^1,2L.Krämer Ruggiu et al. (>10)
Geochimica et Cosmochimica Acta (in Press) Link to Article [https://doi.org/10.1016/j.gca.2022.09.020]
¹Aix Marseille Univ, CNRS, IRD, INRAE, CEREGE, Aix-en-Provence, France
²Analytical-, Environmental- and Geo-Chemistry, Vrije Universiteit Brussel, Brussels, Belgium
Copyright Elsevier

We discuss if the detection of aqueous alteration depends on the techniques that are used. We apply different methods to estimate the extent of aqueous alteration on four ungrouped carbonaceous chondrites showing limited aqueous alteration and thermal metamorphism: Chwichiya 002, El Médano (EM) 200, Northwest Africa (NWA) 12957 and NWA 11750, classified as C3 or C3.00-ung. The aim is to propose a reliable methodology to identify the most primitive chondrites. Chwichiya 002, NWA 11750 and NWA 12957 display very primitive matrices and could be amongst the most primitive chondrites currently known, similar to the least altered lithologies of the CM chondrites Paris (CM2.9) and Asuka (A) 12085 (CM2.8), A 12236 (CM2.9) and A 12169 (CM3.0). The structure of organic matter and Cr2O3 in ferroan olivines show that the four meteorites have been less heated than the least metamorphosed standard/reference type 3 chondrite, Semarkona (LL3.00), with Chwichiya 002, NWA 12957 and NWA 11750 similar to the CO3.0s, Acfer 094 (C2-ung) and Paris meteorites. Chwichiya 002 and NWA 12957 show similar alteration phases and degree of alteration, with high abundances of amorphous material with embedded metal and sulfide, resembling Glass with Embedded Metal and Sulfide (GEMS)-like materials, and tochilinite-cronstedtite intergrowths (TCIs) as the major alteration phases. The matrix in NWA 11750 contains aggregates of nanoscale olivine crystals and abundant carbonates, observed as micrometer-sized carbonate veins surrounding chondrules, and as nanoscale carbonates mixed with the fine-grained materials. It also contains abundant grains of metal and a low abundance of phyllosilicates. El Medano 200 shows a high abundance of magnetite (∼ 10 vol%), nanoscale phyllosilicates, troilite, and organic matter. The variability of the secondary alteration phases in the meteorites suggests different alteration mechanisms, likely depending on both the starting composition of the meteorites and the composition of the fluids of alteration.

Scanning and transmission electron microscopy (SEM and TEM) allow the identification of primitive phases and the composition and spatial distribution of the secondary phases. X-ray diffraction (XRD) can detect alteration products, including some amorphous phases, although this is limited by the small coherence domains of small TCIs and other phyllosilicates. Transmission infrared (IR) spectroscopy can detect phyllosilicate and carbonate, but is ineffective for the detection of amorphous phases, metal, or sulfide. Both matrix defocused electron microprobe analyses (EMPA) and thermogravimetric analysis (TGA) allow detection of hydrated minerals, such as phyllosilicates and carbonates, but are strongly influenced by the presence of organic matter and do not reflect the overall alteration state of a meteorite. We conclude that the assessment of the primitivity of a chondrite is highly technique dependent. We propose a combination of XRD and the Cr2O3 in ferroan olivines or Raman spectroscopy for a rapid characterization of the alteration state of a chondrite and the detection of the most primitive meteorites. Finally, the combination of XRD and TEM allows for the detection of all primary and secondary phases and represents an ideal methodology for the characterization and detailed study of primitive chondrites and the different types of incipient aqueous alteration.

¹Rajdeep Dasgupta,¹Emily Falksen,¹Aindrila Pal,^1,2Chenguang Sun
Geochimica et Cosmochimica Acta (in Press) Link to Article [https://doi.org/10.1016/j.gca.2022.09.012]
¹Department of Earth, Environmental and Planetary Sciences, Rice University, Houston, TX 77005, USA
²Department of Geological Sciences, Jackson School of Geosciences, The University of Texas at Austin, Austin, TX 78712
Copyright Elsevier

Evolution of nitrogen (N), a life-essential volatile element, in highly reduced magmatic systems is a key for the origin of N on rocky planets formed via accretion of reduced chondritic parent body materials, planetesimals, and embryos that underwent partial or complete differentiation. However, the storage capacity of N in phases relevant for reduced silicate systems undergoing thermal processing is poorly known. To investigate the stability of N-bearing phases in partially molten silicate-rich systems as well as solubility of nitrogen in silicate melts and minerals, we performed laboratory experiments on a 80:20 synthetic basalt-Si3N4 mixture at 1.5-3.0 GPa and 1300-1600 °C in graphite capsules, yielding oxygen fugacity ranging from ∼IW– 3.0 to ∼IW – 4.0. All experiments produced silicate melt + nierite + Fe-rich alloy melt + N-rich vapor ± sinoite ± cpx. Sinoite was restricted to above while cpx was restricted below 1400-1500 °C. Nitrogen solubility and Nitrogen Concentration at Silicon-Nitride Saturation (NCNS) in silicate melts increases with increasing pressure and temperature and ranges between 3.6 and 9.5 wt %. Using our high pressure N solubility data and similar data at ambient and lower pressures, we derived a new N solubility model in silicate melts. Solubility of nitrogen in cpx was between 1.51 and 2.05 wt% and resulted in cpx/silicate melt partition coefficients for nitrogen, of ∼0.4 to ∼0.2. These are distinctly higher than those previously estimated at more oxidizing conditions, suggesting N maybe much less incompatible during thermal processing of rocky reservoirs at highly reducing conditions. Partition coefficient of N between Fe-rich alloy melt and cpx, was found to be between 1.6 and 2.1. The application of our N solubility data and model suggests that mobilization of N from the deeper, partially molten reservoirs to shallower reservoirs is possible in reduced planetesimals and internally differentiated meteorite parent bodies – leading to net loss of N via melt degassing or reprecipitation of N-bearing solid phases, depending on whether the surficial shell is oxidized or reduced, respectively. Similarly, comparison of the first measured values from our highly reducing experiments with those estimated at more oxidizing conditions suggest that N would be much less incompatible during internal and external magma ocean processing of rocky bodies under highly reducing conditions. Therefore, enrichment of N in the atmospheres of Earth and Venus is likely a result of more oxidizing penultimate phase of accretion, which would lead to N being more readily partitioned to residual liquid, which would also more readily degas at oxidizing conditions.