The potential of phosphorus in clinopyroxene as a geospeedometer: Examples from mantle xenoliths

We investigate the potential to use concentrations and zoning patterns of phosphorus (P) in clinopyroxene as indicators of the rates of igneous and metasomatic processes, comparable to recent applications of P in olivine but applicable to more evolved rocks and lower temperatures of crystallization. Few high-P pyroxenes have been previously reported, and none have been analyzed in detail for the mechanism of P enrichment or the implications for mineral growth kinetics. Here, we report the discovery and characteristics of exotic phosphorus-rich secondary clinopyroxene in glassy pockets and veins in composite mantle xenoliths from the Cima Volcanic Field (California, USA) and the Middle Atlas Mountains (Morocco, West Africa). These glass-bearing xenoliths preserve evidence of melt infiltration events and the contrasting behavior of P in their pyroxene crystals constrains the different rates of reaction and extents of equilibration that characterized infiltration in each setting. We report optical petrography and chemical analysis of glasses and minerals for major elements by electron microprobe microanalyzer and trace elements by laser-ablation Inductively Coupled Plasma Mass Spectrometry. The Cima Volcanic Field specimen shows one end-member behavior, with unzoned P-rich clinopyroxene in a melt pocket. We attribute this occurrence to a slow crystallization process that occurred after the melt temperature reached near-equilibrium with the host rock and during which the P concentration in the melt was buffered by apatite saturation. In the Morocco xenolith, by contrast, clinopyroxene exhibits zonation with P increasing all the way to the rim, in contact with the glass. We ascribe this feature to a rapid growth process in which excess P was incorporated into the growing clinopyroxene from a diffusive boundary layer. We demonstrate quantitative agreement between the enrichment of P and other trace elements and their expected diffusion and partitioning behavior during rapid growth. We suggest that P has not been widely reported in clinopyroxene in large part because it has rarely been looked for and that its analysis offers considerable promise as a kinetic indicator both in xenoliths and volcanic rocks.