1,2Matthew J. Genge, 1Bridie Davies, 1,2Martin D. Suttle, 3Matthias van Ginneken, 4Andrew G. Tomkins
Geochimica et Cosmochimica Acta (in Press) Link to Article [https://doi.org/10.1016/j.gca.2017.09.004]
1Department of Earth Science and Engineering, Imperial College London, Exhibition Road, London SW7 11BW, UK
2Earth Sciences Department, The Natural History Museum, Cromwell Road, London SW7 2BW, UK
3Earth System Science, Vrije Universiteit Brussel, Pleinlaan, 2 B-1050 Brussel, Belgium
4School of Earth, Atmosphere & Environment, Monash University, Melbourne, Victoria 3800, Australia
I-type cosmic spherules are micrometeorites that formed by melting during atmospheric entry and consist mainly of iron oxides and FeNi metal. I-types are important because they can readily be recovered from sedimentary rocks allowing study of solar system events over geological time. We report the results of a study of the mineralogy and petrology of 88 I-type cosmic spherules recovered from Antarctica in order to evaluate how they formed and evolved during atmospheric entry, to constrain the nature of their precursors and to establish rigorous criteria by which they may be conclusively identified within sediments and sedimentary rocks. Two textural types of I-type cosmic spherule are recognised: (1) metal bead-bearing (MET) spherules dominated by Ni-poor (<1.5 w%) wüstite and FeNi metal (10-95 wt% Ni) with minor magnetite, and (2) metal bead-free (OX) spherules dominated by Ni-rich wüstite (0.5-22.5 wt%) and magnetite. Two varieties of OX spherule are distinguished, magnetite-poor dendritic spherules and magnetite-rich coarse spherules. Six OXMET particles having features of both MET and OX spherules were also observed. The wüstite to magnetite ratios and metal contents of the studied particles testify to their formation by melting of extraterrestrial FeNi grains during progressive oxidation in the atmosphere. Precursors are suggested to be mainly kamacite and rare taenite grains. Vesicle formation within metal beads and extrusion of metallic liquid into surrounding wüstite grain boundaries suggests an evaporated iron sulphide or carbide component within at least 23% of particles. The Ni/Co ratios of metal vary from 14 to >100 and suggest that metal from H-group ordinary, CM, CR and iron meteorites may form the majority of particles. Oxidation during entry heating increases in the series MET<magnetite-poor OX<magnetite-rich OX spherules owing to differences in particle size, entry angle and velocity. Magnetite-poor OX spherules are shown to form by crystallisation of non-stoichiometric wüstite at the liquidus followed by sub-solidus decomposition to magnetite, whilst in magnetite-rich OX spherules magnetite crystallises directly at the liquidus. Magnetite rims found on most particles are suggested to form by oxidation during sub-solidus flight. The separation of metal beads due to deceleration is proposed to have been minor with most OX spherules shown to have been in equilibrium with metal beads containing >80 wt% Ni comprising a particle mass fraction of <0.2. Non-equilibrium effects in the exchange of Ni between wüstite and metal, and magnetite and wüstite are suggested as proxies for the rate of oxidation and cooling rate respectively. Variations in magnetite and wüstite crystal sizes are also suggested to relate to cooling rate allowing relative entry angle of particles to be evaluated. The formation of secondary metal in the form of sub-micron Ni-rich or Pt-group nuggets and as symplectite with magnetite was also identified and suggested to occur largely due to the exsolution of metallic alloys during decomposition of non-stoichiometric wüstite. Weathering is restricted to replacement of metal by iron hydroxides. The following criteria are recommended for the conclusive identification of I-type spherules within sediments and sedimentary rocks: (i) spherical particle morphologies, (ii) dendritic crystal morphologies, (iii) the presence of wüstite and magnetite, (iv) Ni-bearing wüstite and magnetite, and (v) the presence of relict FeNi metal.