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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. [ABSTRACT FROM AUTHOR]

Abstract: In the central Rhodope mountains of Greece a carbonate-bearing metaperidotite lens ∼200×500m in size crops out as part of the high- to ultrahigh-pressure metamorphic Upper Sidironero Complex ∼500m SE of the Gorgona Village, north of Xanthi town. It is composed primarily of coarse grained (3–20mm in size) olivine and orthopyroxene, medium grained clinohumite and medium to fine grained tremolite, chlorite, dolomite, magnesite, talc, antigorite and various spinel phases. Whole-rock chemistry, mineral textures and compositions, and phase diagram calculations show that the metaperidotite was subjected to a prograde HP metamorphism, isofacial with the surrounding migmatitic gneisses, metapelites and amphibolites. The prograde character of metamorphism is demonstrated by inclusions of talc, antigorite, chlorite, dolomite, magnesite and Ti-clinohumite in ferrit-chromite, olivine, and orthopyroxene, as well as of olivine in orthopyroxene, and by the typical change in composition of zoned spinel minerals from ferrit-chromite in the core to chromian spinel at the rim. The prograde path is characterized by successive growth of amphibole, Ti-clinohumite, olivine and orthopyroxene, followed by the breakdown of Ti-clinohumite to olivine+Mg-ilmenite and of chlorite to olivine+spinel, probably during exhumation. The construction of a partial petrogenetic P–T grid in the system CaO–MgO–Al2O3–SiO2–CO2–H2O (CMASCH) for Ca-poor ultramafic bulk compositions has proven highly useful for the reconstruction of the metamorphic evolution and a P–T path, indicating that the use of univariant reactions in mixed volatile systems is highly warranted. The P–T path is clearly constrained to pressures below 1.5–1.7GPa by the absence of clinopyroxene. These pressures are slightly lower than those recorded in the closely associated Jurassic eclogites and much lower than those recorded in the diamond-bearing gneisses 5km to the south in the same tectonic unit. The carbonate-bearing metaperidotite from Gorgona probably represents a fragment of the hydrated mantle wedge. This is indicated by the REE compositions which differ from those of ophiolitic peridotites and resemble those of spinel or garnet peridotites of sub-continental origin. The ultramafic slice was incorporated tectonically into the subduction channel, most likely by tectonic erosion in the Early Jurassic, but did not experience ultrahigh-pressure metamorphism like the nearby metapelites that exhumed along the same subduction channel. [Copyright &y& Elsevier]

Abstract: Four different types of parageneses of the minerals calcite, dolomite, diopside, forsterite, spinel, amphibole (pargasite), (Ti–)clinohumite and phlogopite were observed in calcite–dolomite marbles collected in the Kimi-Complex of the Rhodope Metamorphic Province (RMP). The presence of former aragonite can be inferred from carbonate inclusions, which, in combination with an analysis of phase relations in the simplified system CaO–MgO–Al2O3–SiO2–CO2 (CMAS–CO2) show that the mineral assemblages preserved in these marbles most likely equilibrated at the aragonite–calcite transition, slightly below the coesite stability field, at ca. 720 °C, 25 kbar and a CO2 ~0.01. The thermodynamic model predicts that no matter what activity of CO2, garnet has to be present in aluminous calcite–dolomite-marble at UHP conditions. [Copyright &y& Elsevier]