Oxidation state of iron in hydrous phono-tephritic melts

The oxidation state of iron in hydrous ultrapotassic (phono-tephritic) melts coexisting with mixed H2O-CO2 fluids was experimentally studied at 1200 and 1250{degree sign}C and pressures from 50 to 500 MPa. The oxygen fugacity (fO2) varied from NNO-2.9 to NNO+2.6 in logfO2, relative to the Ni-NiO oxygen buffer (NNO), as imposed by external redox conditions in experimental vessels and internal variations in water activity from 0.05 to 1 inside the capsules. The iron redox state of the quenched melts was determined by colorimetric wet-chemical analysis. This analytical method was optimized to measure the Fe2+/ΣFe ratio of mg-sized samples within ±0.03 (2σ). The accuracy and precision was tested with international reference materials and with standards analyzed by other methods. The Fe2+/ΣFe ratio of the experimental glasses covered a range of 0.41 to 0.85. A small negative effect of dissolved water on Fe2+/ΣFe at given fO2 was found, consistent with the thermodynamic model of Moretti (2005). No effect of pressure and temperature on the redox state of iron was resolvable in the investigated P-T range. Compared to hydrous ferrobasaltic melts that were studied previously under similar conditions, systematically lower Fe2+/ΣFe ratios were found for the phono-tephritic melts, in particular at low oxygen fugacities. This effect is attributed to the much higher K2O contents of the phono-tephrite (7.5 compared to 0.3 wt%), but the difference in ΣFeO (7.8 wt% in the phono-tephrite and 12.9 wt% in the ferrobasalt) may have an influence as well. Comparison of the experimentally obtained relationship between logfO2 and Fe3+/Fe2+ for the studied hydrous ultrapotassic melts with commonly used empirical and thermodynamic models suggest that these models can be successfully applied to phono-tephritc melts, although such compositions were not implemented in the model calibrations. Furthermore, the new data can be used to improve the models with respect to the effects of compositional variables, such as H2O or K2O, on the redox state of iron in silicate melts

Oxidation state of iron in hydrous phono-tephritic melts

The oxidation state of iron in hydrous ultrapotassic (phono-tephritic) melts coexisting with mixed H2O-CO2 fluids was experimentally studied at 1200 and 1250{degree sign}C and pressures from 50 to 500 MPa. The oxygen fugacity (fO2) varied from NNO-2.9 to NNO+2.6 in logfO2, relative to the Ni-NiO oxygen buffer (NNO), as imposed by external redox conditions in experimental vessels and internal variations in water activity from 0.05 to 1 inside the capsules. The iron redox state of the quenched melts was determined by colorimetric wet-chemical analysis. This analytical method was optimized to measure the Fe2+/ΣFe ratio of mg-sized samples within ±0.03 (2σ). The accuracy and precision was tested with international reference materials and with standards analyzed by other methods. The Fe2+/ΣFe ratio of the experimental glasses covered a range of 0.41 to 0.85. A small negative effect of dissolved water on Fe2+/ΣFe at given fO2 was found, consistent with the thermodynamic model of Moretti (2005). No effect of pressure and temperature on the redox state of iron was resolvable in the investigated P-T range. Compared to hydrous ferrobasaltic melts that were studied previously under similar conditions, systematically lower Fe2+/ΣFe ratios were found for the phono-tephritic melts, in particular at low oxygen fugacities. This effect is attributed to the much higher K2O contents of the phono-tephrite (7.5 compared to 0.3 wt%), but the difference in ΣFeO (7.8 wt% in the phono-tephrite and 12.9 wt% in the ferrobasalt) may have an influence as well. Comparison of the experimentally obtained relationship between logfO2 and Fe3+/Fe2+ for the studied hydrous ultrapotassic melts with commonly used empirical and thermodynamic models suggest that these models can be successfully applied to phono-tephritc melts, although such compositions were not implemented in the model calibrations. Furthermore, the new data can be used to improve the models with respect to the effects of compositional variables, such as H2O or K2O, on the redox state of iron in silicate melts

Experimental calbration and implications of olivine-melt vanadium oxybarometry for hydrous magmas from Mutnovsky volcano (Kamchatka)

A promising method for the quantification of the redox conditions (oxygen fugacity, fO2) in basaltic systems, which might be applied to quenched melt inclusions in olivine, exploits the partitioning of vanadium between olivine and coexisting silicate melt (DV Ol‐M). Strong correlation of DV Ol‐M with fO2 was investigated in a number of experimental works on dry mafic and ultramafic melts in a wide range of fO2 conditions at pressures of 1 atm and 0.5–2 GPa, temperature range of 1150–1530°C (e.g., Canil&Fedortchouk, 2001; Mallmann&O’Neill, 2009; 2013). Only a few melt compositions equilibrated with olivine at T≤1250°C were studied so far. Although it was shown that melt composition, pressure and temperature have small effect on DV Ol‐M, more data are required to extend the calibration of the V oxybarometry to hydrous low‐temperature basalts representing island arc magmas

Atomic resolution transmission electron microscopy visualisation of channel occupancy in beryl in different crystallographic directions

The causes of colour in beryl have been a research topic for decades. For some varieties, such as emerald (green, coloured by Cr3+ and/or V3+), the main cause of colour is substitutions by metal atoms within the framework. However, the causes for the yellow and blue colours in heliodor, golden beryl and aquamarine are still debated. It is generally agreed that Fe ions are responsible for the colour, but there are differing conclusions about the valence states of these ions, the occupied positions and the colour-inducing processes involved. The colour of aquamarine is commonly attributed to intervalence charge transfer (IVCT) between Fe3+ and Fe2+. Various combinations of sites have been proposed to host the Fe ions engaging in this IVCT. Here we present a new approach to address the topic of colour generation: atomic resolution scanning transmission electron microscopy (STEM). For the first time, atomic resolution images of a beryl (natural aquamarine) are presented in the three crystallographic directions [0001], [1-210] and [1-100]. Ions are clearly resolved in the channels. From the ratio of channel occupation and the correlation of the atoms per formula unit (apfu) calculations we conclude that Fe resides in the framework, not in the channels. The projections in the [1-210] direction directly show that the cavity channel site 2a is occupied, most likely by Cs, in agreement with recent results in the literature.publishedVersio

Sulfur partitioning between magmatic phases at sulfide-sulfate transition - Implications for metal mobility

Sulfur is a volatile component that participates in a number of processes from magma generation to volcanic eruption affecting magma properties and controlling mobility of many different elements. These effects depend on abundance and proportions of redox-sensitive S species and on their partitioning between magmatic phases..