| Article ID | Journal | Published Year | Pages | File Type |
|---|---|---|---|---|
| 4705891 | Geochimica et Cosmochimica Acta | 2008 | 17 Pages |
The two most abundant network-modifying cations in magmatic liquids are Ca2+ and Mg2+. To evaluate the influence of melt structure on exchange of Ca2+ and Mg2+ with other geochemically important divalent cations (m-cations) between coexisting minerals and melts, high-temperature (1470–1650 °C), ambient-pressure (0.1 MPa) forsterite/melt partitioning experiments were carried out in the system Mg2SiO4–CaMgSi2O6–SiO2 with ⩽1 wt% m-cations (Mn2+, Co2+, and Ni2+) substituting for Ca2+ and Mg2+. The bulk melt NBO/Si-range (NBO/Si: nonbridging oxygen per silicon) of melt in equilibrium with forsterite was between 1.89 and 2.74. In this NBO/Si-range, the NBO/Si(Ca) (fraction of nonbridging oxygens, NBO, that form bonds with Ca2+, Ca2+–NBO) is linearly related to NBO/Si, whereas fraction of Mg2+–NBO bonds is essentially independent of NBO/Si. For individual m-cations, rate of change of KD(m−Mg) with NBO/Si(Ca) for the exchange equilibrium, mmelt + Mgolivine ⇌ molivine + Mgmelt, is linear. KD(m−Mg) decreases as an exponential function of increasing ionic potential, Z/r2 (Z: formal electrical charge, r: ionic radius—here calculated with oxygen in sixfold coordination around the divalent cations) of the m-cation. The enthalpy change of the exchange equilibrium, ΔH, decreases linearly with increasing Z/r2 [ΔH = 261(9)–81(3)·Z/r2 (Å−2)]. From existing information on (Ca,Mg)O–SiO2 melt structure at ambient pressure, these relationships are understood by considering the exchange of divalent cations that form bonds with nonbridging oxygen in individual Qn-species in the melts. The negative ∂KD(m−Mg)/∂(Z/r2) and ∂(ΔH)/∂(Z/r2) is because increasing Z/r2 is because the cations forming bonds with nonbridging oxygen in increasingly depolymerized Qn-species where steric hindrance is decreasingly important. In other words, principles of ionic size/site mismatch commonly observed for trace and minor elements in crystals, also govern their solubility behavior in silicate melts.
