The Fe LII,III X-ray emission spectra of Fe and Fe-Ti oxides have been investigated at operating voltages between 2.0 and 30.0 kV using an electron probe. The LII band is due to transitions from antibonding and the LIII band from both bonding and antibonding molecular orbitals. After absorption corrections are applied the LII:LIII integrated intensity ratios increase with operating voltage (e.g., for wustite LII/LIII = 2.5 at 30.0 kV). These features are discussed in terms of higher transition probabilities from bonding molecular orbitals to O18 than to Fe 2p·LII and LIII intensities per unit concentration of Fe are higher in Fe2+-oxides than in more covalent Fe3+-oxides and are further enhanced by the presence of Ti4+. At the present time it does not appear possible to gain more than qualitative information concerning Fe2+:Fe3+ ratios in more complex minerals by measurement of Ln-Lm ratios.

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