Katy Evans

Oxidation state of subarc mantle

The subarc mantle is a primary control on the composition of arc magmas and the formation of arc-related ore deposits. Elevated ferric iron contents in arc lavas have been interpreted as a record of subarc mantle that is oxidized relative to mid-oceanic ridge basalt (MORB), but this conclusion is controversial. Measurements of spinel compositions in primitive arc lavas imply an arc magma source 1-4 log units more oxidized than MORB and ocean island basalts analyzed using the same technique. Samples from seven arcs show a significant correlation (P < 0.0005) between redox budget, subduction zone convergence rate, and subduction zone age. These results support the notion of oxidized arc lavas in the mantle source zone, but resolution of contradictory evidence regarding subarc mantle redox state requires further work.

Redox decoupling and redox budgets: Conceptual tools for the study of earth systems

Redox processes affect many aspects of geological systems. It is therefore useful to distinguish between chemical processes that result in changes in the capacities of reservoirs to oxidize or reduce from those that do not. Two terms are proposed to make this distinction. The first is redox decoupling: the transport of redox- sensitive elements (e.g., H, C, S, Fe) such that reservoirs experience a change in their capacity to oxidize or reduce other material. The second is electrochemical differentiation: the effect of one or more redox decoupling processes that change existing gradients in redox potential. Recognition of redox decoupling requires the use of an extensive rather than an intensive redox variable, because intensive variables do not provide information on fluxes. Redox budget, defined as the number of moles of negative charge that must be added to a sample to reach a reference state, is such a variable. Construction of redox budgets for mid-oceanic-ridge basalt (MORB) lavas and glasses reveals that redox decoupling occurs during crystallization at the Mid-Atlantic, Pacific, and Red Sea ridges, with net oxidation of the crystallized lava. The concepts of electrochemical differentiation, redox decoupling, and redox budget may be useful for researchers studying global cycling, the formation of ore deposits, volcanism, evolution of the mantle, crust and core, redox-related environmental problems, and biotic systems.

Banded iron formation to iron ore: A record of the evolution of Earth environments?

Banded iron formations (BIF) are the protolith to most of the world’s largest iron ore deposits. Previous hypogene genetic models for Paleoproterozoic “Lake Superior” BIF-hosted deposits invoke upwards, down-temperature fl ow of basinal brines via complex silica and carbonate precipitation/dissolution processes. Such models are challenged by the necessary SiO 2 removal. Thermodynamic and mass balance constraints are used to refi ne conceptual models of the formation of BIF-hosted iron ore. These constraints, plus existing isotope and halogen ratio evidence, are consistent with removal of silica by down- or up-directed infi ltration of high-pH hypersaline brines, with or without a contribution from basinal brines. The proposed link to surface environments suggest that Paleoproterozoic BIF-ore upgrade may provide a record of a critical time in the evolution of the Earth’s biosphere and hydrosphere.

Sulfur isotope evolution in sulfide ores from Western Alps: assessing the influence of subduction-related metamorphism

Sulfides entering subduction zones can play an important role in the release of sulfur and metals to the mantle wedge and contribute to the formation of volcanic arc-associated ores. Fractionation of stable sulfur isotopes recorded by sulfides during metamorphism can provide evidence of fluid-rock interactions during metamorphism and give insights on sulfur mobilization. A detailed microtextural and geochemical study was performed on mineralized samples from two ocean floor-related sulfide deposits (Servette and Beth-Ghinivert) in high-pressure units of the Italian Western Alps, which underwent different metamorphic evolutions. The combination of microtextural investigations with δ34S values from in situ ion probe analyses within individual pyrite and chalcopyrite grains allowed evaluation of the effectiveness of metamorphism in modifying the isotopic record and mobilizing sulfur and metals and have insights on fluid circulation within the slab. Textures and isotopic compositions inherited from the protolith are recorded at Beth-Ghinivert, where limited metamorphic recrystallization is attributed to limited interaction with metamorphic fluids. Isotopic modification by metamorphic processes occurred only at the submillimeter scale at Servette, where local interactions with infiltrating hydrothermal fluid are recorded by metamorphic grains. Notwithstanding the differences recorded by the two deposits, neither underwent intensive isotopic reequilibration or records evidence of intense fluid-rock interaction and S mobilization during metamorphism. Therefore, subducted sulfide deposits dominated by pyrite and chalcopyrite are unlikely to release significant quantities of sulfur to the mantle wedge and to arc magmatism sources at metamorphic grades below the lower eclogite facies.

The effect of CO2 on the speciation of bromine in low-temperature geological solutions: an XANES study.

CO(2)-rich solutions are common in geological environments. An XANES (X-ray absorption near-edge structure) study of Br in CO(2)-bearing synthetic fluid inclusions has revealed that Br exhibits a strong pre-edge feature at temperatures from 298 to 423 K. Br in CO(2)-free solutions does not show such a feature. The feature becomes smaller and disappears as temperature increases, but reappears when temperature is reduced. The size of the feature increases with increasing X(CO(2)) in the fluid inclusion, where X(CO(2)) is the mole fraction of CO(2) in the solution [n(CO(2))/(n(CO(2)) + n(H(2)(O)) + n(RbBr)); n indicates the number of moles]. The pre-edge feature is similar to that shown by covalently bonded Br, but observed and calculated concentrations of plausible Br-bearing covalent compounds (Br(2), CH(3)Br and HBr) are vanishingly small. An alternative possibility is that CO(2) affects the hydration of Br sufficiently that the charge density changes to favour the 1s-p level transitions that are thought to cause the pre-edge peak. The distance between the first two post-edge maxima in the XANES also decreases with increasing X(CO(2)). This is attributed to a CO(2)-related decrease in the polarity of the solvent. The proposed causes of the observed features are not integrated into existing geochemical models; thus CO(2)-bearing solutions could be predicted poorly by such models, with significant consequences for models of geological processes such as ore-formation and metamorphism.

Variation in XANES in biotite as a function of orientation, crystal composition, and metamorphic history

Abstract Microscale analysis of ferrous:ferric iron ratios in silicate minerals has the potential to constrain geological processes but has proved challenging because textural information and spatial resolution are limited with bulk techniques, and in situ methods have limited spatial resolution. Synchrotron methods, such as XANES, have been hampered by the sensitivity of spectra to crystal orientation and matrix effects. In an attempt to break this nexus, biotites from Tanzania were characterized with a combination of optical microscopy, electron microprobe, Mössbauer analysis, electron backscatter diffraction (EBSD) and X-ray absorption near edge structure (XANES) spectroscopy. Pre-edge and edge characteristics of the FeKα absorption feature were compared to orientation information derived by EBSD and ferric iron content derived from Mössbauer analysis. Statistically significant correlations between measured spectral features and optic/crystallographic orientation were observed for individual samples. However, orientation corrections derived from these correlations did not reduce the uncertainty in Fe3+/Fetot. The observations are consistent with matrix- and ordering-dependency of the XANES features, and further work is necessary if a general formulation for orientation corrections is to be devised.

Redistribution of Iron and Titanium in High-Pressure Ultramafic Rocks

The redox state of iron in high-pressure serpentinites, which host a significant proportion of Fe3+ in subduction zones, can be used to provide an insight into iron cycling and constrain the composition of subduction zone fluids. In this study, we use oxide and silicate mineral textures, interpretation of mineral parageneses, mineral composition data, and whole rock geochemistry of high-pressure retrogressed ultramafic rocks from the Zermatt-Saas Zone to constrain the distribution of iron and titanium, and iron oxidation state. These data provide an insight on the oxidation state and composition of fluids at depth in subduction zones. Oxide minerals host the bulk of iron, particularly Fe3+. The increase in mode of magnetite and observation of magnetite within antigorite veins in the investigated ultramafic samples during initial retrogression is most consistent with oxidation of existing iron within the samples during the infiltration of an oxidizing fluid since it is difficult to reconcile addition of Fe3+ with the known limited solubility of this species. However, high Ti contents are not typical of serpentinites and also cannot be accounted for by simple mixing of a depleted mantle protolith with the nearby Allalin gabbro. Titanium-rich phases coincide with prograde metamorphism and initial exhumation, implying the early seafloor and/or prograde addition and late mobilization of Ti. If Ti addition has occurred, then the introduction of Fe3+, also generally considered to be immobile, cannot be disregarded. We explore possible transport vectors for Ti and Fe through mineral texture analysis.

Resolving the role of carbonaceous material in gold precipitation in metasediment-hosted orogenic gold deposits

Carbonaceous material (CM) is commonly associated with gold and sulfides in metasediment-hosted orogenic gold deposits. The role of CM in Au deposition is controversial; CM has been proposed to contribute to gold deposition by reducing Au bisulfide complexes, or by facilitating sulfidation, which destabilizes Au in bisulfide complexes with resultant Au deposition. Integration of petrographic observations, thermodynamic models, and geochemical data from metasediment-hosted orogenic gold deposits in New Zealand, Australia, Canada, and West Africa reveals genetic links between sulfides, CM, and mineralization. The results are consistent with the coexistence of CM and pyrite as a consequence of their codeposition from ore fluids, with a minor proportion of CM originally in situ in the host rocks. Au is deposited when pyrite and CM deposition decreases H 2 S concentration in ore fluids, destabilizing Au(HS) 2 – complexes. Most CM in gold deposits is deposited from CO 2 and CH 4 in ore fluids. These findings are applicable to similar deposits worldwide.

On equilibrium in non-hydrostatic metamorphic systems

Metamorphic geology has accumulated a huge body of observation on mineral assemblages that reveal strong patterns in occurrence, summarised for example in the idea of metamorphic facies. On the realisation that such patterns needed a simple explanation, there has been considerable a posteriori success from adopting the idea that equilibrium thermodynamics can be used on mineral assemblages to make sense of the patterns in terms of, for example, the pressure and temperature of formation of mineral assemblages. In doing so, a particularly simple implicit assumption is made, that mineral assemblages operate essentially hydrostatically. Structural geologists have studied the same rocks for different ends, but, remarkably, the phenomena they are interested in depend on non-hydrostatic stress. We look at the effect of such behaviour on mineral equilibria. With adoption of some plausible assumptions about how metamorphism in the crust works, the consequence of minerals being non-hydrostatically stressed is commonly second order in equilibrium calculations.