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The spectral properties of anhydrous carbonates and nitrates are dominated by strong, sharp vibrational bands due to the CO32− and NO3− anions observed as absorption bands in near-infrared spectra, as Reststrahlen features or absorption bands in mid-IR spectra, depending on particle size, and as peaks in Raman spectra. These spectral features provide a reliable means to identify the occurrence of carbonates and nitrates on planetary surfaces, which in turn contribute to our understanding of the environment and chemistry of planetary bodies. Four modes occur for carbonates and nitrates due to symmetric stretching (ν1), out-of-plane bending (ν2), asymmetric stretching (ν3), and in-plane bending (ν4). The vibrational absorptions of these spectral features vary with the mineral structure and the size of the cation, where the calcite-, dolomite-, aragonite-, and alkali-type structures result in different spectral features. Mid-IR bands for carbonates and nitrates occur from 1,040 to 1,105 cm−1 for ν1, from 810 to 906 cm−1 for ν2, from 1,275 to 1,590 cm−1 for ν3, and from 670 to 756 cm−1 for ν4. In Raman spectra the carbonate and nitrate absorptions are observed near 1,050–1,080 cm−1 for ν1, near 880 cm−1 for ν2, near 1,415–1,430 cm−1 for ν3, and near 680–700 cm−1 for ν4. NIR spectra include bands due to overtones and combinations at ∼1.75, 1.9, 2.0, 2.3, 2.5, 3.4, 4.0, and 4.6 μm for carbonates and ∼1.8, 2.0, 2.2, 2.4, 2.6, 3.5, 4.1, and 4.8 μm for nitrates. This study provides data for remote determination of carbonate and nitrate chemistry and will enable better characterization of these minerals on planetary bodies including Mars, Ceres, and Bennu.

Perseverance landed at the Octavia E. Butler landing site next to the Seitah dune region in Jezero crater on 18 February 2021, in close proximity...

Carbonate minerals have been detected in Jezero crater, an ancient lake basin that is the landing site of the Mars 2020 Perseverance rover, and within the regional olivine‐bearing (ROB) unit in the Nili Fossae region surrounding this crater. It has been suggested that some carbonates in the margin fractured unit, a rock unit within Jezero crater, formed in a fluviolacustrine environment, which would be conducive to preservation of biosignatures from paleolake‐inhabiting lifeforms. Here, we show that carbonate‐bearing rocks within and outside of Jezero crater have the same range of visible‐to‐near‐infrared carbonate absorption strengths, carbonate absorption band positions, thermal inertias, and morphologies. Thicknesses of exposed carbonate‐bearing rock cross‐sections in Jezero crater are ∼75–90 m thicker than typical ROB unit cross‐sections in the Nili Fossae region, but have similar thicknesses to ROB unit exposures in Libya Montes. These similarities in carbonate properties within and outside of Jezero crater is consistent with a shared origin for all of the carbonates in the Nili Fossae region. Carbonate absorption minima positions indicate that both Mg‐ and more Fe‐rich carbonates are present in the Nili Fossae region, consistent with the expected products of olivine carbonation. These estimated carbonate chemistries are similar to those in martian meteorites and the Comanche carbonates investigated by the Spirit rover in Columbia Hills. Our results indicate that hydrothermal alteration is the most likely formation mechanism for non‐deltaic carbonates within and outside of Jezero crater., Key Points Carbonates within and outside of Jezero crater have similar spectra, thermal inertias, morphologies, and thicknessesCarbonates within and outside of Jezero crater likely formed via the same processesHydrothermal alteration and evaporation are the most likely processes for carbonate formation within and outside of Jezero crater

Jezero crater, an ancient lake basin that is the landing site of the Mars 2020 Perseverance rover, contains a carbonate-bearing rock unit termed the margin fractured unit. Some of the carbonates in...

A well-preserved, ancient delta deposit, in combination with ample exposures of carbonate outcrops, makes Jezero Crater in Nili Fossae a compelling astrobiological site. We use Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) observations to characterize the surface mineralogy of the crater and surrounding watershed. Previous studies have documented the occurrence of olivine and carbonates in the Nili Fossae region. We focus on correlations between these two well-studied lithologies in the Jezero crater watershed. We map the position and shape of the olivine 1 μm absorption band and find that carbonates are found in association with olivine which displays a 1 μm band shifted to long wavelengths. We then use Thermal Emission Imaging Spectrometer (THEMIS) coverage of Nili Fossae and perform tests to investigate whether the long wavelength shifted (redshifted) olivine signature is correlated with high thermal inertia outcrops. We find that there is no consistent correlation between thermal inertia and the unique olivine signature. We discuss a range of formation scenarios for the olivine and carbonate associations, including the possibility that these lithologies are products of serpentinization reactions on early Mars. These lithologies provide an opportunity for deepening our understanding of early Mars and, given their antiquity, may provide a framework to study the timing of valley networks and the thermal history of the Martian crust and interior from the early Noachian to today., Plain Language Summary We used Martian orbital data from a hyperspectral instrument on the spacecraft Mars Reconnaissance Orbiter (MRO) to assess the minerals on the surface of Mars at the future landing site of the Mars2020 rover. We found correlations between the minerals olivine and carbonate which are of interest to planetary scientists due to often being associated with volcanic activity (olivine) and life (carbonates). We used spectra of these minerals to infer the likely composition and grain size range of the olivine unit, and we document our new approach. We use our curve fitting approach to identify for the first time a special group of olivine-bearing rocks at Nili Fossae that show the most extremely redshifted absorption bands, and we show herein that these special olivines are not spatially associated with carbonates or clay rocks.

Quantitative estimates of clay minerals on the martian surface, via remote sensing observations, provide constraints on activity, timing, duration, and extent of aqueous processes and the geochemical environment in martian history. We describe an analytical study to begin enabling quantitative estimates of phyllosilicates when mixed with martian analog materials. We characterize the chemistry, mineralogy, particle size distribution, and reflectance spectra of the end-member materials: saponite, montmorillonite, pyroxene, and palagonitic soil. Reflectance spectra were obtained for physical mixtures of saponite and montmorillonite with pyroxene, and saponite with palagonitic soil. We analyzed the diagnostic phyllosilicate spectral signatures in the 2.2–2.4 μm wavelength region in detail for the mixtures. This involved fitting the observed ∼2.3 or ∼2.2 μm band depth, associated with the presence of saponite and montmorillonite, respectively, as a function of the abundance of these materials in the mixtures. Based upon the band depth of the spectral features we find that 3–5 wt.% of the clay minerals in the mixture with pyroxene can be recognized and at 25 wt.% their presence is indisputable in the mixtures. When the saponite is mixed with the lower albedo palagonitic soil, its presence is clearly distinguishable via the 1.4 and 2.3 μm features at 25 wt.% abundance. These relationships, between abundance and band depth, provide an ability to quantitatively address the amount of these materials in mixtures. The trends described here provide guidance for estimating the presence of phyllosilicates in matrices on the martian surface.

This study of the spectral properties of Ca-sulfates was initiated to support remote detection of these minerals on Mars. Gypsum, bassanite, and anhydrite are the currently known forms of Ca-sulfates. They are typically found in sedimentary evaporites on Earth, but can also form via reaction of acidic fluids associated with volcanic activity. Reflectance, emission, transmittance, and Raman spectra are discussed here for various sample forms. Gypsum and bassanite spectra exhibit characteristic and distinct triplet bands near 1.4–1.5 μm, a strong band near 1.93–1.94 μm, and multiple features near 2.1–2.3 μm attributed to H2O. Anhydrite, bassanite, and gypsum all have SO4 combination and overtone features from 4.2–5 μm that are present in reflectance spectra. The mid-IR region spectra exhibit strong SO4 ν3 and ν4 vibrational bands near 1150–1200 and 600–680 cm−1 (~8.5 and 16 μm), respectively. Additional weaker features are observed near 1005–1015 cm−1 (~10 μm) for ν1 and near 470–510 cm−1 (~20 μm) for ν2. The mid-IR H2O bending vibration occurs near 1623–1630 cm−1 (~6.2 μm). The visible/near-infrared region spectra are brighter for the finer-grained samples. In reflectance and emission spectra of the mid-IR region the ν4 bands begin to invert for the finer-grained samples, and the ν1 vibration occurs as a band instead of a peak and has the strongest intensity for the finer-grained samples. The ν2 vibration is a sharp band for anhydrite and a broad peak for gypsum. The band center of the ν1 vibration follows a trend of decreasing frequency (increasing wavelength) with increasing hydration of the sample in the transmittance, Raman, and reflectance spectra. Anhydrite forms at elevated temperatures compared to gypsum, and at lower temperature, salt concentration, and pH than bassanite. The relative humidity controls whether bassanite or gypsum is stable. Thus, distinguishing among gypsum, bassanite, and anhydrite via remote sensing can provide constraints on the geochemical environment.

[1] Mineral detection on Mars largely relies on laboratory data of minerals and mineral mixtures. The objective of this study is to provide reflectance spectra in the visible/near-infrared (VNIR) and mid-IR regions, X-ray diffraction (XRD) data and Mossbauer spectra of a suite of carbonate, phyllosilicate and olivine mixtures in order to facilitate identification and characterization of these minerals on Mars. Remote sensing observations indicate that combinations of these minerals are present in ancient rocks on Mars around the Isidis Basin and in Gusev crater. Magnesite, nontronite, and forsterite size fractions

Carbonate rocks in the Mojave Desert are presented as potential analogues for the carbonates on Mars. Rocks collected from the Little Red Hill site contain iron oxide-bearing coatings that greatly suppress the spectral features due to carbonate of the underlying material and impart a spectral slope. The Mojave Desert was formerly a lush pedogenic soil environment that, over time, transformed into the current arid climate with abundant rock varnish. One niche for microbes in the current desolate environment is inside and underneath the rocks where the microbes profit from solar protection by the iron oxide rock coatings. Carbonates were long predicted to be present on Mars and have recently been detected by instruments on Phoenix and MER and using hyperspectral orbiters such as the Compact Reconnaissance Imaging Spectrometer for Mars (CRISM), the Planetary Fourier Spectrometer (PFS) and the Thermal Emission Spectrometer (TES). We describe here the results of a study of carbonate rocks from the Little Red Hill site of the Mojave Desert that includes X-ray diffraction (XRD), chemistry and visible-infrared reflectance spectroscopy. Coatings on the carbonate rocks greatly reduced the strength of the carbonate bands and caused changes in the shape of some bands. We compare these data with a carbonate outcrop at Nili Fossae, Mars. If microbes once inhabited Mars, similar carbonate rocks with iron oxide coatings could have provided a UV-protected niche there as well. Thus, analysis of carbonate-bearing regions on Mars by future landers would be useful sites to search for biosignatures.

Geochemical models for Mars predict carbonate formation during aqueous alteration. Carbonate-bearing rocks had not previously been detected on Mars' surface, but Mars Reconnaissance Orbiter mapping reveals a regional rock layer with near-infrared spectral characteristics that are consistent with the presence of magnesium carbonate in the Nili Fossae region. The carbonate is closely associated with both phyllosilicate-bearing and olivine-rich rock units and probably formed during the Noachian or early Hesperian era from the alteration of olivine by either hydrothermal fluids or near-surface water. The presence of carbonate as well as accompanying clays suggests that waters were neutral to alkaline at the time of its formation and that acidic weathering, proposed to be characteristic of Hesperian Mars, did not destroy these carbonates and thus did not dominate all aqueous environments.

Coordinated visible/near-infrared reflectance/mid-infrared reflectance and emissivity spectra of four groups of phyllosilicates were undertaken to provide insights into the differences within and among groups of smectites, kaolinite-serpentines, chlorites and micas. Identification and characterization of phyllosilicates via remote sensing on Earth and Mars can be achieved using the OH combination bands in the 2.2–2.5 μm region and the tetrahedral SiO4 vibrations from ~8.8–12 μm (~1140–830 cm–1) and ~20–25 μm (500–400 cm–1). The sharp and well resolved OH combination bands in the 2.2–2.5 μm region provide unique fingerprints for specific minerals. Al-rich phyllosilicates exhibit OH combination bands near 2.2 μm, while these bands are observed near 2.29–2.31, 2.33–2.34 μm and near 2.35–2.37 μm for Fe3+-rich, Mg-rich and Fe2+-rich phyllosilicates, respectively. When a tetrahedral substitution of Al or Fe3+ for Si occurs, the position of the Si(Al,Fe)O4 stretching mode absorption shifts. Depending on the size of the cation, the Si(Al,Fe)O4 bending mode near 500 cm–1 is split into multiple bands that may be distinguished via hyperspectral remote sensing techniques. The tetrahedral SiO4 vibrations are also influenced by the octahedral cations, such that Al-rich, Fe-rich and Mg-rich phyllosilicates can be discriminated in reflectance and emissivity spectra based on diagnostic positions of the stretching and bending bands. Differences among formation conditions for these four groups of phyllosilicates are also discussed. Hyperspectral remote sensing can be used to identify specific phyllosilicates using electronic and vibrational features and thus provide constraints on the chemistry and formation conditions of soils.

The Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) has returned observations of the Nili Fossae region indicating the presence of Mg- carbonate in small (, 21 pages, 7 figures, 2 tables

The conformations of Glu-plasminogen and defined proteolytic fragments, in the presence and absence of 6-aminohexanoic acid (6-AHA), trans-4-(aminomethyl)cyclohexanecarboxylic acid (t-AMCHA), and benzamidine, were studied using three methods: size-exclusion high-performance liquid chromatography (SE-HPLC), small-angle X-ray scattering (SAXS), and dynamic laser light scattering (DLLS). The well-documented conformational change of Glu-plasminogen with 6-AHA or t-AMCHA was measured as a decrease in molecular elution time by SE-HPLC (8.93 +/- 0.01 to 8.32 +/- 0.01 min) and increases in radius of gyration (30.7 +/- 0.1 to 49.8 +/- 0.3 A) and Stokes radius (40.6 +/- 0.3 to 48.5 +/- 0.3 A) by SAXS and DLLS, respectively. The addition of benzamidine to Glu-plasminogen resulted in a conformation (radius of gyration 41.0 +/- 0.4 A and Stokes radius 46.6 +/- 0.3 A) distinct from that in the presence of 6-AHA. 6-AHA, but not benzamidine, induced significant conformational changes in Lys-plasminogen and kringles 1 + 2 + 3 + 4 + 5. We conclude that Glu-plasminogen adopts three distinct conformations involving two intramolecular interactions: one mediated by regions of the NH2-terminal peptide and kringle 5, competed for by 6-AHA or benzamidine, and the other possibly between kringles 3 and 4, competed for by 6-AHA but not benzamidine.

[1] Juventae Chasma contains four light-toned sulfate-bearing mounds (denoted here as A–D from west to east) inside the trough, mafic outcrops at the base of the mounds and in the wall rock, and light-toned layered deposits of opal and ferric sulfates on the plateau. Hyperspectral visible/near-infrared Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) spectra were used to identify monohydrated and polyhydrated sulfate (PHS) outcrops of layered material on the bright mounds. Most of the monohydrated sulfate signatures closely resemble those of szomolnokite (FeSO4·H2O), characterized by a water band near 2.08 μm, while some areas exhibit spectral features more similar to those of kieserite (MgSO4·H2O), with a band centered closer to 2.13 μm. The largest PHS outcrops occur on the top of mound B, and their spectral features are most consistent with ferricopiapite, melanterite, and starkeyite, but a specific mineral cannot be uniquely identified at this time. Coordinated analyses of CRISM maps, Mars Orbiter Laser Altimeter elevations, and High Resolution Imaging Science Experiment images suggest that mounds A and B may have formed together and then eroded into separate mounds, while mounds C and D likely formed separately. Mafic minerals (low-Ca pyroxene, high-Ca pyroxene, and olivine) are observed in large ∼2–10 km wide outcrops in the wall rock and in smaller outcrops ∼50–500 m across at the floor of the canyon. Most of the wall rock is covered by at least a thin layer of dust and does not exhibit strong features characteristic of these minerals. The plateau region northwest of Juventae Chasma is characterized by an abundance of light-toned layered deposits. One region contains two spectrally unique phases exhibiting a highly stratified, terraced pattern. CRISM spectra of one unit eroded into swirling patterns with arc-like ridges exhibit a narrow 2.23-μm band assigned to hydroxylated ferric sulfate. A thin layer of a fractured material bearing an opaline silica phase is observed at the contact between the older plateau unit and the younger hydroxylated ferric sulfate-bearing light-toned layered deposits. Hydrothermal processes may have produced an acidic environment that fostered formation of the hydrated silica and hydroxylated ferric sulfate units.

PURPOSE: Gemcitabine-platinum combination activity has been clearly established in a number of phase II studies. It has also been compared against other combinations in many phase III trials. It is generally believed that all such regimens have an equivalent impact on survival. This meta-analysis aims to quantify the treatment effect of gemcitabine plus a platinum agent in the treatment of advanced NSCLC and compare the combination to other regimens used globally. DESIGN: Data from a total of 4556 patients from 13 randomized trials investigating gemcitabine in combination with a platinum agent versus any other platinum-containing regimen were included in a meta-analysis of time-to-event outcomes. RESULTS: A significant reduction in overall mortality in favor of gemcitabine-platinum regimens was observed, hazard ratio (HR) 0.90 (95% CI: 0.84-0.96) with an absolute benefit at 1 year of 3.9%. Median survival was 9.0 months for the gemcitabine-platinum regimens and 8.2 months for the comparator regimens. Sub-group analysis of the first- and second-generation platinum-based comparator regimens also indicated a significant benefit for gemcitabine-platinum regimens, HR 0.84 (CI: 0.71-0.9985). Analysis of third-generation agent plus platinum regimens showed a non-significant trend favoring gemcitabine-platinum regimens, HR 0.93 (CI: 0.86-1.01). There was a significant decrease in the risk of disease progression in favor of gemcitabine-platinum regimens, HR 0.88 (CI: 0.82-0.93). An absolute benefit of 4.2% at 1 year was estimated. Median progression-free survival was 5.1 months for gemcitabine-platinum regimens compared with 4.4 months for the comparator regimens. Sub-group analysis indicated a statistically significant progression-free survival benefit for patients assigned to gemcitabine-platinum treatment compared to first- and second-generation platinum regimens, HR 0.85 (CI: 0.77-0.94), and third-generation agent plus platinum regimens, HR 0.89 (CI: 0.82-0.96).

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