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David Vaniman

Publications and source records attributed to David Vaniman.

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Sulfur cycle in the Valles Caldera volcanic complex, New Mexico – Letter 1: Sulfate sources in aqueous system, and implications for S isotope record in Gale Crater on Mars

Initial in situ sulfur (S) isotope measurements of the Martian bedrock in Gale Crater have revealed an unexpectedly wide range of δ 34 S values (−47 to +28%). Generally, it is unclear what processes could have contributed to these large isotope fractionations. Therefore, we studied S sources and aqueous SO 2− 4 cycling in the Valles Caldera volcanic complex, New Mexico to better understand S isotope fractionations related to S degassing, hydrothermal activity, and low-temperature processes in aqueous environment. Overall, our study demonstrates that volcanic systems show large spatial heterogeneity in δ 34 S. Magmatic S sources are obvious in steam-dominated H 2 S degassing and precipitation of secondary minerals from hydrothermal fluids with low δ 34 S values of +0.9 ±3%. Locally, however, hydrothermal processes have resulted in more negative δ 34 S values in sulfide minerals (−18 to −4%) and more positive δ 34 S values in sulfate minerals (−1 to +3%). Major aqueous SO 2− 4 sources are oxidation of H 2 S from modern hydrothermal gas emission, and oxidation and dissolution of sulfide and sulfate minerals present in the hydrothermally altered bedrock and crater-lake sediments. The δ 34 S of aqueous SO 2− 4 in surface water and groundwater varies widely (−8 to +5%) and is similar to major S endmembers that undergo oxidation and/or dissolution by active hydrological system. Minor SO 2− 4 contributions with more positive δ 34 S values (+9 to +14%) come from deeply circulating geothermal fluids and negligible amounts from atmospheric deposition (+5 to +7% in snow). Elevated SO 2− 4 contents are mainly associated with modern and past H 2 S emissions and oxidations near the surface. On regional scale, however, most of the intracaldera bedrock is S-depleted, thus the SO 2− 4 contents are usually low in the surface aquatic system and younger sedimentary lake deposits formed at times of negligible near surface hydrothermal activity. In general, magmatic-hydrothermal processes apparently cause the largest δ 34 S variation in S-bearing minerals on volcanic terrains. Therefore, we infer that the measured wide range of δ 34 S values in the Gale sediments by the Curiosity rover on Mars can be explained by S isotope composition of magmatic-hydrothermal sulfide and sulfate minerals that were present in the initial igneous/volcanic rocks prior to crater formation. Later aqueous processes involved oxidation and dissolution of S minerals initially present in these rocks and led to subsequent formation of diagenetic fluids and alteration products enriched in SO 2− 4 with relatively large δ 34 S variation. Additionally, physical erosion, transport and deposition of detrital hydrothermal S minerals from igneous/volcanic rocks might be in part responsible for the measured wide range of δ 34 S in Gale Crater. These unique S isotope results, measured in situ on another planet for the first time, imply the importance of magmatic-hydrothermal fluids in S transport on early Mars and their subsequent alteration in low-temperature aqueous environments.

New Mexico

Diagenetic silica enrichment and late-stage groundwater activity in Gale crater, Mars

Diagenetic silica enrichment in fracture-associated halos that crosscut lacustrine and unconformably overlying aeolian sedimentary bedrock is observed on the lower north slope of Aeolis Mons in Gale crater, Mars. The diagenetic silica enrichment is colocated with detrital silica enrichment observed in the lacustrine bedrock yet extends into a considerably younger, unconformably draping aeolian sandstone, implying that diagenetic silica enrichment postdates the detrital silica enrichment. A causal connection between the detrital and diagenetic silica enrichment implies that water was present in the subsurface of Gale crater long after deposition of the lacustrine sediments and that it mobilized detrital amorphous silica and precipitated it along fractures in the overlying bedrock. Although absolute timing is uncertain, the observed diagenesis likely represents some of the most recent groundwater activity in Gale crater and suggests that the timescale of potential habitability extended considerably beyond the time that the lacustrine sediments of Aeolis Mons were deposited.

Geophysical Research Letters

ChemCam activities and discoveries during the nominal mission of the Mars Science Laboratory in Gale crater, Mars

At Gale crater, Mars, ChemCam acquired its first laser-induced breakdown spectroscopy (LIBS) target on Sol 13 of the landed portion of the mission (a Sol is a Mars day). Up to Sol 800, more than 188 000 LIBS spectra were acquired on more than 5800 points distributed over about 650 individual targets. We present a comprehensive review of ChemCam scientific accomplishments during that period, together with a focus on the lessons learned from the first use of LIBS in space. For data processing, we describe new tools that had to be developed to account for the uniqueness of Mars data. With regard to chemistry, we present a summary of the composition range measured on Mars for major-element oxides (SiO 2 , TiO 2 , Al 2 O 3 , FeO T , MgO, CaO, Na 2 O, K 2 O) based on various multivariate models, with associated precisions. ChemCam also observed H, and the non-metallic elements C, O, P, and S, which are usually difficult to quantify with LIBS. F and Cl are observed through their molecular lines. We discuss the most relevant LIBS lines for detection of minor and trace elements (Li, Rb, Sr, Ba, Cr, Mn, Ni, and Zn). These results were obtained thanks to comprehensive ground reference datasets, which are set to mimic the expected mineralogy and chemistry on Mars. With regard to the first use of LIBS in space, we analyze and quantify, often for the first time, each of the advantages of using stand-off LIBS in space: no sample preparation, analysis within its petrological context, dust removal, sub-millimeter scale investigation, multi-point analysis, the ability to carry out statistical surveys and whole-rock analyses, and rapid data acquisition. We conclude with a discussion of ChemCam performance to survey the geochemistry of Mars, and its valuable support of decisions about selecting where and whether to make observations with more time and resource-intensive tools in the rover's instrument suite. In the end, we present a bird's-eye view of the many scientific results: discovery of felsic Noachian crust, first observation of hydrated soil, discovery of manganese-rich coatings and fracture fills indicating strong oxidation potential in Mars' early atmosphere, characterization of soils by grain size, and wide scale mapping of sedimentary strata, conglomerates, and diagenetic materials.

Journal of Analytical Atomic Spectrometry

Heat-producing elements in the lunar mantle: Insights from ion microprobe analyses of lunar pyroclastic glasses

We provide new estimates for the abundance of heat-producing elements in the lunar mantle by using SIMS techniques to measure the concentrations of thorium and samarium in lunar pyroclastic glasses. Lunar pyroclastic glasses are utilized in this study because they represent quenched products of near-primary melts from the lunar mantle and as such, they provide compositional information about the mantle itself. Thorium and samarium were measured because: (1) Th is not significantly fractionated from Sm during partial melting of the pyroclastic glass source regions, which are dominated by olivine and pyroxene. Therefore, the Th/Sm ratios that we measure in the pyroclastic glasses reflect the Th/Sm ratio of the pyroclastic glass source regions. (2) Strong correlations between Th, U, and K on the Moon allow us to use measured Th concentrations to estimate the concentrations of U and K in the pyroclastic glasses. (3) Th, Sm, U, and K are radioactive elements and as such, their concentrations can be used to investigate heat production in the lunar mantle. The results from this study show that the lunar mantle is heterogeneous with respect to heat-producing elements and that there is evidence for mixing of a KREEP component into the source regions of some of the pyroclastic glasses. Because the source regions for many of the glasses are deep (⩾400 km), we propose that a KREEP component was transported to the deep lunar mantle. KREEP enriched sources produce 138% more heat than sources that do not contain KREEP and therefore, could have provided a source of heat for extended periods of nearside basaltic magmatism. Data from this study, in conjunction with models for the fractional crystallization of a lunar magma ocean, are used to show that the average lunar mantle contains 0.15 ppm Th, 0.54 ppm Sm, 0.039 ppm U, and 212 ppm K. This is a greater enrichment in radiogenic elements than some earlier estimates, suggesting a more prolonged impact of radiogenic heat on nearside basaltic volcanism.

Geochimica et Cosmochimica Acta

Identifying the effects of petrologic processes in a closed basaltic system using trace element concentrations in olivines and glasses: Implications for comparative planetology

We use trace-element concentrations in olivines and glasses from a closed basaltic system to identify the effects of petrologic processes on the trace-element record of that system. The closed basaltic system in question is the Makaopuhi Lava Lake (MLL), which is closed with respect to magma mixing. Detailed studies of this lava lake have provided important information about system variables and petrologic processes that have been measured and observed at the lake. These previous studies show that olivine crystallized from the lava lake at all stages of the lake’s evolution, which means that olivine and residual glasses contain a record of the lake’s petrologic history. We use this information, in conjunction with variations in trace-element concentrations in olivines and glasses, to show that mineral crystallization, gravitational settling, convective flow, filter pressing, and mineral-melt interface kinetics have characteristic effects on the trace element record of a closed basaltic system. These results are pertinent to the field of comparative planetology because they can be used to evaluate petrologic information in small samples from other planetary bodies, where information about system variables and/or petrologic processes is limited.

Hawaii