The Mars Science Laboratory Curiosity rover has been traversing strata at the base of Aeolis Mons (informally known as Mount Sharp) since September 2014. The Murray formation makes up the lowest exposed strata of the Mount Sharp group and is composed primarily of finely laminated lacustrine mudstone intercalated with rare crossbedded sandstone that is prodeltaic or fluvial in origin. We report on the first three drilled samples from the Murray formation, measured in the Pahrump Hills section. Rietveld refinements and FULLPAT full pattern fitting analyses of X-ray diffraction patterns measured by the MSL CheMin instrument provide mineral abundances, refined unit-cell parameters for major phases giving crystal chemistry, and abundances of X-ray amorphous materials. Our results from the samples measured at the Pahrump Hills and previously published results on the Buckskin sample measured from the Marias Pass section stratigraphically above Pahrump Hills show stratigraphic variations in the mineralogy; phyllosilicates, hematite, jarosite, and pyroxene are most abundant at the base of the Pahrump Hills, and crystalline and amorphous silica and magnetite become prevalent higher in the succession. Some trace element abundances measured by APXS also show stratigraphic trends; Zn and Ni are highly enriched with respect to average Mars crust at the base of the Pahrump Hills (by 7.7 and 3.7 times, respectively), and gradually decrease in abundance in stratigraphically higher regions near Marias Pass, where they are depleted with respect to average Mars crust (by more than an order of magnitude in some targets). The Mn stratigraphic trend is analogous to Zn and Ni, however, Mn abundances are close to those of average Mars crust at the base of Pahrump Hills, rather than being enriched, and Mn becomes increasingly depleted moving upsection. Minerals at the base of the Pahrump Hills, in particular jarosite and hematite, as well as enrichments in Zn, Ni, and Mn, are products of acid-sulfate alteration on Earth. We hypothesize that multiple influxes of mildly to moderately acidic pore fluids resulted in diagenesis of the Murray formation and the observed mineralogical and geochemical variations. The preservation of some minerals that are highly susceptible to dissolution at low pH (e.g., mafic minerals and fluorapatite) suggests that acidic events were not long-lived and that fluids may not have been extremely acidic (pH>2). Alternatively, the observed mineralogical variations within the succession may be explained by deposition in lake waters with variable Eh and/or pH, where the lowermost sediments were deposited in an oxidizing, perhaps acidic lake setting, and sediments deposited in the upper Pahrump Hills and Marias Pass were deposited lake waters with lower Eh and higher pH

Vera Rubin ridge (VRR) is an erosion‐resistant feature on the northwestern slope of Mount Sharp in Gale crater, Mars, and orbital visible/shortwave infrared measurements indicate it contains red hematite. The Mars Science Laboratory Curiosity rover performed an extensive campaign on VRR to study its mineralogy, geochemistry, and sedimentology to determine the depositional and diagenetic history of the ridge and constrain the processes by which the hematite could have formed. X‐ray diffraction (XRD) data from the CheMin instrument of four samples drilled on and below VRR demonstrate differences in iron, phyllosilicate, and sulfate mineralogy and hematite grain size. Hematite is common across the ridge, and its detection in a gray outcrop suggest localized regions with coarse‐grained hematite, which commonly forms from warm fluids. Broad XRD peaks for hematite in one sample below VRR and the abundance of FeOT in the amorphous component suggest the presence of nanocrystalline hematite and amorphous Fe oxides/oxyhydroxides. Well crystalline akaganeite and jarosite are present in two samples drilled from VRR, indicating at least limited alteration by acid‐saline fluids. Collapsed nontronite is present below VRR, but samples from VRR contain phyllosilicate with d(001) = 9.6 Å, possibly from ferripyrophyllite or an acid‐altered smectite. The most likely cementing agents creating the ridge are hematite and opaline silica. We hypothesize late diagenesis can explain much of the mineralogical variation on the ridge, where multiple fluid episodes with variable pH, salinity, and temperature altered the rocks, causing the precipitation and crystallization of phases that are not otherwise in equilibrium.

Silver nanoparticles (Ag(NP)) are widely utilized in increasing number of medical and consumer products due to their antibacterial properties. Once released to aquatic system, Ag(NP) undergoes oxidative dissolution leading to production of toxic Ag(+). Dissolved Ag(+) can have a severe impact on various organisms, including indigenous microbial communities, fungi, alga, plants, vertebrates, invertebrates, and human cells. Therefore, it is important to investigate fate of Ag(NP) and determine physico-chemicals parameters that control Ag(NP) behavior in the natural environment. Nanoparticle size might have a dominant effect on Ag(NP) dissolution in natural waters. In this work, we investigated size-dependent dissolution of AgNP exposed to ultrapure deionized water (pH ≈ 7) and acetic acid (pH 3) and determined changes in nanoparticle size after dissolution. Silver nanoparticles stabilized by thiol functionalized methoxyl polyethylene glycol (PEGSH) of 6 nm (Ag(NP_)6), 9 nm (Ag(NP_)9), 13 nm (Ag(NP_)13), and 70 nm (Ag(NP_)70) were prepared. The results of dissolution experiments showed that the extent of AgNP dissolution in acetic acid was larger than in water. Solubility of Ag(NP) increased with the size decrease and followed the order Ag(NP_)6 > Ag(NP_)9 > Ag(NP_)13 > Ag(NP_)70 in both water and acetic acid. Transmission electron microscopy (TEM) was applied to characterize changes in size and morphology of the AgNP after dissolution in water. Analysis of Ag(NP) by TEM revealed that the particle morphology did not change during dissolution. The particles remained approximately spherical in shape, and no visible aggregation was observed in the samples. TEM analysis also demonstrated that Ag(NP_)6, Ag(NP_)9, and Ag(NP_)13 increased in size after dissolution likely due to Ostwald ripening.

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The Glen Torridon (GT) region in Gale crater, Mars is a region with strong clay mineral signatures inferred from orbital spectroscopy. The CheMin X-ray diffraction (XRD) instrument onboard the Mars Science Laboratory rover, Curiosity, measured some of the highest clay mineral abundances to date within GT, complementing the orbital detections. GT may also be unique because in the XRD patterns of some samples, CheMin identified new phases, including: (a) Fe-carbonates, and (b) a phase with a novel peak at 9.2 Å. Fe-carbonates have been previously suggested from other instruments onboard, but this is the first definitive reporting by CheMin of Fe-carbonate. This new phase with a 9.2 Å reflection has never been observed in Gale crater and may be a new mineral for Mars, but discrete identification still remains enigmatic because no single phase on Earth is able to account for all of the GT mineralogical, geochemical, and sedimentological constraints. Here, we modeled XRD profiles and propose an interstratified clay mineral, specifically greenalite-minnesotaite, as a reasonable candidate. The coexistence of Fe-carbonate and Fe-rich clay minerals in the GT samples supports a conceptual model of a lacustrine groundwater mixing environment. Groundwater interaction with percolating lake waters in the sediments is common in terrestrial lacustrine settings, and the diffusion of two distinct water bodies within the subsurface can create a geochemical gradient and unique mineral front in the sediments. Ultimately, the proximity to this mixing zone may have controlled the secondary minerals preserved in sedimentary rocks exposed in GT. Plain Language SummaryThe Glen Torridon (GT) region on the lower slopes of the sedimentary mound in Gale Crater, Mars is characterized by terrains with enhanced clay mineral spectral signatures, as identified from orbit. This regional distinction in the landscape was confirmed on the ground with some of the highest clay mineral abundances measured to date by the CheMin X-ray diffraction instrument onboard the Mars Science Laboratory rover, Curiosity. In addition to clay minerals, this region is unique because of two new phase identifications for CheMin: (a) Fe-carbonates, which have been previously suggested from other instruments onboard Curiosity, but definitively identified for the first time with CheMin and (b) a new phase that has never been detected before on Mars. Even on Earth, few examples of this enigmatic phase exist, but here we modeled a mixture of clay minerals that were able to replicate the novel CheMin observations. Conceptually, a lake environment that interacts with discharging groundwater in the subsurface is an ideal setting to form the observed mineralogical trends in the GT region. Ancient lake and ground waters would have THORPE ET AL.

Experiments were performed herein to investigate the rates and products of heterogeneous reduction of Tc(VII) by Fe(II) adsorbed to hematite and goethite, and by Fe(II) associated with a dithionite-citrate-bicarbonate (DCB) reduced natural phyllosilicate mixture [structural, ion-exchangeable, and edge-complexed Fe(II)] containing vermiculite, illite, and muscovite. The heterogeneous reduction of Tc(VII) by Fe(II) adsorbed to the Fe(III) oxides increased with increasing pH and was coincident with a second event of Fe 2þ ðaqÞ adsorption. The reaction was almost instantaneous above pH 7. In contrast, the reduction rates of Tc(VII) by DCB-reduced phyllosilicates were not sensitive to pH or to added Fe 2þ ðaqÞ that adsorbed to the clay. The reduction kinetics were orders of magnitude slower than observed for the Fe(III) oxides, and appeared to be controlled by structural Fe(II). The following affinity series for heterogeneous Tc(VII) reduction by Fe(II) was suggested by the experimental results: aqueous Fe(II) $ adsorbed Fe(II) in phyllosilicates [ion-exchangeable and some edge-complexed Fe(II)] ( structural Fe(II) in phyllosilicates ( Fe(II) adsorbed on Fe(III) oxides. Tc-EXAFS spectroscopy revealed that the reduction products were virtually identical on hematite and goethite that were comprised primarily of sorbed octahedral TcO 2 monomers and dimers with significant Fe(III) in the second coordination shell. The nature of heterogeneous Fe(III) resulting from the redox reaction was ambiguous as probed by Tc-EXAFS spectroscopy, although Mö ssbauer spectroscopy applied to an experiment with 56 Fe-goethite with adsorbed 57 Fe(II) implied that redox product Fe(III) was goethite-like. The Tc(IV) reduction product formed on the DCB-reduced phyllosilicates was different from the Fe(III) oxides, and was more similar to Tc(IV) oxyhydroxide in its second coordination shell. The heterogeneous reduction of Tc(VII) to less soluble forms by Fe(III) oxideadsorbed Fe(II) and structural Fe(II) in phyllosilicates may be an important geochemical process that will proceed at very different rates and that will yield different surface species depending on subsurface pH and mineralogy.

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The Curiosity rover's exploration of rocks and soils in Gale crater has provided diverse geochemical and mineralogical data sets, underscoring the complex geological history of the region. We report the crystalline, clay mineral, and amorphous phase distributions of four Gale crater rocks from an 80‐m stratigraphic interval. The mineralogy of the four samples is strongly influenced by aqueous alteration processes, including variations in water chemistries, redox, pH, and temperature. Localized hydrothermal events are evidenced by gray hematite and maturation of amorphous SiO2 to opal‐CT. Low‐temperature diagenetic events are associated with fluctuating lake levels, evaporative events, and groundwater infiltration. Among all mudstones analyzed in Gale crater, the diversity in diagenetic processes is primarily captured by the mineralogy and X‐ray amorphous chemistry of the drilled rocks. Variations indicate a transition from magnetite to hematite and an increase in matrix‐associated sulfates suggesting intensifying influence from oxic, diagenetic fluids upsection. Furthermore, diagenetic fluid pathways are shown to be strongly affected by unconformities and sedimentary transitions, as evidenced by the intensity of alteration inferred from the mineralogy of sediments sampled adjacent to stratigraphic contacts.