Non-mass-dependent oxygen isotopic fractionation in smokes produced in an electrical discharge

Abstract

We report the first production of non-mass-dependently fractionated silicate smokes from the gas phase at room temperature from a stream of silane and/or pentacarbonyl iron in a molecular hydrogen (or helium) flow mixed with molecular oxygen (or nitrous oxide). The smokes were formed at the Goddard Space Flight Center (GSFC) at total pressures of just under 100 Torr in an electrical discharge powered by a Tesla coil, were collected from the surfaces of the copper electrodes after each experiment and sent to the University of California at San Diego (UCSD) for oxygen isotopic analysis. Transmission electron microscopy studies of the smokes show that they grew in the gas phase rather than on the surfaces of the electrodes. We hypothesize at least two types of fractionation processes occurred during formation of the solids: a mass-dependent process that made isotopically lighter oxides compared to our initial oxygen gas composition followed by a mass-independent process that produced oxides enriched in 17O and 18O. The maximum Delta-17O observed is +4.7 per mil for an iron oxide produced in flowing hydrogen, using O2 as the oxidant. More typical displacements are 1-2 per mil above the equilibrium fractionation line. The chemical reaction mechanisms that yield these smokes are still under investigation.