Can Halogen Enrichment in Reduced Enstatite Chondrites Provide Clues to Volatile Accretion in the Early Earth?

Understanding how the Earth obtained and ultimately retained its volatiles is important for our overall understanding of large scale planetary evolution. Numerous models exist for the heterogeneous accretion of volatiles to early Earth, but accounting for all elements through accretion of typical planetary building blocks (e.g., CI chondrites) is difficult. Proto-planetary collisions resulting in the accretion of volatile-poor material under reducing conditions followed by accretion of volatile-rich material under oxidizing conditions has been suggested in such models [e.g., 1]. The heavy halogens (Cl, Br and I), a group of moderately volatile elements, are excellent tracers of planetary processing due to their low abundance and incompatible nature. Therefore characterizing halogen abundance and distribution in materials that accreted to form the planets, e.g., primitive meteorites, is crucial. One group of primitive meteorites, the enstatite chondrites (EC's), are amongst the most reduced materials in the solar system as evidenced by their unique mineral assemblage. Yet despite forming under ultra-reducing conditions, they are enriched in the moderately volatile elements, such as the halogens. The ECs are of particular interest owing to their oxygen isotopic composition which plots along the terrestrial fractionation line, linking them isotopically to the Earth-Moon system. These samples can thus potentially provide clues on the accretion of moderately volatile element rich material under reducing conditions, such as it may have existed during the early stages of Earth's accretion. Chlorine, Br and I concentrations in ECs were determined through step-heating small neutron-irradiated samples (0.3 to 3.3 mg) and measured by mass spectrometry using the noble gas proxy isotopes ³⁸ArCl/Cl, ⁸⁰KrBr/Br and ¹²⁸XeI/I. The EH chondrites are consistently enriched in the heavy halogens (up to 330 ppm Cl, 2290 ppb Br and 180 ppb I), compared to other ordinary and carbonaceous chondrites measured and have high molar I/Cl (~10^-3) and Br/Cl (~10^-3) ratios. For comparison, the ordinary chondrites have highly variable halogen concentrations and very low molar I/Cl (~10^-6) and Br/Cl (~10^-4) ratios. Halogen concentrations in the ECs are up to ~ 8 times higher for Cl, up to ~ 40 times higher for Br and up to ~ 50 times higher for I, when compared to estimates of halogen concentrations in the primitive mantle [2]. Potential halogen carrier phases in the ECs include Cl-rich feldspathic glass in chondrules, enstatite and/or the halogen-bearing sulfide djerfisherite. Accretion of halogen-rich, reduced material such as that observed here with the ECs could support models for heterogeneous accretion. Ongoing analyses of the primitive enstatite achondrites will shed additional light on these issues. [1] Wänke, H. Dreibus, G., Jagoutz E., Archaean Geochemistry, A. Kröner, G. N. Hanson, A. M. Goodwin, Eds. (Springer, Berlin, 1984), pp. 1-24. [2] Newsom, H.E., 1995. Global Earth Physics, A Handbook of Physical Constants, AGU Reference Shelf, vol. 1. American Geophysical Union, Washington.