Phosphorous incorporation in olivine crystallized from potassium-rich magmas

Olivine phenocrysts in basaltic rocks carry valuable mineral-chemical information on early evolution processes in mafic magmatic systems. Fast intra-crystalline diffusion and re-equilibration weakens this potential for major cation constituents of olivine, but the relative immobility of phosphorous makes this element a promising tracer of early crystallization histories. Although phosphorous zoning patterns and underlying kinetic controls have been studied in recent years, little is known about compositional controls on phosphorous incorporation into igneous olivines. We have analysed olivine phenocrysts, hosting Mg-rich melt inclusions, from a range of mafic potassium-rich lavas from Quaternary volcanic centres in Italy for phosphorous and associated trace elements by laser ablation inductively coupled mass spectrometry (LA-ICP-MS), and intra-crystal zoning by electron probe micro-analysis (EPMA) using Kα X-ray elemental maps and quantitative traverses. The studied olivines are marked by low and variable phosphorous concentrations (generally ≤ 200 ppm, but up to 435 ppm in enriched zones). In most cases, phosphorous zoning is decoupled from zoning in any other element or forsterite content. From a comprehensive database of melt inclusions and host phenocrysts, we infer that the composition of the host melt (silica and phosphorous activities) and olivine crystallization dynamics (interplay between diffusion rate of cation constituents in the melt and crystal growth rate) largely regulate phosphorous incorporation in olivines. Melt composition is likely the most important control under near-equilibrium crystallization conditions, as apparent phosphorous partition coefficients tend to increase with increasing silica activity. A negative relationship between apparent partition coefficients and X PO2.5 indicates that phosphorous partitioning into olivine may deviate from Henry's law behaviour. Melt inclusions are virtually always surrounded by phosphorous-poor zones that are also depleted in Cr and enriched in Al and Ti, suggesting that supply-limited slow growth and coupled-substitution mechanisms largely govern phosphorous uptake here. Our results demonstrate the potential versatility of phosphorous as sensitive indicator of crystal-growth histories and magmatic evolution processes in mafic systems