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Akaganeite on Mars could form from Fe(II) sulfides, but formation conditions remain unconstrained. We investigated akageneite formation by oxidative alteration of natural pyrrhotites exposed to HCl...

Whether hydrogen incorporated in nominally anhydrous mantle minerals plays a role in the strength and longevity of the thick cratonic lithosphere is a matter of debate. In particular, the percolation of hydrogen-bearing melts and fluids could potentially add hydrogen to the mantle lithosphere, weaken its olivines (the dominant mineral in mantle peridotite), and cause delamination of the lithosphere's base. The influence of metasomatism on hydrogen contents of cratonic mantle minerals can be tested in mantle xenoliths from the Slave Craton (Canada) because they show extensive evidence for metasomatism of a layered cratonic mantle. Minerals from mantle xenoliths from the Diavik mine in the Lac de Gras kimberlite area located at the center of the Archean Slave craton were analyzed by FTIR for hydrogen contents. The 18 peridotites, two pyroxenites, one websterite and one wehrlite span an equilibration pressure range from 3.1 to 6.6 GPa and include samples from the shallow (≤145 km), oxidized ultra-depleted layer; the deeper (∼145–180 km), reduced less depleted layer; and an ultra-deep (≥180 km) layer near the base of the lithosphere. Olivine, orthopyroxene, clinopyroxene and garnet from peridotites contain 30–145, 110–225, 105–285, 2–105 ppm H2O, respectively. Within each deep and ultra-deep layer, correlations of hydrogen contents in minerals and tracers of metasomatism (for example light over heavy rare-earth-element ratio (LREE/HREE), high-field-strength-element (HFSE) content with equilibration pressure) can be explained by a chromatographic process occurring during the percolation of kimberlite-like melts through garnet peridotite. The hydrogen content of peridotite minerals is controlled by the compositions of the evolving melt and of the minerals and by mineral/melt partition coefficients. At the beginning of the process, clinopyroxene scavenges most of the hydrogen and garnet most of the HFSE. As the melt evolves and becomes enriched in hydrogen and LREE, olivine and garnet start to incorporate hydrogen and pyroxenes become enriched in LREE. The hydrogen content of peridotite increases with decreasing depth, overall (e.g., from 75 to 138 ppm H2O in the deep peridotites). Effective viscosity calculated using olivine hydrogen content for the deepest xenoliths near the lithosphere-asthenosphere boundary overlaps with estimates of asthenospheric viscosities. These xenoliths cannot be representative of the overall cratonic root because the lack of viscosity contrast would have caused basal erosion of lithosphere. Instead, metasomatism must be confined in narrow zones channeling kimberlite melts through the lithosphere and from where xenoliths are preferentially sampled. Such localized metasomatism by hydrogen-bearing melts therefore does not necessarily result in delamination of the cratonic root.

We have used Mars Exploration Rover Opportunity data to investigate the origin and alteration of lithic types along the western rim of Noachian-aged Endeavour crater on Meridiani Planum. Two geolog...

Curiosity, the Mars Science Laboratory (MSL) rover, landed on Mars in August 2012 to investigate the ~3.5-billion-year-old (Ga) fluvio-lacustrine sedimentary deposits of Aeolis Mons (informally known as Mount Sharp) and the surrounding plains (Aeolis Palus) in Gale crater. After nearly nine years, Curiosity has traversed over 25 km, and the Chemistry and Mineralogy (CheMin) X-ray diffraction instrument on-board Curiosity has analyzed 30 drilled rock and three scooped soil samples to date. The principal strategic goal of the mission is to assess the habitability of Mars in its ancient past. Phyllosilicates are common in ancient Martian terrains dating to ~3.5–4 Ga and were detected from orbit in some of the lower strata of Mount Sharp. Phyllosilicates on Earth are important for harboring and preserving organics. On Mars, phyllosilicates are significant for exploration as they are hypothesized to be a marker for potential habitable environments. CheMin data demonstrate that ancient fluvio-lacustrine rocks in Gale crater contain up to ~35 wt. % phyllosilicates. Phyllosilicates are key indicators of past fluid–rock interactions, and variation in the structure and composition of phyllosilicates in Gale crater suggest changes in past aqueous environments that may have been habitable to microbial life with a variety of possible energy sources.

We performed pulsed-laser irradiation of a chip of the CM2 Murchison carbonaceous chondrite meteorite to simulate micrometeorite impacts on carbonaceous asteroids. Optical reflectance spectroscopy and transmission electron microscopy were performed to characterize the unirradiated and irradiated samples and vapor and melt deposits collected on a glass slide ∼7 mm from the surface of the sample. The spectrum of the deposit on the glass slide shows a red slope between 0.35–2.5 µm, while the irradiated surface of the meteorite shows only slight darkening over the same spectral range. We identified predominant melt products and vesiculated textures in the glass slide deposit, in the fine-grained matrix of the meteorite, and in individual mineral phases of the meteorite chip. Extracted focused ion beam (FIB) sections from the matrix material, an olivine grain, a pentlandite grain, and from the glass slide deposit were analyzed by scanning transmission electron microscopy (STEM). Microstructural and chemical analyses based on the STEM observations show widespread melting and the formation of Fe-bearing nanoparticles (including prevalent Fe–Ni–sulfides) across the surface of the meteorite. The section extracted from the glass slide revealed nanoparticles embedded in a chemically and microstructurally complex deposit, which likely formed as a result of both melting and vaporization processes. These analyses reveal a significantly more compositionally diverse population of nanoparticles compared to what is observed in lunar or ordinary chondritic space weathered samples. We discuss the implications these results have for the space weathering of carbonaceous asteroids and their importance for understanding the surface processes on primitive bodies.

Akaganeite is an Fe(III) (hydr)oxide with a tunnel structure typically occupied by chloride. The mineral can undergo anion-exchange reactions in aqueous solution, resulting in incorporation of other anions together with Cl– into the tunnels. Identification of anions present in akaganeite tunnels may permit characterization of solution compositions in which akaganeite precipitated and/or existed. Akaganeite has been reported in several locations on Mars, including Yellowknife Bay in Gale crater. However, the nature of the tunnel anions has not been investigated. In order to constrain the nature of the tunnel anions in martian akaganeite, synthetic akaganeite (72 mg/g total Cl– content) was reacted with Mars-relevant anions (F–, OH–, and SO42–). Release of Cl– into solution was monitored with ion chromatography. Anion-reacted akaganeite was characterized with instruments analogous to instruments onboard robotic space crafts including X-ray diffraction (XRD), Mossbauer spectroscopy, thermal and evolved gas a...

We have used Mars Exploration Rover Opportunity data to investigate the origin and alteration of lithic types along the western rim of Noachian-aged Endeavour crater on Meridiani Planum. Two geologic units are identified along the rim: the Shoemaker and Matijevic formations. The Shoemaker formation consists of two types of polymict impact breccia: clast rich with coarser clasts in upper units; clast-poor with smaller clasts in lower units. Comparisons terrestrial craters show that the lower units represent more distal ejecta from at least two earlier impacts, and the upper units are proximal ejecta from Endeavour crater. Both are mixtures of target rocks of basaltic composition with subtle compositional variations caused by differences in post-impact alteration. The Matijevic formation and lower Shoemaker units represent pre-Endeavour geology, which we equate with the regional Noachian subdued cratered unit. An alteration style unique to these rocks is formation of smectite and Si- and Al-rich vein-like structures crosscutting outcrops. Post-Endeavour alteration is dominated by sulfate formation. Rim-crossing fracture zones include regions of alteration that produced Mg-sulfates as a dominant phase, plausibly closely associated in time with the Endeavour impact. Calcium-sulfate vein formation occurred over extended time, including before the Endeavour impact and after the Endeavour rim had been substantially degraded, likely after deposition of the Burns formation that surrounds and embays the rim. Differences in Mg, Ca and Cl concentrations on rock surfaces and interiors indicate mobilization of salts by transient water that has occurred recently and may be ongoing.

In August 2015, the Curiosity Mars rover discovered tridymite, a high‐temperature silica polymorph, in Gale crater. The existing model for its occurrence suggests erosion and detrital sedimentation from silicic volcanic rocks in the crater rim or central peak. The chemistry and mineralogy of the tridymite‐bearing rocks, however, are not consistent with silicic volcanic material. Using data from Curiosity, including chemical composition from the Alpha Particle X‐ray Spectrometer, mineralogy from the CheMin instrument, and evolved gas and isotopic analyses from the Sample Analysis at Mars instrument, we show that the tridymite‐bearing rocks exhibit similar chemical patterns with silica‐rich alteration halos which crosscut the stratigraphy. We infer that the tridymite formed in‐place through hydrothermal processes and show additional chemical and mineralogical results from Gale crater consistent with hydrothermal activity occurring after sediment deposition and lithification.

The Cumberland drill sample from the Sheepbed mudstone in Gale Crater, Mars, revealed the first evidence of an indigenous Martian organic molecule, chlorobenzene, with the Sample Analysis at Mars (SAM) instrument on Curiosity. We created in the laboratory a mineralogical analog of the Cumberland sample (CBA) to aid in the understanding of the precursor organic molecule(s) that led to the detection of chlorobenzene. The CBA was analyzed by visible/near-infrared spectrometry, and the results are in accordance with Mastcam multispectral and the Chemical Camera passive analyses of Cumberland on Mars, demonstrating that the CBA is a relevant analog. CBA aliquots were spiked with 0.5 wt. % of benzoic acid and 1–2 wt. % of magnesium perchlorate and were run in SAM Testbed (TB). The TB evolved gas analysis (EGA) showed similarities with the Cumberland EGA on Mars in terms of the major volatiles H2O, CO2, and O2. The TB gas chromatography mass spectrometry displayed the presence of chlorobenzene at 23–28 pmol and dichlorobenzene. CBA aliquots were also analyzed in the laboratory with SAM-like EGA and the results on the laboratory setup confirmed the generation of chlorobenzene by a reaction between the benzoic acid and the magnesium perchlorates. The case for benzoic acid as a potential precursor for the chlorobenzene detected in the Martian regolith is strengthened with this new supporting laboratory data from the CBA. The quantification of chlorobenzene in the TB led to prediction of organic precursor abundance on Mars of hundreds, if not thousands, of parts per millions by weight.

International audience; The SuperCam instrument on the Perseverance Mars 2020 rover uses a pulsed 1064 nm laser to ablate targets at a distance and conduct laser induced breakdown spectroscopy (LIBS) by analyzing the light from the resulting plasma. SuperCam LIBS spectra are preprocessed to remove ambient light, noise, and the continuum signal present in LIBS observations. Prior to quantification, spectra are masked to remove noisier spectrometer regions and spectra are normalized to minimize signal fluctuations and effects of target distance. In some cases, the spectra are also standardized or binned prior to quantification. To determine quantitative elemental compositions of diverse geologic materials at Jezero crater, Mars, we use a suite of 1198 laboratory spectra of 334 well-characterized reference samples. The samples were selected to span a wide range of compositions and include typical silicate rocks, pure minerals (e.g., silicates, sulfates, carbonates, oxides), more unusual compositions (e.g., Mn ore and sodalite), and replicates of the sintered SuperCam calibration targets (SCCTs) onboard the rover. For each major element (SiO2, TiO2, Al2O3, FeOT, MgO, CaO, Na2O, K2O), the database was subdivided into five "folds" with similar distributions of the element of interest. One fold was held out as an independent test set, and the remaining four folds were used to optimize multivariate regression models relating the spectrum to the composition. We considered a variety of models, and selected several for further investigation for each element, based primarily on the root mean squared error of prediction (RMSEP) on the test set, when analyzed at 3 m. In cases with several models of comparable performance at 3 m, we incorporated the SCCT performance at different distances to choose the preferred model. Shortly after landing on Mars and collecting initial spectra of geologic targets, we selected one model per element. Subsequently, with additional data from geologic targets, some models were revised to ensure results that are more consistent with geochemical constraints. The calibration discussed here is a snapshot of an ongoing effort to deliver the most accurate chemical compositions with SuperCam LIBS.

We report the results of geological studies by the Opportunity Mars rover on the Endeavour Crater rim. Four major units occur in the region (oldest to youngest): the Matijevic, Shoemaker, Grasberg, and Burns formations. The Matijevic formation, consisting of fine‐grained clastic sediments, is the only pre‐Endeavour‐impact unit and might be part of the Noachian etched units of Meridiani Planum. The Shoemaker formation is a heterogeneous polymict impact breccia; its lowermost member incorporates material eroded from the underlying Matijevic formation. The Shoemaker formation is a close analog to the Bunte Breccia of the Ries Crater, although the average clast sizes are substantially larger in the latter. The Grasberg formation is a thin, fine‐grained, homogeneous sediment unconformably overlying the Shoemaker formation and likely formed as an airfall deposit of unknown areal extent. The Burns formation sandstone overlies the Grasberg, but compositions of the two units are distinct; there is no evidence that the Grasberg formation is a fine‐grained subfacies of the Burns formation. The rocks along the Endeavour Crater rim were affected by at least four episodes of alteration in the Noachian and Early Hesperian: (i) vein formation and alteration of preimpact Matijevic formation rocks, (ii) low‐water/rock alteration along the disconformity between the Matijevic and Shoemaker formations, (iii) alteration of the Shoemaker formation along fracture zones, and (iv) differential mobilization of Fe and Mn, and CaSO_4‐vein formation in the Grasberg and Shoemaker formations. Episodes (ii) and (iii) possibly occurred together, but (i) and (iv) are distinct from either of these.

Surface conditions on early Mars were likely anoxic, similar to early Earth, but the timing of the evolution to oxic conditions characteristic of contemporary Mars is unresolved. Ferrous trioctahedral smectites are the thermodynamically predicted products of anoxic basalt weathering, but orbital analyses of Noachian-aged terrains find primarily Fe(3+)-bearing clay minerals. Rover-based detection of Fe(2+)-bearing trioctahedral smectites at Gale Crater suggest that ferrous smectites are the unoxidized progenitors of orbitally-detected ferric smectites. To assess this pathway, we conducted ambient-temperature oxidative alteration experiments on four synthetic ferrous smectites having molar Fe/(Mg+Fe) from 1.00 to 0.33. Smectite suspension in air-saturated solutions produced incomplete oxidation (24–38% Fe(3+)/ΣFe). Additional smectite oxidation occurred upon re-exposure to air-saturated solutions after anoxic hydrothermal recrystallization, which accelerated cation and charge redistribution in the octahedral sheet. Oxidation was accompanied by contraction of the octahedral sheet (d((060)) decreased from 1.53–1.56 Å to 1.52 Å), consistent with a shift towards dioctahedral structure. Ferrous smectite oxidation by aqueous hydrogen peroxide solutions resulted in nearly complete Fe(2+) oxidation but also led to partial Fe(3+) ejection from the structure, producing nanoparticulate hematite. Reflectance spectra of oxidized smectites were characterized by (Fe(3+),Mg)(2)-OH bands at 2.28–2.30 μm, consistent with oxidative formation of dioctahedral nontronite. Accordingly, ferrous smectites are plausible precursors to observed ferric smectites on Mars, and their presence in late-Noachian sedimentary units suggests that anoxic conditions may have persisted on Mars beyond the Noachian.

Accurate quantitative analysis of diverse geologic materials is one of the primary challenges faced by the laser-induced breakdown spectroscopy (LIBS)-based ChemCam instrument on the Mars Science Laboratory (MSL) rover. The SuperCam instrument on the Mars 2020 rover, as well as other LIBS instruments developed for geochemical analysis on Earth or other planets, will face the same challenge. Consequently, part of the ChemCam science team has focused on the development of improved multivariate analysis calibrations methods. Developing a single regression model capable of accurately determining the composition of very different target materials is difficult because the response of an element's emission lines in LIBS spectra can vary with the concentration of other elements. We demonstrate a conceptually simple “sub-model” method for improving the accuracy of quantitative LIBS analysis of diverse target materials. The method is based on training several regression models on sets of targets with limited composition ranges and then “blending” these “sub-models” into a single final result. Tests of the sub-model method show improvement in test set root mean squared error of prediction (RMSEP) for almost all cases. The sub-model method, using partial least squares (PLS) regression, is being used as part of the current ChemCam quantitative calibration, but the sub-model method is applicable to any multivariate regression method and may yield similar improvements.

The primary aim of the human-centred design (HCD) approach is to identify the user needs. However, we argue that there is a lack of understanding of, and even awareness of, gender in HCD. This approach sees gender as static and stable regarding male or female such that the implication of principles in products, systems or services appeals to one gender or another linking gender differences, and stereotypes. To illustrate this, the investigation was conducted in the context of fostering sun protection behaviour in young men. Participatory design sessions were deployed to investigate the role of gender in the HCD and how it can be used to foster sun protection behaviour. We have concluded with the development of a novel gender aware HCD approach which opens avenues for design research and practice for increasing emphasis on the influence of the designer’s own gender and their gendered perceptions in their designs.

There has been widespread criticism of the capabilities of engineering graduates produced in the United Kingdom. More than half of employers say that engineering graduate recruits do not reach their expected standards and nearly two thirds think skills gaps are a threat to their business [1]. These failings are identified particularly in the softer rather technical domains including for example design, creativity and communication [1, 2]. A professional body review at the University of Brighton by the and in May 2015 also identified these areas as being particularly weak at the University. From 2016, two University of Brighton academics transitioned from full time lecturing on BSc Product Design programmes to full time lecturing on B.Eng programmes. The University was during this period undertaking an institution wide curriculum review and the design academics (the paper authors) used the opportunity to introduce changes to the design provision in the engineering courses. These changes drew on thirty years of design lecturing, and applied design pedagogies to the more traditional engineering courses. This paper outlines the changes that were made and evaluates the outcomes as perceived by final year undergraduate and postgraduate engineering programmes. Whilst it is notoriously difficult to quantify educational effectiveness, the results suggest that engineering students are highly receptive to the design and educational practices that are traditionally separate between design and engineering pedagogy. It is postulated that the rigid and extensive requirements needed to achieve professional body engineering accreditation is actually unhelpful to the creative development of courses needed to produce engineers of the future. REFERENCES [1] Institute of Engineering and Technology [2] (2015) Skills and Demand in Industry Survey. IET [2] Wakeham, W. (2016) STEM degree provision and graduate employability. UK Government Department of Business, Innovation and Skills & the Higher Education Funding Council for England

Molecular hydrogen (H2) from volcanic emissions is suggested to warm the Martian surface when carbon dioxide (CO2) levels dropped from the Noachian (4100 to 3700 Myr) to the Hesperian (3700 to 3000 Myr). Its presence is expected to shift the conversion of molecular nitrogen (N2) into different forms of fixed nitrogen (N). Here we present experimental data and theoretical calculations that investigate the efficiency of nitrogen fixation by bolide impacts in CO2‐N2 atmospheres with or without H2. Surprisingly, nitric oxide (NO) was produced more efficiently in 20% H2 in spite of being a reducing agent and not likely to increase the rate of nitrogen oxidation. Nevertheless, its presence led to a faster cooling of the shock wave raising the freeze‐out temperature of NO resulting in an enhanced yield. We estimate that the nitrogen fixation rate by bolide impacts varied from 7 × 10−4 to 2 × 10−3 g N·Myr−1·cm−2 and could imply fluvial concentration to explain the nitrogen (1.4 ± 0.7 g N·Myr−1·cm−2) detected as nitrite (NO2 −) and nitrate (NO3 −) by Curiosity at Yellowknife Bay. One possible explanation is that the nitrogen detected in the lacustrine sediments at Gale was deposited entirely on the crater's surface and was subsequently dissolved and transported by superficial and ground waters to the lake during favorable wet climatic conditions. The nitrogen content sharply decreases in younger sediments of the Murray formation suggesting a decline of H2 in the atmosphere and the rise of oxidizing conditions causing a shortage in the supply to putative microbial life., We acknowledge the NASA Mars Science Laboratory Program, Centre National d'Études Spatiales, the Universidad Nacional Autónoma de México (PAPIIT IN109416, IN111619, and PAPIME PE103216), and the Consejo Nacional de Ciencia y Tecnología de México (CONACyT 220626) for their support.

The Sample Analysis at Mars (SAM) instrument on the Curiosity rover has detected evidence of oxychlorine compounds (i.e., perchlorates and chlorates) in Gale crater, which has implications for past habitability, diagenesis, aqueous processes, interpretation of in situ organic analyses, understanding the martian chlorine cycle, and hazards and resources for future human exploration. Pure oxychlorines and mixtures of oxychlorines with Mars-analog phases have been analyzed for their oxygen (O ) and hydrogen chloride (HCl) releases on SAM laboratory analog instruments in order to constrain which phases are present in Gale crater. These studies demonstrated that oxychlorines evolve O releases with peaks between ~200 and 600 C, although the thermal decomposition temperatures and the amount of evolved O decrease when iron phases are present in the sample. Mg and Fe oxychlorines decompose into oxides and release HCl between ~200 and 542 C. Ca, Na, and K oxychlorines thermally decompose into chlorides and do not evolve HCl by themselves. However, the chlorides (original or from oxychlorine decomposition) can react with water-evolving phases (e.g., phyllosilicates) in the sample and evolve HCl within the temperature range of SAM (, The research reviewed in this paper was funded by the Mars Science Laboratory (MSL) project office. M.-P.Z. acknowledges funding from the Ministerio de Ciencia e Innovación (ref. PID2019-104205GB-C21).

The Curiosity rover observed high Mn abundances (>25 wt % MnO) in fracture-filling materials that crosscut sandstones in the Kimberley region of Gale crater, Mars. The correlation between Mn and trace metal abundances plus the lack of correlation between Mn and elements such as S, Cl, and C, reveals that these deposits are Mn oxides rather than evaporites or other salts. On Earth, environments that concentrate Mn and deposit Mn minerals require water and highly oxidizing conditions; hence, these findings suggest that similar processes occurred on Mars. Based on the strong association between Mn-oxide deposition and evolving atmospheric dioxygen levels on Earth, the presence of these Mn phases on Mars suggests that there was more abundant molecular oxygen within the atmosphere and some groundwaters of ancient Mars than in the present day.

In the search for evidence of past aqueous activity by the Mars Exploration Rover Opportunity, fracture-filling veins and rock coatings are prime candidates for exploration. At one location within a segment of remaining rim material surrounding Endeavour Crater, a set of “boxwork” fractures in an outcrop called Esperance are filled by a bright, hydrated, and highly siliceous (SiO2 ~ 66 wt%) material, which has overall a montmorillonite-like chemical composition. This material is partially covered by patches of a thin, dark coating that is sulfate-rich (SO3 ~ 21 wt%) but also contains significant levels of Si, Fe, Ca, and Mg. The simultaneous presence of abundant S, Si, and Fe indicates significant mineralogical complexity within the coating. This combination of vein and coating compositions is unlike previous analyses on Mars. Both materials are heterogeneously eroded, presumably by eolian abrasion. The evidence indicates at least two separate episodes of solute precipitation from aqueous fluids at this location, possibly widely separated in time. In addition to the implications for multiple episodes of alteration at the surface of the planet, aqueous chemical environments such as these would have been habitable at the time of their formation and are also favorable for preservation of organic material.

Mars Reconnaissance Orbiter HiRISE images and Opportunity rover observations of the ~22 km wide Noachian age Endeavour Crater on Mars show that the rim and surrounding terrains were densely fractured during the impact crater-forming event. Fractures have also propagated upward into the overlying Burns formation sandstones. Opportunity’s observations show that the western crater rim segment, called Murray Ridge, is composed of impact breccias with basaltic compositions, as well as occasional fracture-filling calcium sulfate veins. Cook Haven, a gentle depression on Murray Ridge, and the site where Opportunity spent its sixth winter, exposes highly fractured, recessive outcrops that have relatively high concentrations of S and Cl, consistent with modest aqueous alteration. Opportunity’s rover wheels serendipitously excavated and overturned several small rocks from a Cook Haven fracture zone. Extensive measurement campaigns were conducted on two of them: Pinnacle Island and Stuart Island. These rocks have the highest concentrations of Mn and S measured to date by Opportunity and occur as a relatively bright sulfate-rich coating on basaltic rock, capped by a thin deposit of one or more dark Mn oxide phases intermixed with sulfate minerals. We infer from these unique Pinnacle Island and Stuart Island rock measurements that subsurface precipitation of sulfate-dominated coatings was followed by an interval of partial dissolution and reaction with one or more strong oxidants (e.g., O_2) to produce the Mn oxide mineral(s) intermixed with sulfate-rich salt coatings. In contrast to arid regions on Earth, where Mn oxides are widely incorporated into coatings on surface rocks, our results demonstrate that on Mars the most likely place to deposit and preserve Mn oxides was in fracture zones where migrating fluids intersected surface oxidants, forming precipitates shielded from subsequent physical erosion.

Orbital and in-situ data from the surface of Mars indicate that nanophase weathering products are important constituents of martian rocks and soils. Nanophase minerals have the capacity to chemisorb anions like sulfate and phosphate onto their surfaces, but it is not known whether chemisorption is an important or even detectable process via orbital and in-situ observations. The detection of chemisorbed sulfate and phosphate anions on nanophase minerals would constrain the speciation of these anions and past aqueous environmental conditions. Here, we synthesized two nanophase weathering products that are common in terrestrial volcanic soils and have been identified on the martian surface: allophane and nanophase ferric oxide as represented by ferrihydrite. We specifically adsorbed sulfate and phosphate separately onto the nanophase mineral surfaces (4.5 and 1.6 wt% SO42−, and 6.7 and 8.9 wt% PO43− on allophane and ferrihydrite, respectively) and analyzed the untreated and chemisorbed materials using instruments similar to those on orbital and landed Mars missions (including X-ray diffraction, evolved gas analysis, Mossbauer spectroscopy, and VNIR and thermal-IR spectroscopy). Evolved gas analysis is the optimum method to detect chemisorbed sulfate, with SO2(g) being released at >900 °C for allophane and 400–800 °C for ferrihydrite. Chemisorbed sulfate and phosphate anions affect the thermal-IR spectra of allophane and ferrihydrite in the S-O and P-O stretching region when present in abundances of only a few weight percent; S-O and P-O stretching bands are apparent as short-wavelength shoulders on Si-O stretching bands. Sulfate and phosphate anions chemisorbed to allophane have small but measurable effects on the position of the OH-H2O bands at 1.4 and 1.9 μm in near-IR spectra. Chemisorbed sulfate and phosphate anions did not affect the X-ray diffraction patterns, Mossbauer spectra, and visible/near-IR spectra of ferrihydrite. These data suggest that sulfate chemisorbed onto the surfaces of nanophase minerals can be detected with the Sample Analysis at Mars (SAM) instrument on the Mars science laboratory Curiosity rover, and subtle signatures of chemisorbed sulfate and phosphate may be detectable by IR spectrometers on landed missions. The combined use of SAM, the Chemistry and Mineralogy (CheMin) instrument, and the Alpha Particle X-ray Spectrometer (APXS) on Curiosity allows for the most detailed characterization to date of nanophase minerals in martian rocks and soils and the potential presence of chemisorbed anionic complexes.

Hematite spherules from Mauna Kea volcano (Hawaii) resemble Martian hematite spherules at Meridiani Planum in morphology, mineralogy, and geochemistry, and they both formed in association with acid-sulfate alteration of basalt. To gain insights into the processes involved in the formation of these spherules, we have measured the Fe isotopic compositions of unaltered basalts and tephras, as well as a variety of weathering/alteration products including altered basalts, hematite-rich breccia and individual hematite spherules, jarosite-bearing tephras, palagonitic tephras, calcined tephras (high-T dry oxidation) and steam-vent tephras. Compared to other alteration processes that induce little Fe mobility, acid-sulfate alteration produces large Fe isotopic variations ( δ 56 Fe values ranging from −0.15 to +0.94‰). We used rock slabs from a variably altered basaltic rock to constrain the Fe isotope fractionation factor during acid-sulfate alteration of basaltic rocks. We found that the process followed a Rayleigh distillation with an instantaneous fractionation factor of −0.24‰ between the fluid and the residue for δ 56 Fe , resulting in a heavy Fe isotope enrichment in the alteration residue. However, the constant Mn/Fe ratios of the slabs suggest that acid-sulfate leaching does not significantly fractionate Mn/Fe ratios in basalts, which is consistent with the mobilization of iron as Fe(II). We also measured the Fe isotopic compositions and Mn/Fe ratios (using NanoSIMS) of individual hematite spherules from a spherule-rich breccia HWMK745R. The spherules show heavy Fe isotopic enrichments and low Mn/Fe ratios compared to unaltered samples, which is similar to the fractionations encountered in iron formations. A Rayleigh fractionation model suggests that both Fe isotopic compositions and Mn/Fe ratios of the spherules are consistent with ∼80% Fe oxidation and precipitation from an acid-sulfate fluid. Therefore, direct Fe precipitation from a fluid can readily explain the hematite spherule formation, and a more complex scenario involving jarosite precipitation followed by conversion to hematite is not needed. Combined thermodynamic and kinetic constraints also suggest that precipitation of jarosite would be hindered. The study presents a roadmap for studying future returned Martian samples in the laboratory.

The Alpha Particle X-ray Spectrometer (APXS), a field instrument onboard four martian rovers, measures largely unprepared, in situ samples on Mars. The APXS has high precision that enables the determination of elemental concentrations in a wide range of geologic materials. However, lack of sample preparation can lead to heterogeneous matrix effects, and understanding the associated uncertainty is essential for interpreting APXS data. Here we use Particle Induced X-ray Emission spectrometry (PIXE) to analyze a suite of geologic samples from Hawai'i as an analogue study to better understand APXS analyses of martian samples. Wavelength-Dispersive X-ray Fluorescence (WDXRF) analyses of fused glass beads establish higher-accuracy standards for the Hawaiian samples. Sulfate-silicate mixtures were made to evaluate sulfur analysis by PIXE. Results show that the PIXE concentrations for most major elements have 2–6% accuracy, which is comparable to the APXS. However, the PIXE concentrations are systematically high in Al and low in Mg, resulting in lower accuracy (13% and 20%, respectively). Olivine-phyric lavas and most of their altered products have the largest discrepancies with Al concentrations up to 25% high and Mg up to 35% low. Sulfur is systematically high (up to 30% in a basalt matrix) compared to gravimetric S concentrations in the sulfate-silicate mixtures. These systematic deviations in Mg, Al, and S are linked to heterogeneous matrix effects, because PIXE and APXS analyses assume all atoms in a sample to be homogeneously mixed on the sub-micrometer scale, which is not the case. Two key implications for APXS results are: (1) Olivine-bearing samples likely have reported concentrations of Mg that is too low and Al that is too high. Thus, olivine-phyric basalts in Gusev crater and the basaltic sand and soil at three landing sites may have Mg and Al concentrations closer to those of the olivine-phyric shergottites and modelled martian crust than previously thought. (2) Sulfate-silicate mixtures may have overestimated S concentrations reported, resulting in greater uncertainty in the stoichiometry of Ca-sulfates, which is used to deduce the geochemical associations of sulfur in samples.

Clay minerals found in Gale crater, Mars, record surficial chemical weathering and changing conditions in an ancient lake., Clay minerals provide indicators of the evolution of aqueous conditions and possible habitats for life on ancient Mars. Analyses by the Mars Science Laboratory rover Curiosity show that ~3.5–billion year (Ga) fluvio-lacustrine mudstones in Gale crater contain up to ~28 weight % (wt %) clay minerals. We demonstrate that the species of clay minerals deduced from x-ray diffraction and evolved gas analysis show a strong paleoenvironmental dependency. While perennial lake mudstones are characterized by Fe-saponite, we find that stratigraphic intervals associated with episodic lake drying contain Al-rich, Fe3+-bearing dioctahedral smectite, with minor (3 wt %) quantities of ferripyrophyllite, interpreted as wind-blown detritus, found in candidate aeolian deposits. Our results suggest that dioctahedral smectite formed via near-surface chemical weathering driven by fluctuations in lake level and atmospheric infiltration, a process leading to the redistribution of nutrients and potentially influencing the cycling of gases that help regulate climate.

Widespread detections of phyllosilicates in Noachian terrains on Mars imply a history of near-surface fluid-rock interaction. Ferrous trioctahedral smectites are thermodynamically predicted products of basalt weathering on early Mars, but to date only Fe3+-bearing dioctahedral smectites have been identified from orbital observations. In general, the physicochemical properties of ferrous smectites are poorly studied because they are susceptible to air oxidation. In this study, eight Fe2+-bearing smectites were synthesized from Fe2+-Mg-Al silicate gels at 200°C under anoxic conditions. Samples were characterized by inductively coupled plasma optical emission spectrometry, powder X-ray diffraction, Fe K-edge X-ray absorption spectroscopy (XAS), Mossbauer spectroscopy, and visible/near-infrared (VNIR) reflectance spectroscopy. The range of redox states was Fe3+/ΣFe = 0 to 0.06 ± 0.01 as determined by both XAS and, for short integration times, Mossbauer. The smectites have 060 distances (d(060)) between 1.53 and 1.56 A, indicating a trioctahedral structure. d(060) and XAS-derived interatomic Fe-(Fe,Mg,Al) distance scaled with Fe content. Smectite VNIR spectra feature OH/H2O absorption bands at 1.4 and 1.9 µm, (Fe2+,Mg,Al)3-OH stretching bands near 1.4 µm, and Fe2+Fe2+Fe2+-OH, MgMgMg-OH, AlAl(Mg,Fe2+)-OH, and AlAl-OH combination bands at 2.36 µm, 2.32 µm 2.25 µm, and 2.20 µm, respectively. The spectra for ferrous saponites are distinct from those for dioctahedral ferric smectites, permitting their differentiation from orbital observations. X-ray diffraction patterns for synthetic high-Mg ferrosaponite and high-Mg ferrian saponite are both consistent with the Sheepbed saponite detected by the chemistry and mineralogy (CheMin) instrument at Gale Crater, Mars, suggesting that anoxic basalt alteration was a viable pathway for clay mineral formation on early Mars.

© 2015 by Walter de Gruyter. The Mars Science Laboratory (MSL) rover Curiosity has documented a section of fluvio-lacustrine strata at Yellowknife Bay (YKB), an embayment on the floor of Gale crater, approximately 500 m east of the Bradbury landing site. X-ray diffraction (XRD) data and evolved gas analysis (EGA) data from the CheMin and SAM instruments show that two powdered mudstone samples (named John Klein and Cumberland) drilled from the Sheepbed member of this succession contain up to ∼20 wt% clay minerals. A trioctahedral smectite, likely a ferrian saponite, is the only clay mineral phase detected in these samples. Smectites of the two samples exhibit different 001 spacing under the low partial pressures of H2O inside the CheMin instrument (relative humidity 2+ in olivine to Fe3+ in magnetite, and perhaps in smectites provided a potential energy source for organisms.

The ChemCam Laser-Induced Breakdown Spectroscopy (LIBS) instrument onboard the Mars Science Laboratory (MSL) rover Curiosity has obtained > 300,000 spectra of rock and soil analysis targets since landing at Gale Crater in 2012, and the spectra represent perhaps the largest publicly-available LIBS datasets. The compositions of the major elements, reported as oxides (SiO2, TiO2, Al2O3, FeOT, MgO, CaO, Na2O, K2O), have been re-calibrated using a laboratory LIBS instrument, Mars-like atmospheric conditions, and a much larger set of standards (408) that span a wider compositional range than previously employed. The new calibration uses a combination of partial least squares (PLS1) and Independent Component Analysis (ICA) algorithms, together with a calibration transfer matrix to minimize differences between the conditions under which the standards were analyzed in the laboratory and the conditions on Mars. While the previous model provided good results in the compositional range near the average Mars surface composition, the new model fits the extreme compositions far better. Examples are given for plagioclase feldspars, where silicon was significantly over-estimated by the previous model, and for calcium-sulfate veins, where silicon compositions near zero were inaccurate. The uncertainties of major element abundances are described as a function of the abundances, and are overall significantly lower than the previous model, enabling important new geochemical interpretations of the data.

The Mars Science Laboratory Curiosity rover landed in Gale crater in August 2012 to investigate the strata of lower Aeolis Mons (i.e., Mount Sharp) and characterize their depositional and diagenetic environments. Visible/short-wave infrared spectra from orbit of these strata show variations in phyllosilicate, sulfate, and Fe-oxide minerals, suggesting these units record environmental changes that occurred during the early Hesperian. Curiosity has traversed over 15 km and has climbed through Approx. 200 m of stratigraphic section, made up of predominantly fluviolacustrine (i.e., the Bradbury group and the Murray formation) and aeolian (i.e., the Stimson formation) units. Multiple geochemical and mineralogical instruments are onboard Curiosity to study these ancient rocks, including the Chemistry and Mineralogy (CheMin) instrument, which is an X-ray diffractometer (XRD) and X-ray fluorescence spectrometer, and the Alpha Particle X-ray Spectrometer (APXS).

There is abundant evidence for liquid water on early Mars, but the debate remains whether early Mars was warm and wet or cold and icy with punctuated periods of melting. To further investigate the hypothesis of a cold and icy early Mars, we collected rocks and sediments from the Collier and Diller glacial valleys in the Three Sisters volcanic complex in Oregon. We analyzed rocks and sediments with X-ray diffraction (XRD), scanning and transmission electron microscopies with energy dispersive spectroscopy (SEM, TEM, EDS), and visible, short-wave infrared (VSWIR) and thermal-IR (TIR) spectroscopies to characterize chemical weathering and sediment transport through the valleys. Here, we focus on the composition and mineralogy of the weathering products and how they compare to those identified on the martian surface. Phyllosilicates (smectite), zeolites, and poorly crystalline phases were discovered in pro- and supra-glacial sediments, whereas Si-rich regelation films were found on hand samples and boulders in the proglacial valleys. Most phyllosilicates and zeolites are likely detrital, originating from hydrothermally altered units on North Sister. TEM-EDS analyses of the

Ferrian saponite from the eastern Santa Monica Mountain, near Griffith Park (Los Angeles, California), was investigated as a mineralogical analog to smectites discovered on Mars by the CheMin X-ray diffraction instrument onboard the Mars Science Laboratory (MSL) rover. The martian clay minerals occur in sediment of basaltic composition and have 02 l diffraction bands peaking at 4.59 A, consistent with tri-octahedral smectites. The Griffith saponite occurs in basalts as pseudomorphs after olivine and mesostasis glass and as fillings of vesicles and cracks and has 02 l diffraction bands at that same position. We obtained chemical compositions (by electron microprobe), X-ray diffraction patterns with a lab version of the CheMin instrument, Mossbauer spectra, and visible and near-IR reflectance (VNIR) spectra on several samples from that locality. The Griffith saponite is magnesian, Mg/(Mg+∑Fe) = 65–70%, lacks tetrahedral Fe 3+ and octahedral Al 3+ , and has Fe 3+ /∑Fe from 64 to 93%. Its chemical composition is consistent with a fully tri-octahedral smectite, but the abundance of Fe 3+ gives a nominal excess charge of +1 to +2 per formula unit. The excess charge is likely compensated by substitution of O 2− for OH − , causing distortion of octahedral sites as inferred from Mossbauer spectra. We hypothesize that the Griffith saponite was initially deposited with all its iron as Fe 2+ and was oxidized later. X-ray diffraction shows a sharp 001 peak at 15 A, 00 l peaks, and a 02 l diffraction band at the same position (4.59 A) and shape as those of the martian samples, indicating that the martian saponite is not fully oxidized. VNIR spectra of the Griffith saponite show distinct absorptions at 1.40, 1.90, 2.30–2.32, and 2.40 μm, arising from H 2 O and hydroxyl groups in various settings. The position of the ~2.31 μm spectral feature varies systematically with the redox state of the octahedrally coordinated Fe. This correlation may permit surface oxidation state to be inferred (in some cases) from VNIR spectra of Mars obtained from orbit, and, in any case, ferrian saponite is a viable assignment for spectral detections in the range 2.30–2.32 μm.

The X-ray diffraction/X-ray fluorescence instrument CheMin on the Curiosity rover is a shoebox-sized device using transmission geometry and an energy-discriminating CCD detector. The instrument has returned the first X-ray diffraction data for soil and drilled samples from Mars outcrops, revealing a suite of primary basaltic minerals, amorphous components and varied hydrous alteration products including phyllosilicates., The Mars Science Laboratory landed in Gale crater on Mars in August 2012, and the Curiosity rover then began field studies on its drive toward Mount Sharp, a central peak made of ancient sediments. CheMin is one of ten instruments on or inside the rover, all designed to provide detailed information on the rocks, soils and atmosphere in this region. CheMin is a miniaturized X-ray diffraction/X-ray fluorescence (XRD/XRF) instrument that uses transmission geometry with an energy-discriminating CCD detector. CheMin uses onboard standards for XRD and XRF calibration, and beryl:quartz mixtures constitute the primary XRD standards. Four samples have been analysed by CheMin, namely a soil sample, two samples drilled from mudstones and a sample drilled from a sandstone. Rietveld and full-pattern analysis of the XRD data reveal a complex mineralogy, with contributions from parent igneous rocks, amorphous components and several minerals relating to aqueous alteration. In particular, the mudstone samples all contain one or more phyllosilicates consistent with alteration in liquid water. In addition to quantitative mineralogy, Rietveld refinements also provide unit-cell parameters for the major phases, which can be used to infer the chemical compositions of individual minerals and, by difference, the composition of the amorphous component.