous lunar interior for hydrogen isotopes.

Zinc and germanium enrichments have been discovered in sedimentary rocks in Gale Crater, Mars, by the Alpha Particle X-ray Spectrometer on the rover Curiosity. Concentrations of Zn (910 ± 840 ppm) and Ge (65 ± 58 ppm) are tens to hundreds of times greater than in Martian meteorites and estimates for average silicate Mars. Enrichments occur in diverse rocks including minimally to extensively altered basaltic and alkalic sedimentary rocks. The magnitude of the enrichments indicates hydrothermal fluids, but Curiosity has not discovered unambiguous hydrothermal mineral assemblages. We propose that Zn- and Ge-rich hydrothermal deposits in the source region were dispersed in siliciclastic sediments during transport into the crater. Subsequent diagenetic mobilization and fractionation of Zn and Ge is evident in a Zn-rich sandstone (Windjana; Zn ~4000 ppm, Ge ~85 ppm) and associated Cl-rich vein (Stephen; Zn ~8000 ppm, Ge ~60 ppm), in Ge-rich veins (Garden City; Zn ~2200 ppm, Ge ~650 ppm), and in silica-rich alteration haloes leached of Zn (30–200 ppm). In moderately to highly altered silica-rich rocks, Ge remained immobile relative to leached elements (Fe, Mn, Mg, and Ca), consistent with fluid interaction at pH ≪ 7. In contrast, crosscutting Ge-rich veins at Garden City suggest aqueous mobilization as Ge-F complexes at pH

We describe occurrences of palladoan melonite in intimate intergrowths with cobaltite-gersdorffite from the Neoproterozoic dunite-wehrlite-gabbro complexes of Kingash and Kuskanak, Eastern Sayans, Russia. The observed compositional trends of melonite are consistent with the overallvariations examined on the basis of numerous literature sources. The levels of Bi in NiTe2are normally limited to ≤0.25 Bi atoms per formula unit (apfu), under natural conditions. Greater levels (≤0.5 Bi apfu) are associated with the (Pd + Pt) enrichment in the palladoanvarieties. The telluride–sulfarsenide intergrowths probably formed at Kingash and Kuskanak late in the crystallization history of the ore zones, from microdroplets of residual melt rich in semimetals (Te, Bi, As) and noble metals (Pd and Ag), below the solidus of the enclosing gabbroicrocks and within a narrow range of temperatures (500–550°C). On the basis of our observations made on specimens of melonite and synthetic Ni(Te,Bi)2–x(x = 0.6), we infer that the limit of incorporation of Bi into a melonitetype phase is ≤0.5 Bi apfu.

Volcanic glasses are rarely preserved in the rock record, and the quality of preservation generally declines with increasing age. Records preserved in ancient basaltic glasses therefore provide important links between processes operating in the distant past, and those that are active on the Earth today. Microbial colonization has been linked to the formation of characteristic structures in basaltic glass, including tubules and granule-filled tubules, which are thought to be produced by microbially mediated glass dissolution. Structures of similar occurrence and morphology but filled almost entirely with fine-grained titanite have been documented in some ancient metabasalts. It has been suggested that the ancient titanite-mineralized structures are mineralized equivalents of hollow tubules in modern glassy basaltic rocks, but a direct link has not been firmly established. We report the discovery of tubular bioalteration structures in fresh and minimally altered basaltic glasses of middle Jurassic (164 Ma) age from the Stonyford Volcanic Complex (SFVC), Coast Range Ophiolite, California. Tubular structures hosted in unaltered basaltic glass are typically hollow, whilst those in zones of zeolitic alteration are mineralized by titanite. Tubules are continuous across zeolite-glass interfaces, which mark an abrupt change from titanite-filled to hollow tubules, demonstrating that titanite growth occurs preferentially within pre-existing tubular structures. Titanite mineralization in the SFVC represent a link between tubular structures in modern basaltic glass and titanite-mineralized features of similar morphology and spatial distribution in ancient metabasalts. Our observations support a link between textures in modern glassy basaltic rocks and some of the oldest-known putative ichnofossils.

Hollow tubular structures in subaqueously-emplaced basaltic glass may represent trace fossils caused by microbially-mediated glass dissolution. Mineralized structures of similar morphology and spatial distribution in ancient, metamorphosed basaltic rocks have widely been interpreted as ichnofossils, possibly dating to similar to 3.5 Ga or greater. Doubts have been raised, however, regarding the biogenicity of the original hollow tubules and granules in basaltic glass. In particular, although elevated levels of biologically-important elements such as C, S, N, and P as well as organic compounds have been detected in association with these structures, a direct detection of unambiguously biogenic organic molecules has not been accomplished. In this study, we describe the direct detection of proteins associated with tubular textures in basaltic glass using synchrotron X-ray spectromicroscopy. Protein-rich organic matter is shown to be associated with the margins of hollow and partly-mineralized tubules. Furthermore, a variety of tubule-infilling secondary minerals, including Ti-rich oxide phases, were observed filling and preserving the microtextures, demonstrating a mechanism whereby cellular materials may be preserved through geologic time.

Lunar impact melt deposits have unusual surface properties, unlike any measured terrestrial lava flow. Radar observations suggest that they are incredibly rough at decimeter scales, but they appear smooth in high-resolution, meter-scale optical images. The cause of their unusual surface roughness is unknown. In this work, we investigate the properties of impact melt deposits from seven lunar craters, ranging in size from 7.5 to 96 km in diameter, in an effort to understand the cause of their unique surface texture. We use data from the Lunar Reconnaissance Orbiter's (LRO) Mini-RF instrument to characterize the small-scale roughness of the deposits, data from the LRO Camera (LROC) to characterize their meter-scale morphology, and data from Chandrayaan-1's Moon Mineralogy Mapper (M3) to characterize their composition. This represents the most comprehensive study of the composition of lunar melt deposits completed to date. In particular, we applied a customized spectral unmixing model to the M3 data using laboratory spectra acquired from a range of possible lunar endmembers: pyroxene, olivine, fast-quenched lunar glass simulants, and impact melts and breccias (both synthetic and natural). We found that spectra derived from lunar melt deposits are typically modeled as a mix of the pyroxene and/or impact melts and breccias endmembers. Our modeled results suggest that lunar melt deposits are either crystalline deposits of pyroxene-rich rocks, or a mixture of glassy material and pyroxene minerals. The latter interpretation could explain the roughness observed in the Mini-RF data, if the melt deposits have a glassy surficial layer that shatters during impact gardening to produce decimeter scale blocks.

The ~15 Ma, 26 km diameter Ries impact structure in south-central Germany was one of the first terrestrial impact structures where evidence of impact-associated hydrothermal alteration was recognized. Previous studies suggested that pervasive, high-temperature hydrothermal activity was restricted to the area within the “inner ring” (i.e., the crater-fill impactite units). Here we present mineralogical evidence for localized hydrothermal activity in the ejecta beyond the crater rim in two previously unstudied settings: a pervasively altered lens of suevite ejecta directly overlying the Bunte Breccia at the Aumuhle quarry; and suevite ejecta at depth overlain by ~20 m of lacustrine sediments sampled by the Wornitzostheim 1965 drill core. A comprehensive set of X-ray diffraction analyses indicates five distinct alteration regimes (1) surficial ambient weathering characterized by smectite and a minor illitic component; (2) locally restricted hydrothermal activity characterized by an illitic component and minor smectite; (3) hydrothermal activity at depth characterized by smectite, a minor illitic component, and calcite; (4) hydrothermal activity at depth characterized by smectite, a minor illitic component, calcite, zeolites, and clinochlore; and (5) pervasive hydrothermal activity at depth characterized by smectite, a minor illitic component, and minor clinochlore. These data spatially extend the Ries postimpact hydrothermal system suggesting a much more extensive, complex, and dynamic system than previously thought. Constraining the mineralogical alteration regimes at the Ries impact structure may also further our understanding of impact-associated phyllosilicate formation on Mars with implications for climate models and habitability.

Meteorite impacts on Earth and Mars can generate hydrothermal systems that alter the primary mineralogies of rocks and provide suitable environments for microbial colonization. We investigate a calcite–marcasite-bearing vug at the ~23 km diameter Haughton impact structure, Devon Island, Nunavut, Canada, using imaging spectroscopy of the outcrop in the field (0.65–1.1 μm) and samples in the laboratory (0.4–2.5 μm), point spectroscopy (0.35–2.5 μm), major element chemistry, and X-ray diffraction analyses. The mineral assemblages mapped at the outcrop include marcasite; marcasite with minor gypsum and jarosite; fibroferrite and copiapite with minor gypsum and melanterite; gypsum, Fe3+ oxides, and jarosite; and calcite, gypsum, clay, microcline, and quartz. Hyperspectral mapping of alteration phases shows spatial patterns that illuminate changes in alteration conditions and formation of specific mineral phases. Marcasite formed from the postimpact hydrothermal system under reducing conditions, while subsequent weathering oxidized the marcasite at low temperatures and water/rock ratios. The acidic fluids resulting from the oxidation collected on flat-lying portions of the outcrop, precipitating fibroferrite + copiapite. That assemblage then likely dissolved, and the changing chemistry and pH resulting from interaction with the calcite-rich host rock formed gypsum-bearing red coatings. These results have implications for understanding water–rock interactions and habitabilities at this site and on Mars.

The presence of potential microbial trace fossils (endolithic microborings) has been well documented in oceanic basaltic pillow lavas, hyaloclastites, tuffs, and transitional subglacial marine lavas in the past 30 yr. Despite their evident abundance in oceanic to subglacial environments, they have not been observed in continental basalts that were not erupted in marine or subglacial settings. To expand the record of putative endolithic microborings in volcanic rocks to nonmarine, continental lacustrine environments, we examined hydrovolcanic pyroclastic deposits in the Fort Rock volcanic field, central Oregon. This study presents the textures, mineralogy, and geochemistry of basaltic tuffs containing possible endolithic microborings comparable in morphology, size, and distribution to those described in earlier oceanic and subglacial basalt studies. We observed a variety of tubular and granular textures that show evidence of biogenic morphologies and behavior, and a primary geological context that expresses their age and syngenicity. Petrographic relationships with secondary phases (chabazite, nontronite, calcite) indicate that the construction of microtunnels occurred in saline, alkaline fluids at temperatures of 25–80 °C. In addition, positive correlations were observed between the extent of aqueous (abiotic) alteration and both the abundance of microtunnels and morphological type. These correlations suggest that microtunnels were more readily formed where there was greater abiotic alteration-fluid flux and that the resulting change in chemical composition of those fluids may have had a direct influence on the formation process or possibly the type of constructing microbe. This work adds to understanding of factors controlling microtunnel formation and is the first account of putative endolithic microborings in a continental lacustrine setting. This new information may also have implications in the search for habitable extraterrestrial environments, such as on Mars.

Modern Martian dust is similar in composition to the global soil unit and bulk basaltic Mars crust, but it is enriched in S and Cl. The Alpha Particle X-ray Spectrometer (APXS) on the Mars Science Laboratory Curiosity rover analyzed air fall dust on the science observation tray (o-tray) in Gale Crater to determine dust oxide compositions. The o-tray dust has the highest concentrations of SO3 and Cl measured in Mars dust (SO3 8.3%; Cl 1.1 wt %). The molar S/Cl in the dust (3.35 ± 0.34) is consistent with previous studies of Martian dust and soils (S/Cl = 3.7 ± 0.7). Fe is also elevated ~25% over average Mars soils and the bulk crust. These enrichments link air fall dust with the S-, Cl-, and Fe-rich X-ray amorphous component of Gale Crater soil. Dust and soil have the same S/Cl, constraining the surface concentrations of S and Cl on a global scale.

Our understanding of the impact cratering process continues to evolve and, even at well-known and well-studied structures, there is still much to be learned. Here, we present the results of a study on impact-generated melt phases within ejecta at Barringer Crater, Arizona, one of the first impact craters on Earth to be recognized and arguably the most famous. We report on previously unknown impact melt-bearing breccias that contain dispersed fragments of the projectile as well as impact glasses that contain a high proportion of projectile material – higher than any other glasses previously reported from this site. These glasses are distinctly different from so-called “melt beads” that are found as a lag deposit on the present-day erosion surface and that we also study. It is proposed that the melts in these impact breccias were derived from a more constrained sub-region of the melt zone that was very shallow and that also had a larger projectile contribution. In addition to low- and high-Fe melt beads documented previously, we document Ca–Mg-rich glasses and calcite globules within silicate glass that provide definitive evidence that carbonates underwent melting during the formation of Barringer Crater. We propose that the melting of dolomite produces Ca–Mg-rich melts from which calcite is the dominant liquidus phase. This explains the perhaps surprising finding that despite dolomite being the dominant rock type at many impact sites, including Barringer Crater, calcite is the dominant melt product. When taken together with our estimate for the amount of impact melt products dispersed on, and just below, the present-day erosional surface, it is clear that the amount of melt produced at Barringer Crater is higher than previously estimated and is more consistent with recent numerical modeling studies. This work adds to the growing recognition that sedimentary rocks melt during hypervelocity impact and do not just decompose and/or devolatilize as was previously thought. This has implications for understanding the processes and products of impacts into sedimentary rocks and for estimating the amount of climatically active gases released by impact events.

We investigate an outcrop of ∼187 Ma lacustrine pillow basalts of the Talcott Formation exposed in Meriden, Connecticut, USA, focusing on coordinated analyses of one pillow lava to characterize the aqueous history of these basalts in the Hartford Basin. This work uses a suite of multidisciplinary measurements, including hyperspectral imaging, other spectroscopic techniques, and chemical and mineralogical analyses, from the microscopic scale up to the scale of an outcrop. The phases identified in the sample are albite, large iron oxides, and titanite throughout; calcite in vesicles; calcic clinopyroxene, aegirine, and Fe/Mg-bearing clay in the rind; and fine-grained hematite and pyroxenes in the interior. Using imaging spectroscopy, the chemistry and mineralogy results extend to the hand sample and larger outcrop. From all of the analyses, we suggest that the pillow basalts were altered initially after emplacement, either by heated lake water or magmatic fluids, at temperatures of at least 400–600 °C, and the calcic clinopyroxenes and aegirine identified in the rind are a preserved record of that alteration. As the hydrothermal system cooled to slightly lower temperatures, clays formed in the rind, and, during this alteration, the sample oxidized to form hematite in the matrix of the interior and Fe 3+ in the pyroxenes in the rind. During the waning stages of the hydrothermal system, calcite precipitated in vesicles within the rind. Later, diagenetic processes albitized the sample, with albite replacing plagioclase, lining vesicles, and accreting onto the exterior of the sample. This albitization or Na-metasomatism occurred when the lake within the Hartford Basin evaporated during a drier past climatic era, resulting in Na-rich brines. As Ca-rich plagioclase altered to albite, Ca was released into solution, eventually precipitating as calcite in previously-unfilled vesicles, dominantly in the interior of the pillow. Coordinated analyses of this sample permit identification of the alteration phases and help synthesize the aqueous history of pillow lavas of the Talcott Formation. These results are also relevant to Mars, where volcanically-resurfaced open basin lakes have been found, and this Hartford Basin outcrop may be a valuable analog for any potential volcano–lacustrine interactions. The results can also help to inform the utility and optimization of potentially complementary, synergistic, and uniquely-suited techniques for characterization of hydrothermally-altered terrains.

Studies of shock metamorphism of feldspar typically rely on qualitative petrographic observations, which, while providing invaluable information, can be difficult to interpret. Shocked feldspars, therefore, are now being studied in greater detail by various groups using a variety of modern techniques. We apply in situ micro-X-ray diffraction (μXRD) to shocked lunar and terrestrial plagioclase feldspar to contribute to the development of a quantitative scale of shock deformation for the feldspar group. Andesine and labradorite from the Mistastin Lake impact structure, Labrador, Canada, and anorthite from Earth's Moon, returned during the Apollo program, were examined using optical petrography and assigned to subgroups of the optical shock level classification system of Stöffler (1971). Two-dimensional μXRD patterns from the same samples revealed increased peak broadening in the chi dimension (χ), due to strain-related mosaicity, with increased optical signs of deformation. Measurement of the full width at half maximum along χ (FWHMχ) of these peaks provides a quantitative way to measure strain-related mosaicity in plagioclase feldspar as a proxy for shock level.

27 Al magic-angle spinning nuclear magnetic resonance (MAS NMR) and 27 Al triple quantum (3Q) MAS NMR spectroscopy have been performed at 21.1 Tesla (T), as a direct probe of environment around Al in synthetic Ca-Tschermak’s clinopyroxene, CaAlAlSiO 6 , henceforward referred to as CaTs. For comparison, 27 Al MAS NMR of CaTs has also been performed at 14.1 T. The 27 Al 3QMAS NMR spectrum of CaTs has revealed various local environments around octahedral and tetrahedral Al, both ordered and disordered, symmetrical, and distorted. Rietveld refinement of powder X-ray diffraction data has confirmed the high-temperature, long-range disordered C 2/ c structure for this sample. The 27 Al MAS NMR spectra of CaTs look broadly similar at 14.1 and 21.1 T. Both spectra exhibit two distinct peaks at the octahedral site and an irregularly shaped, broad tetrahedral site. The line widths are significantly broader at lower field and the 27 Al 3QMAS NMR spectrum at 21.1 T exhibits several additional peaks. At least three peaks were resolved at the octahedral site (in both the MAS spectrum along F2 and the 3Q spectrum along F1), whereas two peaks are clearly resolved at the tetrahedral site at 21.1 T. One tetrahedral peak, observed at both fields, is broad in F1 and narrow in F2, spread along the isotropic shift diagonal, indicating a highly disordered but relatively symmetric environment. The second peak, newly observed at 21.1 T, is narrow in F1 but very broad in F2, indicating an ordered but highly distorted environment. This peak has not been observed at lower magnetic field strengths. Octahedral peak assignments have been made according to the number of Al atoms in the six tetrahedral sites around M1, where an increasing number of NNN tetrahedral Al (2Al, 3Al, and 4Al) is correlated with displacement of the chemical shift to higher frequency. Assigned sites are similar to the local tetrahedral environments around M1 in ordered P 2 1 / n or C 2 structures, suggesting the presence of ordered domains in this otherwise disordered C 2/ c structure. To aid in the interpretation of these tetrahedral Al environments, density functional theory (DFT) calculations have been performed using two approximations of the CaTs crystal structure: fully ordered tetrahedral chains or fully disordered tetrahedral chains. These calculations suggest that the tetrahedral Al site is a sensitive indicator of order-disorder in CaTs. Tetrahedral Al sites in ordered tetrahedral chains (Si-O-Al-O-Si…) are predicted to have only large C Q , whereas tetrahedral Al sites in disordered systems (Al-O-Al-O-Al…) are predicted to have only small C Q . Both environments appear to exist in the synthetic CaTs sample in this study. Cation order-disorder has implications for thermobarometry based on CaTs-containing pyroxenes. The discovery of the new highly distorted tetrahedral site at ultrahigh magnetic field suggests that highly distorted Al sites in silicate minerals may be NMR-invisible in 27 Al 3QMAS NMR spectra acquired at lower fields, and these will have been systematically overlooked. This underscores the necessity to collect 27 Al NMR spectra of silicates at the highest available magnetic field strength.

Two-dimensional X-ray diffraction data contain information about not only the type of mineral phases present in an assemblage, but also the textural or grain size relationships between minerals in a sample. For minerals within a certain grain size range, ~0.1 to 100 μm, the appearance and characteristics of a Debye ring can reveal the mean grain size of a sample. In this contribution, using mineral and rock samples of known grain size ranges, we investigate the applicability of calculating the grain size of a material using a two-dimensional X-ray diffraction crystallite size analysis method for micrometer-sized materials. A radial integration technique was used to derive the number of grains contributing to produce diffraction spots in the Debye ring. Monomineralic pyroxene and magnetite samples of known grain size ranges were analyzed, and the calculated grain size was observed to broadly correlate with the sample size except at the upper and lower extremes. To evaluate the technique on broader geological materials, polymineralic basalt samples with known grain size ranges were analyzed, and the calculated grain sizes did not correlate with the size of the rock fragments, but did correlate closely with the size of the individual mineral grains. Using a Bruker D8 Discover X-ray diffractometer with a 300 μm nominal incident beam diameter, the effectiveness of the applied method appeared limited to the grain size range of ~15–63 μm for monomineralic samples. The method is further limited by several complicating factors and assumptions, including the requirement for the crystallite size to correlate with the sample grain size. The effective range of this method will vary with different instrumental and experimental conditions. When applying this method to calculate the grain size of geological materials, the calculated result should be interpreted as a minimum estimate of the grain size.

Under acidic, weathering conditions, silver (Ag) is considered to be highly mobile and can be dispersed within near-surface environments. In this study, a range of regolith materials were sampled from three abandoned open pit mines located in the Iberian Pyrite Belt, Spain. Samples were analyzed for Ag mineralogy, content, and distribution using micro-analytical techniques and high-resolution electron microscopy. While Ag concentrations were variable within these materials, elevated Ag concentrations occurred in gossans. The detection of Ag within younger regolith materials, i.e., terrace iron formations and mine soils, indicated that Ag cycling was a continuous process. Microbial microfossils were observed within crevices of gossan and their presence highlights the preservation of mineralized cells and the potential for biogeochemical processes contributing to metal mobility in the rock record. An acidophilic, iron-oxidizing microbial consortium was enriched from terrace iron formations. When the microbial consortium was exposed to dissolved Ag, more than 90% of Ag precipitated out of solution as argentojarosite. In terms of biogeochemical Ag cycling, this demonstrates that Ag re-precipitation processes may occur rapidly in comparison to Ag dissolution processes. The kinetics of Ag mobility was estimated for each type of regolith material. Gossans represented 0.6–146.7 years of biogeochemical Ag cycling while terrace iron formation and mine soils represented 1.9–42.7 years and 0.7–1.6 years of Ag biogeochemical cycling, respectively. Biogeochemical processes were interpreted from the chemical and structural characterization of regolith material and demonstrated that Ag can be highly dispersed throughout an acidic, weathering environment.

Ore minerals of niobium and tantalum are typically associated with pegmatites and rare metal granites; these include columbite, tantalite, wodginite, titanowodginite, microlite and pyrochlore. Solubility and crystallization mechanisms for columbite-(Mn) and tantalite-(Mn) have been extensively studied in haplogranitic melts, with little research into other ore minerals. In this study the solubilities of wodginite, titanowodginite, microlite and pyrochlore are compared to those for columbite-(Mn) and tantalite-(Mn) in a flux-rich haplogranitic melt of alumina saturation index (ASI) 1.0 (ASILi of 0.83) at 700–850 °C and 200 MPa. The effect of melt composition on the solubilities of wodginite, titanowodginite, and microlite compared to tantalite-(Mn) is also investigated in highly fluxed haplogranitic melts of ASI 1.0, 1.10, and 1.24 (ASILi of 0.83, 0.90, 1.02), at 700 °C and 800 °C and 200 MPa. The log solubility product (logKsp) at 750 °C and melt ASI of 1.0 is highest for tantalite-(Mn) (−2.32 mol2/kg2) followed by columbite-(Mn) (−2.68 mol2/kg2), and pyrochlore (−3.71 mol3/kg3) titanowodginite (−3.73 mol3/kg3), wodginite (−3.77 mol3/kg3), and microlite (−3.78 mol3/kg3), the latter four of which are almost identical within error. However, solubility can also be expressed as a mineral-melt partition coefficient, with higher partition coefficients reflecting lower solubilities. The tantalum mineral-melt partition coefficients of wodginite (27.0), titanowodginite (30.2), and tantalite-(Mn) (29.6) are identical within error; microlite is higher (80.3, reflected by lower concentrations of tantalum in the melt for stoichiometric saturation) because it contains a major melt cation, sodium. The niobium mineral-melt partition coefficient for columbite-(Mn) (66.1) is higher than for pyrochlore (50.1). Wodginite, titanowodginite, pyrochlore, columbite-(Mn) and tantalite-(Mn) have similar temperature and melt composition dependences, but conversely, microlite solubility increases with ASI. As all studied minerals have been shown to have similar relative solubilities at stoichiometric saturation, it can be concluded that, in general, the presence of bivalent (Ca, Mn, Fe) and some tetravalent cations (Sn, Ti) control which tantalum and niobium phases crystallize in rare metal deposits.

Precipitation of calcium carbonate (CaCO3(s) ) can be driven by microbial activity. Here, a systematic approach is used to identify the morphological and mineralogical characteristics of CaCO3(s) precipitated during the heterotrophic growth of micro-organisms isolated from polar environments. Focus was placed on establishing mineralogical features that are common in bioliths formed during heterotrophic activity, while in parallel identifying features that are specific to bioliths precipitated by certain microbial phylotypes. Twenty microbial isolates that precipitated macroscopic CaCO3(s) when grown on B4 media supplemented with calcium acetate or calcium citrate were identified. A multimethod approach, including scanning electron microscopy, high-resolution transmission electron microscopy, and micro-X-ray diffraction (μ-XRD), was used to characterize CaCO3(s) precipitates. Scanning and transmission electron microscopy showed that complete CaCO3(s) crystal encrustation of Arthrobacter sp. cells was common, while encrustation of Rhodococcus sp. cells did not occur. Several euhedral and anhedral mineral formations including disphenoid-like epitaxial plates, rhomboid-like aggregates with epitaxial rhombs, and spherulite aggregates were observed. While phylotype could not be linked to specific mineral formations, isolates tended to precipitate either euhedral or anhedral minerals, but not both. Three anhydrous CaCO3(s) polymorphs (calcite, aragonite, and vaterite) were identified by μ-XRD, and calcite and aragonite were also identified based on TEM lattice-fringe d value measurements. The presence of certain polymorphs was not indicative of biogenic origin, although several mineralogical features such as crystal-encrusted bacterial cells, or casts of bacterial cells embedded in mesocrystals are an indication of biogenic origin. In addition, some features such as the formation of vaterite and bacterial entombment appear to be linked to certain phylotypes. Identifying phylotypes consistent with certain mineralogical features is the first step toward discovering a link between these crystal features and the precise underlying molecular biology of the organism precipitating them.

Guyanaite, naturally occurring β-CrOOH, has been identified in a xenolith of Cr-rich omphacitite from the Moses Rock diatreme in the Navajo Volcanic Field of the southwestern United States. It occurs as the dominant phase in small clusters of accessory minerals, intergrown with kosmochlor-rich omphacite, zincian chromite, eskolaite, and carmichaelite. The assemblage is interpreted as the result of metasomatism of chromite-bearing serpentinite by slab-derived fluids during subduction of the Farallon Plate in Laramide time. At the time of entrainment of the xenolith, the rock was undergoing prograde metamorphism, with guyanaite dehydrating to eskolaite plus water. This reaction, and the coeval dehydration of the inferred accompanying host serpentinites (which would have been much more volumetrically significant), provided water for hydration of the subcontinental upper mantle, contributing to uplift of the Colorado Plateau. Recognition of guyanaite as a component of a subducted slab supports recent proposals, based on laboratory experiments, that high-pressure polymorphs of other common crustal oxy-hydroxide minerals such as boehmite and goethite (i.e., high-pressure δ-AlOOH and ɛ-FeOOH) can also transport and store water in the mantle.

A temperature-controlled sample stage with an operational range of ~60 °C above or below ambient laboratory temperature (~ −35 to 85 °C) was constructed for in situ X-ray diffraction of minerals and materials using a Bruker D8 Discover diffractometer with θ-θ geometry. The stage was primarily designed for characterizing mirabilite-bearing samples from a Mars analog High Arctic perennial cold spring at an in situ temperature. Operation of the stage was demonstrated through the analysis of a synthetic sample of the hydrated sodium sulfate, mirabilite (Na 2 SO 4 ·10H 2 O). Mirabilite was held at −25 °C for approximately two hours without significant dehydration and then incrementally warmed to ambient laboratory temperature at 5 °C intervals, during the acquisition of in situ diffraction data. At ambient laboratory temperature, the mirabilite dehydrated and only polycrystalline thenardite (Na 2 SO 4 ) remained. Preliminary analysis of the cold spring precipitates demonstrates that when mirabilite is present in the sample the dehydration reaction is occurring between collection and analysis at ambient laboratory temperature. This temperature-controlled stage was designed for versatility and ease of X-ray access, with applications that can extend to many geological and planetary settings, including Mars analog environments.

Recovery of phosphorus from wastewater as calcium phosphate could diminish the need for mining of scarce phosphate rock resources. This study introduces a novel approach to phosphorus recovery by precipitation of calcium phosphate granules in anaerobic treatment of black water. The granules formed in the Upflow Anaerobic Sludge Blanket (UASB) reactor at lab- and demonstration-scale were analyzed for chemical composition and mineralogy by Inductively Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES), Electron microprobe (EMP), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy and micro X-ray Diffraction (XRD). The granules had a diameter of 1–2 mm, organic content of 33 wt%, and phosphorus content of 11–13 wt%. Three calcium phosphate phases were identified in the granules: hydroxyapatite, calcium phosphate hydrate and carbonated hydroxyapatite. Without any addition of chemicals, 7 gP/person/year can be recovered with the calcium phosphate granules, representing 2% of the incoming phosphorus in the UASB reactor. As the heavy metal content was lower compared to other phosphorus recovery products, phosphate rock and phosphorus fertilizer, the calcium phosphate granules could be considered as a new phosphorus product.

It has long been suggested that hydrothermal systems might have provided habitats for the origin and evolution of early life on Earth, and possibly other planets such as Mars. In this contribution we show that most impact events that result in the formation of complex impact craters (i.e., >2–4 and >5–10 km diameter on Earth and Mars, respectively) are potentially capable of generating a hydrothermal system. Consideration of the impact cratering record on Earth suggests that the presence of an impact crater lake is critical for determining the longevity and size of the hydrothermal system. We show that there are six main locations within and around impact craters on Earth where impact-generated hydrothermal deposits can form: (1) crater-fill impact melt rocks and melt-bearing breccias; (2) interior of central uplifts; (3) outer margin of central uplifts; (4) impact ejecta deposits; (5) crater rim region; and (6) post-impact crater lake sediments. We suggest that these six locations are applicable to Mars as well. Evidence for impact-generated hydrothermal alteration ranges from discrete vugs and veins to pervasive alteration depending on the setting and nature of the system. A variety of hydrothermal minerals have been documented in terrestrial impact structures and these can be grouped into three broad categories: (1) hydrothermally-altered target-rock assemblages; (2) primary hydrothermal minerals precipitated from solutions; and (3) secondary assemblages formed by the alteration of primary hydrothermal minerals. Target lithology and the origin of the hydrothermal fluids strongly influences the hydrothermal mineral assemblages formed in these post-impact hydrothermal systems. There is a growing body of evidence for impact-generated hydrothermal activity on Mars; although further detailed studies using high-resolution imagery and multispectral information are required. Such studies have only been done in detail for a handful of martian craters. The best example so far is from Toro Crater (Marzo, G.A., Davila, A.F., Tornabene, L.L., Dohm, J.M., Fairen, A.G., Gross, C., Kneissl, T., Bishop, J.L., Roush, T.L., Mckay, C.P. [2010]. Icarus 208, 667–683). We also present new evidence for impact-generated hydrothermal deposits within an unnamed ∼32-km diameter crater ∼350 km away from Toro and within the larger Holden Crater. Synthesizing observations of impact craters on Earth and Mars, we suggest that if there was life on Mars early in its history, then hydrothermal deposits associated with impact craters may provide the best, and most numerous, opportunities for finding preserved evidence for life on Mars. Moreover, hydrothermally altered and precipitated rocks can provide nutrients and habitats for life long after hydrothermal activity has ceased.

Dioctahedral clays from an active continental geothermal system have been studied to assess their usefulness as proxies of paleo-hydrological and thermal conditions in the subsurface. Drill cuttings from Well WK244 in the Te Mihi area of the Wairakei Geothermal Field, New Zealand, were analyzed to determine the mineralogical, morphological, and isotopic characteristics of hydrothermal clays in these samples. Mixed-layer illite-dioctahedral smectite (I-S) and R0 chlorite-trioctahedral smectite are the main clay minerals, with I-S clays varying downward from R1 to R3 ordering and 50 to >90% illite over 160 m. The proportion of illite in I-S correlates positively with downhole temperature (r = 0.98) and I-S morphology changes from high aspect ratio ribbons, laths, and hairy fibers to pseudo-hexagonal plates with depth. Swelling clay percentages determined using the methylene blue method show a strong positive correlation with %S in I-S (r = 0.91), validating use of methylene blue as a rapid field tool for characterizing the smectite to illite transition in this active geothermal environment. The oxygen isotopic composition of I-S (dd18OI-S) decreases systematically with depth, and mostly reflects a progressive increase in subsurface temperature during clay formation. Estimates of water/rock ratios calculated using δ18OI-S values display stratigraphic variability that corresponds to variations in permeability. Oxygen isotopic measurements of I-S are a useful tool for understanding reservoir and permeability evolution in such geothermal systems and their related fossil analogs.

Spectroscopy in planetary science often provides the only information regarding the compositional and mineralogical make up of planetary surfaces. The methods employed when curve fitting and modelling spectra can be confusing and difficult to visualize and comprehend. Researchers who are new to working with spectra may find inadequate help or documentation in the scientific literature or in the software packages available for curve fitting. This problem also extends to the parameterization of spectra and the dissemination of derived metrics. Often, when derived metrics are reported, such as band centres, the discussion of exactly how the metrics were derived, or if there was any systematic curve fitting performed, is not included. Herein we provide both recommendations and methods for curve fitting and explanations of the terms and methods used. Techniques to curve fit spectral data of various types are demonstrated using simple-to-understand mathematics and equations written to be used in Microsoft Excel software, free of macros, in a cut-and-paste fashion that allows one to curve fit spectra in a reasonably user-friendly manner. The procedures use empirical curve fitting, include visualizations, and ameliorates many of the unknowns one may encounter when using black-box commercial software. The provided framework is a comprehensive record of the curve fitting parameters used, the derived metrics, and is intended to be an example of a format for dissemination when curve fitting data. An introduction to empirical curve fitting UVvisNIR, and other spectra.An introduction to semi-automated methods for Gaussian Fitting.An introduction to common data analysis techniques used by reflectance spectroscopists.Curve fitting using Microsoft Excel.

The Wood Lake meteorite was found in the Muskoka region of Ontario in July 2003. We examine the mineralogy, physical properties, shock, and weathering state of this recently reported Canadian meteorite. Bulk physical properties for Wood Lake (bulk density 3.57 ± 0.10 g/cm3, grain density 3.64 ± 0.01 g/cm3, and magnetic susceptibility log χ = 5.17) are typical of slightly weathered H chondrite falls and consistent with visual observations of its observed low weathering state (W1). Reconnaissance X-ray micro computed tomography of a Wood Lake fragment yields a similar bulk density (3.56 g/cm3) and allows for a three-dimensional description of the meteorite. Petrographic and electron probe microanalysis examination of the Wood Lake meteorite reveal sharp definition of chondrule margins, occasional mesostasis chondrule glass, only minor development of recrystallized matrix feldspar, and little variation in silicate chemical compositions, indicating Wood Lake to be an H4 ordinary chondrite. Mineral chemistry for Wood Lake olivine (Fa18.6 ± 0.7, n = 26) and low-Ca pyroxene (Fs17.5 ± 2.6, n = 16) agrees well with H chondrite averages for these minerals. The bulk of the stone has undergone a low to moderate level of shock (S3), as indicated in thin section by undulose optical extinction and the presence of planar dislocations in olivine and pyroxene grains. Moderate distortion of olivine crystal structures observed using in situ micro X-ray diffraction quantifies the shock deformation as a full width half maximum (FWHMχ) of 3.38° ± 1.13° (16 reflections from seven olivine grains), consistent with shock stage S3 ordinary chondrites. Wood Lake is confirmed as a new Canadian meteorite find that likely arrived on Earth not long before it was recovered.

Recent observations of carbonate minerals in ancient Martian rocks have been interpreted as evidence for the former presence of circumneutral solutions optimal for carbonate precipitation. Sampling from surface and subsurface regions of the low-pH system of Río Tinto has shown, unexpectedly, that carbonates can form under diverse macroscopic physicochemical conditions ranging from very low to neutral pH (1.5-7.0). A multi-technique approach demonstrates that carbonate minerals are closely associated with microbial activity. Carbonates occur in the form of micron-size carbonate precipitates under bacterial biofilms, mineralization of subsurface colonies, and possible biogenic microstructures including globules, platelets and dumbbell morphologies. We propose that carbonate precipitation in the low-pH environment of Río Tinto is a process enabled by microbially-mediated neutralization driven by the reduction of ferric iron coupled to the oxidation of biomolecules in microbially-maintained circumneutral oases, where the local pH (at the scale of cells or cell colonies) can be much different than in the macroscopic environment. Acidic conditions were likely predominant in vast regions of Mars over the last four billion years of planetary evolution. Ancient Martian microbial life inhabiting low-pH environments could have precipitated carbonates similar to those observed at Río Tinto. Preservation of carbonates at Río Tinto over geologically significant timescales suggests that similarly-formed carbonate minerals could also be preserved on Mars. Such carbonates could soon be observed by the Mars Science Laboratory, and by future missions to the red planet.

Enigmatic millimetre-scale micro-concretions with pseudocrystal faces and dominated by green clay minerals occur in unfossiliferous siliciclastic mudstone of the Lower Ordovician (479.0-466.0 Ma) Tonggao Formation, South China. The fossil-free mudstone unit is associated with local biodiversity decline. The mineralogy and mineral chemistry of these concretions were unknown previously, and this study comprises a preliminary investigation. The concretions are dominated by Fe-rich phyllosilicate minerals including glauconite and clinochlore, with minor quartz and traces of magnetite. The tex- tural relations between the micro-concretions and the surrounding matrix, and the preservation of original mudstone lamina- tions within the concretions, point to an origin during early diagenesis. The mineralogy and chemistry of these concretions are consistent with an origin in a restricted, hypersaline, relatively deep-water environment, in accordance with stratigraphi- cal and paleonotological data. These micro-concretions provide clues for a stressed environment with poor water circulation and anomalies of salinity and oxygen. Resume : Des micro-concretions enigmatiques d'echelle millimetrique, avec des faces pseudocristallines et dominees par des mineraux argileux verts, se trouvent dans des mudstones siliclastiques non fossiliferes de la Formation de Tonggao de l'Ordovicien inferieur (479,0-466,0 Ma), dans le sud de la Chine. L'unite mudstone sans fossile est associee a un declin de la biodiversite locale. La mineralogie et la chimie des mineraux de ces concretions n'etaient pas connues anterieurement et la presente etude comprend une investigation preliminaire. Les concretions sont dominees par des mineraux phyllosilicates riches en Fe, incluant la glauconite et le clinochlore, avec un peu de quartz et des traces de magnetite. Les relations textura- les entre les micro-concretions et la matrice environnante ainsi que la preservation des laminations originales du mudstone a l'interieur des concretions signalent une origine au debut d'une diagenese. La mineralogie et la chimie de ces concretions correspondent a une origine dans un environnement aqueux limite, hypersalin et relativement profond, ce qui concorde avec les donnees stratigraphiques et paleontologiques. Ces micro-concretions fournissent des indices qu'il s'agissait d'un environ- nement perturbe avec une mauvaise circulation d'eau et des teneurs anormales en sel et en oxygene. (Traduit par la Redaction)

Zr 3 Al is an intermetallic compound with a cubic structure whereas the isoelectronic compound Ti 3 Al is hexagonal. Crystallographic, microstructural and mechanical study of an alloy containing all the three elements is use in advancing our knowledge of the phase behavior across this pseudobinary alloy. A nominal composition of the Zr 2 TiAl alloy was prepared by arc melting and subsequently vacuum annealed at 1050 °C for 30 days and 1000 °C for 20 days. Scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDAX) showed the presence of three phases in the material. Among the three phases, the major phase was the stoichiometric Zr 2 TiAl alloy. From the SEM micrograph, it was seen that the major phase grains varied in size from 10 μm to 50 μm. Of the two minor phases present in the specimen, one is rich in Ti and the other in Al. In order to identify the peaks due to individual phases, micro-beam XRD was carried out, enabling the identification of all the three unambiguously. The stoichiometric alloy (Zr 2 TiAl) has L2 1 structure (space group Fm3m), the Ti-rich phase has DO 19 structure (space group P6 3 /mmc) and the Al-rich phase has A a structure (space group I4/mmm) Further, mechanical characterization of this alloy was carried out using nano-indentation and the typical hardness was found to be 8.5 GPa on the grain and 7.4 GPa at the grain boundary.

The analysis of sulphur isotopic compositions in three sets of surface sulphate samples from the soil zone in the Haughton impact structure shows that they are distinct. They include surface gypsum crusts remobilized from the pre-impact gypsum bedrock (mean δ34S +31‰), efflorescent copiapite and fibroferrite associated with hydrothermal marcasite (mean δ34S −37‰), and gypsum-iron oxide crusts representing weathering of pyritic crater-fill sediments (mean δ34S +7‰). Their different compositions reflect different histories of sulphur cycling. Two of the three sulphates have isotopically light (low δ34S) compositions compared with the gypsum bedrock (mean δ34S +31‰), reflecting derivation by weathering of sulphides (three sets of pyrite/marcasite samples with mean δ34S of −41, −20 and −8‰), which had in turn been precipitated by microbial sulphate reduction. Thus, even in the absence of the parent sulphides due to surface oxidation, evidence of life would be preserved. This indicates that on Mars, where surface oxidation may rule out sampling of sulphides during robotic exploration, but where sulphates are widespread, sulphur isotope analysis is a valuable tool that could be sensitive to any near-surface microbial activity. Other causes of sulphur isotopic fractionation on the surface of Mars are feasible, but any anomalous fractionation would indicate the desirability of further analysis.

– Queen Alexandra Range (QUE) 94204, an enstatite achondrite, is a coarse-grained, highly recrystallized, chondrule-free and unbrecciated rock dominated (about 70 vol%) by anhedral, equigranular crystals of orthoenstatite of nearly endmember composition (Fs0.1–0.4, Wo0.3–0.4) with interstitial plagioclase, kamacite, and troilite. Abundance of approximately 120° triple junctions and the close association of metal–sulfide and plagioclase-rich melts indicate that QUE 94204 has undergone limited partial melting with inefficient melt extraction. Mineral chemistry indicates a high degree of thermal metamorphism. Kamacite in QUE 94204 contains between 2.09 and 2.55 wt% Si, similar to highly metamorphosed EL chondrites. Plagioclase has between 4.31 and 6.66 wt% CaO, higher than other E chondrites but closer in composition to plagioclase from metamorphosed EL chondrites. QUE 94204 troilite contains up to 2.55 wt% Ti, consistent with extensive thermal metamorphism of an E chondrite-like precursor. Results presented in this study indicate that QUE 94204 is the result of low degree, (about 5–20 vol%, probably toward the lower end of this range) partial melting of an E chondrite protolith. Textural and chemical evidence suggests that during the metamorphism of QUE 94204, melts formed first at the Fe,Ni-FeS cotectic near approximately 900 °C, followed by plagioclase-pyroxene silicate partial melts near approximately 1100 °C. Neither the Fe,Ni-FeS nor the plagioclase-pyroxene melts were efficiently segregated or extracted. QUE 94204 belongs to a grouplet of similar “primitive enstatite achondrites” that are analogous to the acapulcoites-lodranites, but that have resulted from the partial melting of an E chondrite-like protolith.

Meteorite impacts are among the very few processes common to all planetary bodies with solid surfaces. Among the effects of impact on water-bearing targets is the formation of post-impact hydrothermal systems and associated mineral deposits. The Haughton impact structure (Devon Island, Nunavut, Canada, 75.2 °N, 89.5 °W) hosts a variety of hydrothermal mineral deposits that preserve assemblages of primary hydrothermal minerals commonly associated with secondary oxidative/hydrous weathering products. Hydrothermal mineral deposits at Haughton include intra-breccia calcite-marcasite vugs, small intra-breccia calcite or quartz vugs, intra-breccia gypsum megacryst vugs, hydrothermal pipe structures and associated surface "gossans," banded Fe-oxyhydroxide deposits, and calcite and quartz veins and coatings in shattered target rocks. Of particular importance are sulfide-rich deposits and their associated assemblage of weathering products. Hydrothermal mineral assemblages were characterized structurally, texturally, and geochemically with X-ray diffraction, micro X-ray diffraction, optical and electron microscopy, and inductively coupled plasma atomic emission spectroscopy. Primary sulfides (marcasite and pyrite) are commonly associated with alteration minerals, including jarosite (K,Na,H(3)O)Fe(3)(SO(4))(2)(OH)(6), rozenite FeSO(4)·4(H(2)O), copiapite (Fe,Mg)Fe(4)(SO(4))(6)(OH)(2)·20(H(2)O), fibroferrite Fe(SO(4))(OH)·5(H(2)O), melanterite FeSO(4)·7(H(2)O), szomolnokite FeSO(4)·H(2)O, goethite α-FeO(OH), lepidocrocite γ-FeO(OH) and ferrihydrite Fe(2)O(3)·0.5(H(2)O). These alteration assemblages are consistent with geochemical conditions that were locally very different from the predominantly circumneutral, carbonate-buffered environment at Haughton. Mineral assemblages associated with primary hydrothermal activity, and the weathering products of such deposits, provide constraints on possible microbial activity in the post-impact environment. The initial period of active hydrothermal circulation produced primary mineral assemblages, including Fe sulfides, and was succeeded by a period dominated by oxidation and low-temperature hydration of primary minerals by surface waters. Active hydrothermal circulation can enable the rapid delivery of nutrients to microbes. Nutrient availability following the cessation of hydrothermal circulation is likely more restricted; therefore, the biological importance of chemical energy from hydrothermal mineral deposits increases with time. Weathering of primary hydrothermal deposits and dissolution and reprecipitation of mobile weathering products also create many potential habitats for endolithic microbes. They also provide a mechanism that may preserve biological materials, potentially over geological timescales.