Investigation of the water sorption properties of Mars-relevant micro- and mesoporous minerals

Encouraged by recent results of the Mars Odyssey spacecraft mission and the OMEGA team (Mars Express) concerning water in equatorial latitudes between ±45° on Mars and the possible existence of hydrated minerals, we have investigated the water sorption properties of natural zeolites and clay minerals close to martian atmospheric surface conditions as well as the properties of Mg-sulfates and gypsum. To quantify the stability of hydrous minerals on the martian surface and their interaction with the martian atmosphere, the water adsorption and desorption properties of nontronite, montmorillonite, chabazite and clinoptilolite have been investigated using adsorption isotherms at low equilibrium water vapor pressures and temperatures, modeling of the adsorption equilibrium data, thermogravimetry (TG), differential scanning calorimetry (DSC), and proton magic angle spinning nuclear magnetic resonance measurements (¹H MAS NMR). Mg-sulfate hydrates were also analyzed using TG/DSC methods to compare with clay mineral and zeolites. Our data show that these microporous minerals can remain hydrated under present martian atmospheric conditions and hold up to 2.5-25 wt% of water in their void volumes at a partial water vapor pressure of 0.001 mbar in a temperature range of 333-193 K. Results of the ¹H MAS NMR measurements suggest that parts of the adsorbed water are liquid-like water and that the mobility of the adsorbed water might be of importance for adsorption-water-triggered chemistry and hypothetical exobiological activity on Mars.     

New findings for the equilibrated enstatite chondrite Grein 002

Abstract— We report new petrographic and chemical data for the equilibrated EL chondrite Grein 002, including the occurrence of osbornite, metallic copper, abundant taenite, and abundant diopside. As inferred from low Si concentrations in kamacite, the presence of ferroan alabandite, textural deformation, chemical equilibration of mafic silicates, and a subsolar noble gas component, we concur with Grein 002's previous classification as an EL4‐5 chondrite. Furthermore, the existence of pockets consisting of relatively coarse, euhedral enstatite crystals protruding large patches of Fe‐Ni alloys suggests to us that this EL4‐5 chondrite has been locally melted. We suspect impact induced shock to have triggered the formation of the melt pockets. Mineralogical evidence indicates that the localized melting of metal and adjacent enstatite must have happened relatively late in the meteorite's history. The deformation of chondrules, equilibration of mafic silicates, and generation of normal zoning in Fe, Zn‐sulfides took place during thermal alteration before the melting event. Following parent body metamorphism, daubreelite was exsolved from troilite in response to a period of slow cooling at subsolidus temperatures. Exsolution of schreibersite from the coarse metal patches probably occurred during a similar period of slow cooling subsequent to the event that induced the formation of the melt pockets. Overall shock features other than localized melting correspond to stage S2 and were likely established by the final impact that excavated the Grein 002 meteoroid.     

New ages from the Mauritanides Belt: recognition of Archean IOCG mineralization at Guelb Moghrein,Mauritania

The Guelb Moghrein Fe oxide–Cu–Au–Co (IOCG) deposit is located in the northern part of the Mauritanides chain at the western edge of the West African Craton. It is commonly held that the orogenic belt has experienced a polyphase tectonothermal evolution, including two Panafrican and one Variscan event. Dating of two distinct morphological types of hydrothermal monazite and xenotime from Guelb Moghrein yielded in situ U–Pb ages of 2492 ± 9 and 1742 ± 12 Myr respectively. Such ages have not been reported previously from the region which is conspicuous by the widespread occurrence of banded iron formations, more akin to Proterozoic or Archean than to Paleozoic settings. The supracrustal rocks are thought, therefore, to represent a greenstone terrane that was mineralized by hydrothermal fluids during the late Archean and reactivated by middle Proterozoic fluid flow. Final emplacement at the current position on the West African Craton was at ～300 Ma during Gondwana–Laurentia collision.     

13C/12C ratio double cyclicity in a Miocene browncoal: isotopic signals and orbital forcing

A detailed stable carbon isotopic profile of a late Miocene browncoal seam from the Lower Rhine Embayment, Germany, reveals two clear separate cycles of different frequency: this is the first instance of this type of isotopic signature being recognized within coals. The ratio of the two frequencies suggests this isotopic signal possibly resulted from climatic or vegetational responses to orbital forcing. The cyclicity has been enhanced by the application of conventional filtering methods on the data set. An analysis of the seam's palynology indicates a correlation between heavier isotopic compositions and the presence of Sequoiapollenites polyformosus , whose parent plant is believed to have favoured moist climates and higher groundwater tables.     

Structural control of low-sulfidation epithermal gold mineralization in the Rosario–Bunawan district, East Mindanao Ridge, Philippines

The Rosario–Bunawan district is situated about 200 km north of Davao City, the capital of the Mindanao Island, Southern Philippines. Gold is produced from the Co-O mine, containing about 2,034,000 t of ore at 10.9 g/t Au, and in numerous small-scale operations by local miners. Epithermal gold mineralization in the Rosario–Bunawan district and the Co-O mine is confined to narrow (0.2–4 m) low-sulfidation quartz–chalcedony–calcite veins in volcanic and volcaniclastic wall rocks. Three major vein orientations are distinguished: (1) the NNW–SSE-trending set with a sinistral strike-slip sense of deformation (Philippine Fault trend); (2) the ENE–WSW-trending dextral strike-slip set (Palawan trend) and associated veins in the Riedel geometry; and (3) the WNW–ESE-trending conjugate set (Co-O trend). Three structural stages are defined: (1) extensional shear or shear veins formed in the Co-O, the Philippine Fault, and Palawan trends during regional NW–SE compression and near vertical vein opening (D₁); (2) reactivation of veins in the Philippine Fault, veins associated with the Palawan, and, to a lesser extent, the Co-O trends during E–W compression and near horizontal N–S-oriented vein opening (D₂). New D₂ extensional shear or shear veins formed in the Philippine Fault, and structures associated with the Palawan and associated Riedel trends; (3) the D₃-stage block faulting subsequently displaced all of the auriferous veins. The auriferous Rosario–Bunawan district is situated between two splays of the Philippine Fault, which acted as a lateral ramp system during the oblique convergence of the Philippine Sea plate and the Eurasian plate. The oblique convergence resulted in a change from a compressional (D₁) to a transpressional (D₂) regime, which was a prerequisite for the two-stage vein opening and hydrothermal mineralization, leading to an economic gold enrichment. D₁ compressional tectonics may have caused an elevated geothermal gradient in shallow crustal levels, forming the heat source for the fluid plumbing system, which is at variance to typical epithermal deposits formed in extensional zones. D₂ thrusting of a limestone nappe together with syn-tectonic diorite intrusions may have further increased the geothermal gradient, maintaining the fluid plumbing system. The limestone nappe may, at the same time, have represented an aquitard forcing the hydrothermal fluids into the volcanic and volcaniclastic wall rocks, which is regarded as critical for the two-stage gold mineralization in the Rosario–Bunawan district.     

The H2O and CO2 adsorption properties of phyllosilicate-poor palagonitic dust and smectites under martian environmental conditions

The recent detection of up to ∼10 wt% water-equivalent H heterogeneously distributed in the upper meter of the equatorial regions of the martian surface and the presence of the 3-μm hydrations feature across the entire planet raises the question whether martian surficial dust can account for this water-equivalent H. We have investigated the H₂O and CO₂ adsorption properties of palagonitic dust (<5 μm size fraction of phyllosilicate-poor palagonitic tephra HWMK919) as a martian dust analog and two smectites under simulated martian equatorial surface conditions. Our results show that the palagonitic dust, which contains hydrated and hydroxylated volcanic glass of basaltic composition, accommodates significantly more H₂O under comparable humidity and temperature conditions than do the smectites nontronite and montmorillonite.     

Making continental crust through slab melting: Constraints from niobium-tantalum fractionation in UHP metamorphic rutile

The formation of the continental crust (CC) is one of the most important processes in the evolution of the silicate Earth. Exactly how the CC formed is the subject of ongoing debate that focuses on its subchondritic Nb/Ta ratio. Nb and Ta are “geochemical identical twins,” so they usually do not fractionate from each other. Here, we show that rutile grains from hydrous rutile-bearing eclogitic layers recovered from drillcores in the Dabie-Sulu ultrahigh pressure terrain have highly variable Nb/Ta values (ranging from 5.4 to 29.1, with an average of 9.8 ± 0.6), indicating major fractionation of Nb and Ta most likely occurred during blueschist to amphibole-eclogite transformation in the absence of rutile. It is suggested that the released fluids with subchondritic Nb/Ta were transported to, and retained by, hydrous rutile-bearing eclogite in colder regions, resulting in suprachondritic Nb/Ta ratios for drier eclogite in hotter regions. Further dehydration of hydrous rutile-bearing eclogites cannot transfer the fractionated Nb/Ta values to the CC due to the low solubility of Nb and Ta in fluids in the presence of rutile, while dehydration-melting results in a major component of the CC, the tonalite-trondhjemite-granodiorite (TTG) component, which is responsible for the low Nb/Ta of the CC. Consequently, residual eclogites have variable but overall suprachondritic Nb/Ta.