Widespread oxidized and hydrated amorphous silicates in CR chondrites matrices: Implications for alteration conditions and H2 degassing of asteroids

Abstract

The CR chondrites carry one of the most pristine records of the solar nebula materials that accreted to form planetesimals. They have experienced very variable degrees of aqueous alteration, ranging from incipient alteration in their matrices to the complete hydration of all of their components. In order to constrain their chemical alteration pathways and the conditions of alteration, we have investigated the mineralogy and Fe oxidation state of silicates in the matrices of 8 CR chondrites, from type 3 to type 1. Fe-L edge X-ray Absorption Near Edge Structure (XANES) was performed on matrix FIB sections using synchrotron-based scanning transmission X-ray microscopy (STXM). The Fe3+/∑Fe ratio of submicron silicate particles was obtained and coordinated with TEM observations.In all the least altered CR chondrites (QUE 99177, EET 87770, EET 92042, LAP 02342, GRA 95229 and Renazzo), we find that the matrices consist of abundant submicron Fe-rich hydrated amorphous silicate grains, mixed with nanometer-sized phyllosilicates. The Fe3+/∑Fe ratios of both amorphous and nanocrystalline regions are very high with values ranging from 68 to 78%. In the most altered samples (Al Rais and GRO 95577), fine-grained phyllosilicates also have a high Fe3+/∑Fe ratio (around 70%), whereas the coarse, micrometer-sized phyllosilicates are less oxidized (down to 55%) and have a lower iron content.These observations suggest the following sequence: submicron Fe2+-amorphous silicate particles were the building blocks of CR matrices; after accretion they were quickly hydrated and oxidized, leading to a metastable, amorphous gel-like phase. Nucleation and growth of crystalline phyllosilicates was kinetically-limited in most type 3 and 2 CRs, but increased as alteration became more extensive in Al Rais and GRO 95577. The decreasing Fe3+/∑Fe ratio is interpreted as a result of the transfer of Fe3+ from silicates to oxides during growth, while aqueous alteration progressed (higher temperature, longer duration, change of fluid composition). In a fully closed system, equilibrium thermodynamics suggest that the water to rock ratios, typically assumed to be low (<1) for chondrites, should primarily control the iron valency of the silicates and predict a lower Fe3+/∑Fe ratio. Such a high Fe3+/∑Fe value could be accounted for, however, if the system was partially open, at least with respect to H2 (and other gases as well). Rapid degassing of the fluid would have favored more oxidizing fluid conditions. Recently proposed scenarios involving some degree of water D/H increase through Rayleigh isotopic fractionation are supported by these results.