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..

Sulfur degassing at Erta Ale (Ethiopia) and Masaya (Nicaragua) volcanoes: Implications for degassing processes and oxygen fugacities of basaltic systems

We investigate the relationship between sulfur and oxygen fugacity at Erta Ale and Masaya volcanoes. Oxygen fugacity was assessed utilizing Fe3+/∑Fe and major element compositions measured in olivine‐hosted melt inclusions and matrix glasses. Erta Ale melts have Fe3+/∑Fe of 0.15–0.16, reflecting fO2 of ΔQFM 0.0 ± 0.3, which is indistinguishable from fO2 calculated from CO2/CO ratios in high‐temperature gases. Masaya is more oxidized at ΔQFM +1.7 ± 0.4, typical of arc settings. Sulfur isotope compositions of gases and scoria at Erta Ale (δ34Sgas − 0.5‰; δ34Sscoria + 0.9‰) and Masaya (δ34Sgas + 4.8‰; δ34Sscoria + 7.4‰) reflect distinct sulfur sources, as well as isotopic fractionation during degassing (equilibrium and kinetic fractionation effects). Sulfur speciation in melts plays an important role in isotope fractionation during degassing and S6+/∑S is 0.67 in Masaya melt inclusions. No change is observed in Fe3+/∑Fe or S6+/∑S with extent of S degassing at Erta Ale, indicating negligible effect on fO2, and further suggesting that H2S is the dominant gas species exsolved from the S2−‐rich melt (i.e., no redistribution of electrons). High SO2/H2S observed in Erta Ale gas emissions is due to gas re‐equilibration at low pressure and fixed fO2. Sulfur budget considerations indicate that the majority of S injected into the systems is emitted as gas, which is therefore representative of the magmatic S isotope composition. The composition of the Masaya gas plume (+4.8‰) cannot be explained by fractionation effects but rather reflects recycling of high δ34S oxidized sulfur through the subduction zone

Exploring the Origin of the Bering Sea: Initial Results of Cruise SO249-2 (17th July – 13th August 2016)

The Bering Sea is one of the largest marginal seas on Earth with still poorly understood origin and evolution. Cruise SO249-2 of the German research vessel Sonne explored the western half of Bering Sea by multibeam mapping, sediment profiling and dredge sampling in the framework of the joint German-Russian-U.S. American project BERING. Focus areas were A) the Chukotka-Beringian margins, once the possible site of Cretaceous arc volcanism prior to Eocene initiation of the Aleutian arc, B) the enigmatic Shirshov Ridge, separating the Komandorsky from the Aleutian Basin, C) Beta Rise, an area of anomalous high heat flow in the Komandorsky basin, D) the Volcanlogists Massif and adjacent volcanic and tectonic structures and E) the Komandorsky block, the westernmost section of the modern arc.....

High spatial resolution analysis of the iron oxidation state in silicate glasses using the electron probe

The iron oxidation state in silicate melts is important for understanding their physical properties, although it is most often used to estimate the oxygen fugacity of magmatic systems. Often high spatial resolution analyses are required, yet the available techniques, such as μXANES and μMössbauer, require synchrotron access. The flank method is an electron probe technique with the potential to measure Fe oxidation state at high spatial resolution but requires careful method development to reduce errors related to sample damage, especially for hydrous glasses. The intensity ratios derived from measurements on the flanks of FeLα and FeLβ X-rays (FeLβf/FeLαf) over a time interval (time-dependent ratio flank method) can be extrapolated to their initial values at the onset of analysis. We have developed and calibrated this new method using silicate glasses with a wide range of compositions (43–78 wt% SiO2, 0–10 wt% H2O, and 2–18 wt% FeOT, which is all Fe reported as FeO), including 68 glasses with known Fe oxidation state. The Fe oxidation state (Fe2+/FeT) of hydrous (0–4 wt% H2O) basaltic (43–56 wt% SiO2) and peralkaline (70–76 wt% SiO2) glasses with FeOT > 5 wt% can be quantified with a precision of ±0.03 (10 wt% FeOT and 0.5 Fe2+/FeT) and accuracy of ±0.1. We find basaltic and peralkaline glasses each require a different calibration curve and analysis at different spatial resolutions (∼20 and ∼60 μm diameter regions, respectively). A further 49 synthetic glasses were used to investigate the compositional controls on redox changes during electron beam irradiation, where we found that the direction of redox change is sensitive to glass composition. Anhydrous alkali-poor glasses become reduced during analysis, while hydrous and/or alkali-rich glasses become oxidized by the formation of magnetite nanolites identified using Raman spectroscopy. The rate of reduction is controlled by the initial oxidation state, whereas the rate of oxidation is controlled by SiO2, Fe, and H2O content

Petrogenesis of crustal wehrlites in the Oman ophiolite: Experiments and natural rocks

In the Wadi Haymiliyah of the Oman ophiolite (Haylayn block), discordant wehrlite bodies ranging in size from tens to hundreds of meters intrude the lower crust at different levels. We combined investigations on natural wehrlites from the Wadi Haymiliyah section with an experimental study on the phase relations in a wehrlitic system in order to constrain the petrogenesis of the crustal wehrlites of the Oman ophiolite. Secondary ion mass spectrometry analyses of clinopyroxenes from different wehrlite bodies imply that the clinopyroxenes were crystallized from tholeiitic, mid-ocean ridge (MORB)–type melts. The presence of primary magmatic amphiboles in some wehrlites suggests a formation under hydrous conditions. Significantly enhanced 87Sr/86Sr isotope ratios of separates from these amphiboles imply that the source of the corresponding magmatic fluids was either seawater or subduction zone–related. The experiments revealed that under wet conditions at relatively low temperatures, a MORB magma has the potential to produce wehrlite in the ocean crust by accumulation of early olivine and clinopyroxene. These show typically high Mg# which is a consequence of the oxidizing effect of the prevailing high aH2O. First plagioclases crystallizing after clinopyroxene under wet conditions are high in An content, in contrast to the corresponding dry system. Trace element compositions of clinopyroxenes of those wehrlites from the Moho transition zone are too depleted in HREE to be in equilibrium with present-day MORB, implying a genetic relation to the V2 lavas of the Oman ophiolite, which are interpreted to be the result of fluidenhanced melting of previously depleted mantle. We present a model on the petrogenesis of the crustal wehrlites in an upper mantle wedge above an initial, shallow subduction zone at the beginning of the intraoceanic thrusting