The diffusivity of phosphorus in San Carlos olivine (SCO) was measured at near-atmospheric pressure and 650-850 °C by in-diffusion of P from a surface powder source consisting of pre-reacted SCO and AlPO 4 . The experiments were conducted in evacuated silica-glass ampoules at oxygen fugacities fixed by solid-state buffers, generally Ni-NiO but also including two experiments buffered at wüstite-magnetite. Phosphorus uptake profiles were characterized by Rutherford backscattering spectroscopy (RBS) and nuclear reaction analysis (NRA). The temperature dependence of P diffusion in SCO conforms to the expected Arrhenius relation D = D 0 exp(-E a /RT), where the constants are as follows: log(D 0 , m 2 /s) = -10.06 ± 0.80 and E a = 229 ± 16 kJ/mol. These values characterize P as a relatively slow diffuser in olivine-slower by about an order of magnitude than Cr and Ca at basalt near-liquidus temperatures-but substantially faster than Si.With a view toward modeling P uptake during rapid growth of natural olivines, P diffusion was also characterized in dry MORB basalt melt over the temperature range 1250-1500 °C at 1 GPa, using traditional diffusion couples contained in graphite. Phosphorus diffusion profiles in the quenched and depressurized samples were quantified by laser-ablation ICP/MS. Phosphorus diffusion in basaltic melt is similar to that of Si, with log(D 0 , m 2 /s) = -6.30 ± 0.7 and E a = 147 ± 22 kJ/mol.The new data for P diffusion in olivine and basalt melt can be used to explore the acquisition of finescale zoning in natural olivine phenocrysts through kinetic models, as well as the survival of P zoning in olivine with time spent at elevated temperature. Models of growth entrapment of a P-enriched near-surface layer in the olivine lattice indicate that crystal growth at plausible sustained rates is indeed likely to result in regions of anomalously high P content in the resulting crystal. Phosphorus concentrations above the equilibrium partitioning value can also result from development of a diffusive boundary layer in the melt against a rapidly growing crystal, but this mechanism is ineffective at typical sustained olivine growth rates, requiring dendrite-forming growth speeds. Preservation of P zoning on the scale of a few micrometers apparently requires cooling within a few months of formation of the zoning.

The discovery of large lithium isotopic gradients in geologic media has motivated recent work examining the kinetic fractionation of Li isotopes in silicate materials. Here, piston-cylinder experiments were used to determine Li diffusivities in rhyolitic melts containing ~6 wt. % H 2 O at 1 GPa pressure and 790-875 ºC. Lithium transport in wet rhyolitic melt is almost an order of magnitude faster than diffusion in dry obsidian glass over the investigated temperature range. Li isotope profiles collected by ion microprobe show that the kinetic exponent β = 0.228 for diffusive fractionation of Li isotopes in wet rhyolite. This value is very close to β = 0.215 determined by Richter et al. (2003) for Li isotope diffusion in a dry basalt-rhyolite couple at 1350 °C. The similarity of the two values indicates little or no dependence of β Li in silicate melts on either temperature or melt composition. The new data confirm a very high potential for diffusive fractionation of 6 Li from 7 Li and can be confidently used to model deviations in δ 7 Li to determine the time-temperature histories of natural rhyolite samples.

Metamorphic devolatilization of subducted slabs generates aqueous fluids that ascend into the mantle wedge, driving the partial melting that produces arc magmas. These magmas have oxygen fugacities some 10–1,000 times higher than magmas generated at mid-ocean ridges. Whether this oxidized magmatic character is imparted by slab fluids or is acquired during ascent and interaction with the surrounding mantle or crust is debated. Here we study the petrology of metasedimentary rocks from two Tertiary Aegean subduction complexes in combination with reactive transport modelling to investigate the oxidative potential of the sedimentary rocks that cover slabs. We find that the metasedimentary rocks preserve evidence for fluid-mediated redox reactions and could be highly oxidized. Furthermore, the modelling demonstrates that layers of these oxidized rocks less than about 200 m thick have the capacity to oxidize the ascending slab dehydration flux via redox reactions that remove H2, CH4 and/or H2S from the fluids. These fluids can then oxidize the overlying mantle wedge at rates comparable to arc magma generation rates, primarily via reactions involving sulfur species. Oxidized metasedimentary rocks need not generate large amounts of fluid themselves but could instead oxidize slab dehydration fluids ascending through them. Proposed Phanerozoic increases in arc magma oxygen fugacity may reflect the recycling of oxidative weathering products following Neoproterozoic–Palaeozoic marine and atmospheric oxygenation.

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Vanadium is a multivalent element that can speciate as V2+, V3+, V4+, and V5+ over a range of geologically relevant oxygen fugacities (fO2). The abundance of V in planetary materials can be exploited as a proxy for fO2 when its partitioning behavior is known. The mineral rutile (TiO2) is an important carrier of the high field strength elements Nb and Ta in the solid Earth, but it can also incorporate substantial quantities of vanadium (up to ~2000 ppm; e.g., Zack et al. 2002). However, little work has been done to systematically investigate how the partitioning of V in rutile-bearing systems changes as a function of both fO2 and composition. We measured the partitioning of V and 19 other trace elements (Sc, Cr, Y, Zr, Nb, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Yb, Lu, Hf, and Ta) between rutile and three silicate melt compositions equilibrated at 1 atm pressure, 1300 °C and fO2 values from two log units below the quartz-fayalite-magnetite oxygen buffer (QFM-2) to air (QFM+6.5). Rutile/melt partition coefficients (DVrt/melt) change dynamically over an eight-log unit range of fO2 and are greatest at fO2 = QFM-2 in all compositions. Vanadium solubility in rutile declines continuously as fO2 increases from QFM-2 and approaches unity in air. Trace-element partitioning between rutile and melt is also correlated with melt composition, with the greatest values of Drt/melt measured in the most polymerized melt systems containing the least TiO2. We do not find any circumstances where V becomes incompatible in rutile. Our results indicate that rutile is a considerable sink for V at terrestrial fO2 values and will contribute to the retention of V in refractory slab residues in subduction zones. In agreement with previous work, we find that DTart/melt>DNbrt/melt under all conditions investigated, suggesting that rutile fractionation does not lead to low Nb/Ta ratios in Earth's continental crust.