The geochemistry of pyroxenes from the lower layered series of the Jimberlana intrusion, Western Australia
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Most of the Al3+ entering the pyroxenes does so by substituting for tetrahedral Si4+. This creates a charge imbalance that requires the simultaneous entry of Cr3+, Ti4+, Fe3+ or Al3+ into octahedral sites. Cr3+, because of its high crystal field stabilisation energy (CFSE), is the most important of these elements to enter the early-formed pyrosenes but it is replaced by Ti4+ later in fractionation when the Cr3+ content of the melt becomes depleted. The dependence of Cr3+ and Ti4+ on charge balance controls their partition between coexisting pyroxenes and olivines. Ca-rich pyroxene which contains more Al3+ than Ca-poor pyroxene also has more Ti4+ and Cr3+ whereas olivine, which contains negligible Al3+, has low Cr3+ and Ti4+. The Al3+ content of pyroxenes is influenced by changes in P, T, {Mathematical expression}and {Mathematical expression}of the magma and by the nature of the ion providing charge balance in the octahedral site. Of these {Mathematical expression}is dominant and variations in the Al3+ content of the Jimberlana pyroxenes correspond closely with the expected changes in the {Mathematical expression}of the melt. The substitution of divalent ions, such as Mn2+ and Ni2+, in the pyroxene lattice is by replacement of Fe2+ or Mg2+ in the octahedral M3 and M2 sites and is therefore independent of charge balance. If there are no size restrictions, the principal factor to be considered is the CFSE the ion receives in octahedral co-ordination. Ni2+, which receives a high CFSE, partitions strongly between the early-formed pyroxenes and olivines and therefore becomes depleted in the magma with fractionation. Conversely Mn2+, which receives zero CFSE, concentrates in the magma with fractionation and becomes a more important substitute in the later-formed pyroxenes. Its geochemical behaviour is controlled by its size. The narrow miscibility gap of the Jimberlana pyroxenes and the high En content of the Ca-poor pyroxenes at the bronzite pigeonite changeover suggest that these pyroxenes crystallised at a higher temperature than pyroxenes of comparable composition from other intrusions.
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Contributions to Mineralogy and Petrology