The densities of 10 melts in the CaO-FeO-Fe2O3-SiO2 system were determined in equilibrium with air, in the temperature range of 1200 to 1550°C, using the double-bob Archimedean technique. Melt compositions range from 6 to 58 wt% SiO2, 14 to 76 wt% Fe2O3 and 10 to 46 wt% CaO. The ferric-ferrous ratios of glasses drop-quenched from loop fusion equilibration experiments were determined by 57Fe Mössbauer spectroscopy.

Melt densities range from 2.689 to 3.618 gm/cm3 with a mean standard deviation from replicate experiments of 0.15%. Least-squares regressions of molar volume versus molar composition have been performed and the root mean squared deviation shows that a linear combination of partial molar volumes for the oxide components (CaO, FeO, Fe2O3 and SiO2) cannot describe the data set within experimental error. Instead, the inclusion of excess terms in CaFe3+ and CaSi (product terms using the oxides) is required to yield a fit that describes the experimental data within error. The nonlinear compositional-dependence of the molar volumes of melts in this system can be explained by structural considerations of the roles of Ca and Fe3+.

The volume behavior of melts in this system is significantly different from that in the Na2O-FeO-Fe2O3-SiO2 system, consistent with the proposal that a proportion of Fe3+ in melts in the CaO-FeO-Fe2O3-SiO2 system is not tetrahedrally-coordinated by oxygen, which is supported by differences in 57Fe Mössbauer spectra of glasses. Specifically, this study confirms that the 57Fe Mössbauer spectra exhibit an area asymmetry and higher values of isomer shift of the ferric doublet that vary systematically with composition and temperature (this study; Dingwell and Virgo, 1987, 1988). These observations are consistent with a number of other lines of evidence (e.g., homogeneous redox equilibria, Dickenson and Hess, 1986; viscosity, Dingwell and Virgo, 1987,1988). Two species of ferric iron, varying in proportions with temperature, composition and redox state, are sufficient to describe the above observations.

The presence of more than one coordination geometry for Fe3+ in low pressure silicate melts has several implications for igneous petrogenesis. The possible effects on compressibility, the pressure dependence of the redox ratio, and redox enthalpy are briefly noted.