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238 records · Page 14

Ultraviolet Photooxidation of Smectite-Bound Fe(II) and Implications for the Origin of Martian Nontronites

Clay minerals detected with orbital and in situ instruments in ancient Martian terrains constrain Mars' climate and aqueous alteration history. Early in its history, Mars experienced an atmospheric redox change and iron-bearing clay minerals may preserve the effects of that transition. Ferrous smectites, the thermodynamically predicted product of chemical weathering of basalts under anoxic conditions, may have undergone oxidation by exposure to chemical oxidants in the atmosphere or regolith, or by direct photooxidation at the surface. To assess these potential oxidation pathways, ferrous trioctahedral smectites of varying initial iron content were synthesized and subjected to oxidation by ultraviolet (UV) irradiation. Experimental UV irradiation under an anoxic atmosphere equivalent to approximately 7 years of flux on the Martian surface caused partial oxidation of smectite-bound Fe (Fe3+/ΣFe = 16–18%) and octahedral sheet contraction. Metal-OH vibrational bands in visible/near infrared (VNIR) reflectance spectra of oxidized smectites changed in band depth and asymmetry with higher iron content. X-ray diffraction patterns of UV irradiated samples indicate the formation of a mixed di- and trioctahedral smectite or a secondary nontronite phase, possibly on the surfaces of higher iron content smectites. These experiments suggest that UV irradiation is able to oxidize structurally bound iron in smectites without the presence of other chemical oxidants. Photooxidation may have influenced the mineralogy, both syndepositionally and postdepositionally, of Martian alteration assemblages formed near the surface and this process needs not be limited to one part of their formation history. Plain Language Summary: Martian mineral assemblages observed with orbiters and rover instruments allow us to understand the planet's past climate and aqueous activity. Hydrated minerals that contain Fe(II) are of particular interest as they would have been affected by the early atmosphere becoming more oxidizing overtime, changing the structural iron into Fe(III). In this study, we synthesized Fe(II) smectites with varying iron content and irradiated them with an ultraviolet (UV) light source to test whether they could be photooxidized. Iron in the smectite minerals was incompletely oxidized by UV radiation after being exposed for the equivalent of approximately 7 years of exposure on the early Mars surface. The smectites with higher iron content showed more changes with photooxidation in their visible/near infrared spectra as well as in their X-ray diffraction patterns, two datasets collected by instruments on currently active Martian missions. These results suggest that UV photooxidation is a plausible contributor to the mineralogy and redox state of clay mineral assemblages observed at the Martian surface.

V. B. Rivera Banuchi↗

Pervasive aqueous alteration in the early Solar System revealed by potassium isotopic variations in Ryugu samples and carbonaceous chondrites

C-type asteroids are the presumed home to carbonaceous chondrites, some of which contain abundant life-forming volatiles and organics. For the first time, samples from a C-type asteroid (162173 Ryugu) were successfully returned to Earth by JAXA’s Hayabusa2 mission. These pristine samples, uncontaminated by the terrestrial environment, allow a direct comparison with carbonaceous chondrites. This study reports the stable K isotopic compositions (expressed as δ 41 K) of Ryugu samples and seven carbonaceous chondrites to constrain the origin of K isotopic variations in the early Solar System. Three aliquots of Ryugu particles collected at two touchdown sites have identical δ 41 K values, averaged at -0.194 ± 0.038‰ (2SD). The K isotopic composition of Ryugu falls within the range of δ 41 K values measured on representative CI chondrites, and together, they define an average δ 41 K value of -0.185 ± 0.078‰ (2SE), which provides the current best estimate of the K isotopic composition of the bulk Solar System. Samples of CI chondrites with δ 41 K values that deviate from this range likely reflect terrestrial contaminations or compositional heterogeneities at sampled sizes. In addition to CI chondrites, substantial K isotopic variability is observed in other carbonaceous chondrites and within individual chondritic groups, with δ 41 K values inversely correlated with K abundances in many cases. These observations indicate widespread fluid activity occurred in chondrite parent bodies, which significantly altered the original K abundances and isotopic compositions of chondrules and matrices established at their accretion.

Asteroid Ryugu↗

Application of New Partition Coefficients to Modeling Plagioclase

Previously, studies that determined the partition coefficient for an element, i, between plagioclase and the residual basaltic melt (Di plag) have been conducted using experimental conditions dissimilar from the Moon, and thus these values are not ideal for modeling plagioclase fractionation in a lunar system. However, recent work [1] has determined partition coefficients for plagioclase at lunar oxygen fugacities, and resulted in plagioclase with Anorthite contents ≥An90; these are significantly more calcic than plagioclase in previous studies, and the An content has a profound effect on partition coefficient values [2,3]. Plagioclase D-values, which are dependent on the An content of the crystal [e.g., 2-6], can be determined using published experimental data and the correlative An contents. Here, we examine new experimental data from [1] to ascertain their effect on the calculation of equilibrium liquids from Apollo 16 sample 60635,2. This sample is a coarse grained, subophitic impact melt composed of ~55% plagioclase laths with An94.4-98.7 [7,8], distinctly more calcic than of previous partition coefficient studies (e.g., [3-6, 9-10]). Sample 60635,2 is notable as having several plagioclase trace element analyses containing a negative Europium anomaly (-Eu) in the rare-earth element (REE) profile, rather than the typical positive Eu anomaly (+Eu) [7-8] (Fig. 1). The expected +Eu is due to the similarity in size and charge with Ca2+, thereby allowing Eu2+ to be easily taken up by the plagioclase crystal structure, in contrast to the remaining REE3+. Some 60635,2 plagioclase crystals only have +Eu REE profiles, some only have -Eu REE profiles, and some +Eu and -Eu analyses in different areas on a single crystal [7, 8]. Moreover, there does not seem to be any core-rim association with the +Eu or -Eu analyses, nor does there appear to be a correlation between the size, shape, or location of a particular crystal within the sample and the sign of its Eu anomaly, which suggests a complex evolution. In order to investigate this sample further, we can calculate the equilibrium liquids, but with An contents distinct from previous experimental studies, we must calculate the appropriate partition coefficients for each trace element analysis.

Fagan, A. L.↗

Active Volcanoes of Kamchatka as Suitable Terrestrial Analogs for Future Landing Missions and for Change Detection Analysis on Venus

The next decade will see the return to Venus due to a number of missions which have been recently selected and proposed for launch. The selected missions NASA DAVINCI and VERITAS, Roscosmos Venera-D, and ESA EnVision, along with the proposed missions ISRO Shukrayaan- 1, and CNSA VOICE, will open a new era for the exploration of the Earth’s hellish twin planet. These missions will shed new light on the science questions such as: (a) whether recent volcanic activity is locally constrained, or active volcanism occurs on a global scale; (b) the rate of the present-day volcanic activity; (c) the styles of volcanism on Venus, including possible occurrences of pyroclastic/explosive volcanism; and (d) how does the extreme environment on Venus effect volcanic activity. In preparation for these future missions to Venus, the Analogs for VENus’ GEologically Recent Surfaces (AVENGERS) initiative has the scope to select and analyze a number of active terrestrial volcanoes as suitable analogs for the identification and analysis of active volcanism on Venus. The Roscosmos Venera-D is the only mission, among the currently selected or planned mission, equipped with a lander to analyze the elemental and mineralogical composition of the surface. Therefore, it is crucial to find applicable volcanic areas on Earth to perform operational tests such as surface drilling and in-situ elemental composition analysis. To this regard, we propose the analysis of active volcanoes of the Kamchatka Peninsula, which is in a geodynamic setting (subduction) contrasting to that of the volcanic rises on Venus (hot spot). Thus, Kamchatka may represent a helpful geodynamic endmember to put the expected landing site of the Venera-D mission within the context of the entire variety of volcanic landforms and surface chemistry. The Kamchatka Peninsula is located on the eastern margin of the Eurasian plate, in proximity to the Kuril-Kamchatka subduction zone. The frequent eruptions characterizing the volcanoes of the Kamchatka Peninsula make them a suitable terrestrial analog for the possible detection of ongoing eruptions on Venus by future missions, which can be achieved by comparing a sequence of radar images of the same volcano and its surroundings taken at different times. Moreover, it is possible to collect samples of both unweathered and weathered volcanic deposits, to analyze their near infrared spectra in the laboratory for direct comparison with the spectra to be provided by the future missions to Venus. The chemical analyses of Venusian surface materials from the previous Soviet Venera and Vega missions are consistent with that of tholeiitic basalts. Since the volcanism of the Kamchatka Peninsula is characterized by both basaltic lava flows eruptions and pyroclastic activity, performing operational tests in the Kamchatka Peninsula also offers the unique opportunity to provide us the tools to potentially interpret the diverse output given by both effusive and explosive volcanic products.

Piero D'Incecco↗