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© 2017, Springer-Verlag GmbH Germany. Subduction of serpentinised mantle transfers oxidised and hydrated mantle lithosphere into the Earth, with consequences for the oxidation state of sub-arc mantle and the genesis of arc-related ore deposits. The role of subducted serpentinised mantle lithosphere in earth system processes is uncertain because subduction fluxes are poorly constrained. Most subducted serpentinised mantle is serpentinised on the ocean floor settings. Yet this material is poorly represented in the literature because it is difficult to access. Large volumes of accessible serpentinite are available in ophiolite complexes, and most interpretations of subduction fluxes associated with ultramafic rocks are based on ophiolite studies. Seafloor and ophiolite serpentinisation can occur under different conditions, so it is necessary to assess if ophiolite serpentinites are a good proxy for seafloor serpentinites. Serpentinites sampled during ODP cruise 209 were compared with serpentinites from New Caledonia. The ODP209 serpentinites were serpentinised by modified seawater in a shallow hydrothermal seafloor setting. The New Caledonia serpentinites were serpentinised in a mantle wedge setting by slab-derived fluids, with possible contributions from oceanic serpentinisation and post-obduction serpentinisation. Petrological, whole rock and mineralogical analyses were combined to compare the two sample sets. Petrologically, the evolution of serpentinisation was close to identical in the two environments. However, more oxidised iron, Cl, S and C is present in serpentine from the ODP209 serpentinites relative to the New Caledonia serpentinites. Given these observations, the use of serpentinites from different geodynamic settings as a proxy for abyssal serpentinites from spreading settings must be undertaken with caution.

© 2017. American Geophysical Union. The redox state of iron in high-pressure serpentinites, which host a significant proportion of Fe 3+ 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 Fe 3+ . 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 Fe 3+ 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 Fe 3+ , also generally considered to be immobile, cannot be disregarded. We explore possible transport vectors for Ti and Fe through mineral texture analysis.

© 2017 The behavior of Fe during serpentinization largely controls the potential for oxidation-reduction reactions and energy budget for serpentinite-hosted microbial communities. We present Fe isotope data for mineral separates from a partially serpentinized dunite from New Caledonia to understand the behavior of Fe during serpentinization processes. Our new Fe isotope data in mineral separates is compared to existing data from whole rock studies of serpentinites, which have generally concluded that Fe mobility during serpentinization is restricted to the highest temperatures of serpentinization in subduction zones. Measurements of mineral separates from New Caledonia show significant Fe isotope fractionations, with serpentine-brucite mixtures having the lowest d 56 Fe ~ -0.35‰ and magnetite having the highest d 56 Fe ~ +0.75‰. Olivine, orthopyroxene, and the whole rock composition are all within error of d 56 Fe = 0.00‰. Fe isotope thermometry between mineral phases reveals two distinct temperatures of equilibration, one for the mantle olivine and pyroxene (~1325 °C), and a second, much lower temperature (~335 °C) for the serpentinite assemblage. The combined isotopic, mineralogical and geochemical data indicate that during the magnetite-forming stage of serpentinization, a pore fluid in equilibrium with the mineralogical assemblage evolves to higher Fe concentrations as serpentinization proceeds. When this pore fluid is removed from the serpentinizing environment, the total abundance of Fe removed from the rock in the pore fluid is much less than the bulk rock Fe and has a minimal effect on the overall rock composition.

Magnetite breakdown during subduction of serpentinised ultramafic rocks may produce oxidised fluids that oxidise the deep Earth and/or the sub-arc mantle, either via direct transport of ferric iron, or via redox reactions between ferric iron and other elements, such as sulfur. However, so far, there is no consensus on the oxidation state of fluids released during subduction of ultramafic rocks, or the factors that control this oxidation state. Subducted samples from a magma-poor rifted margin and a supra-subduction zone geodynamic setting were compared to examine evidence of changes in opaque phase assemblage and ferric iron content as a consequence of subduction, and as a function of geodynamic setting. Thermodynamic calculations in the system Fe–Ni–O–H–S and Fe–Ni–O–S at the pressures and temperatures of interest were used to constrain oxygen activities and fluid compositions. Samples from New Caledonia, which exemplify supra-subduction zone mantle, contain awaruite (FeNi3) and equilibrated with hydrogen-bearing fluids at oxygen activity less than the FMQ (fayalite–magnetite–quartz) buffer. In contrast, samples from the Zermatt Saas Zone ophiolite, Western Alps, which are thought to represent mantle from a subducted magma-poor rifted margin, contain magnetite plus sulfur-rich phases such as pyrite (FeS2), and are inferred to have equilibrated with hydrogen-poor fluids at oxygen activity greater than FMQ. This major difference is independent of differences in subduction pressure–temperature conditions, variation in peridotite protolith composition, or the nature of adjacent units. We propose that the Zermatt Saas Zone samples would have undergone more complete serpentinisation prior to subduction than the supra-subduction zone (SSZ) New Caledonian samples. This difference explains the different fluid compositions, because incompletely serpentinised rocks containing olivine and brucite retain or evolve awaruite-bearing assemblages that buffer fluid compositions to h

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 H2S concentration in ore fluids, destabilizing Au(HS)2-complexes. Most CM in gold deposits is deposited from CO2 and CH4 in ore fluids. These findings are applicable to similar deposits worldwide.

Intimately intergrown micron-scale framboidal pyrite, carbonaceous material (CM), chalcopyrite, sphalerite and cobaltite form polyframboids in prehnite-pumpellyite facies rocks of the Otago Schist, New Zealand. This study quantifies the metal contents of these polyframboids using synchrotron X-ray fluorescence (SXRF) and laser ablation inductively coupled plasma spectrometry (LA-ICP-MS). Trace elements Au, Zn, As, Mo, Co, Ni, Cu, Ag and Pb are significantly enriched in the polyframboids. The distribution of Zn most closely follows that of CM, and was probably absorbed into the structure of the polyframboids during biogenic processes. The concentrations of Au and Ag are positively corrected with the Zn concentration in the polyframboids (R2 of Au-Zn and Ag-Zn are 0.81 and 0.89, respectively.). The concentration of other trace elements, such as As, Co and Cu, which occur adjacent to Zn on elemental maps, show a weak relationship with Zn and may have been incorporated into the polyframboids during later processes. These polyframboids are a probable source for gold and other elements in the orogenic gold mineralization system of the Otago Schist. Metamorphic transformation of the polyframboids may have released the metallic elements into the mineralizing fluid during prograde metamorphism of the schist belt.

Subduction of hydrated lithospheric mantle introduces H O, ferric iron, oxidized carbon and sulphur to the subduction zone system. The fate of these components is poorly known, but is intimately linked to the global geochemical cycles of iron, carbon and sulphur, the genesis of arc-related ore deposits, the temporal evolution of mantle redox state and subduction-related earthquakes and magmatism. thermocalc is used to provide first-order constraints on the effect of subduction zone metamorphism on metamorphic redistribution of iron, carbon, sulphur and water in ultramafic rocks via construction of P−T and T-X(O) pseudosections with open system calculation of the effect of fluid loss. The calculations replicate observed mineral assemblages in high-P to low-T ultramafic rocks at P−T conditions consistent with those suggested by other workers. The results are consistent with open system fluid loss without significant fluid infiltration. Water loss is complete by 850 C, the corresponding depth of fluid loss being consistent with that inferred for earthquakes in subducting slabs. Losses of carbon and sulphur are relatively minor, at around <5% and <1%, respectively, so it is envisaged that most carbon and sulphur subducted in ultramafic lithologies is transported to >5 GPa, below the depths of the source zone for arc volcanoes.Oxygen activity for rocks in closed systems that evolve with a fixed redox budget is calculated to change from ΔFMQ −1 at 350 C to over ΔFMQ +3 at 850 C. This result emphasizes the need to consider redox budget as well as oxygen activity when the results of experiments performed at fixed oxygen activity relative to some buffer are interpreted in the context of natural systems. In open systems, devolatilization is calculated to increase the redox budget and oxygen activity of the residue via loss of methane and H S at the brucite-out and serpentine-out reactions respectively. No fluid-induced mechanism for oxidation of sub-arc mantle by transfer of

Liberation of fluids during subduction of oceanic crust is thought to transfer sulfur into the overlying sub-arc mantle. However, despite the importance of sulfur cycling through magmatic arcs to climate change, magma oxidation and ore formation, there has been little investigation of the metamorphic reactions responsible for sulfur release from subducting slabs. Here, we investigate the relative stability of anhydrite (CaSO4) and pyrite (FeS2) in subducted basaltic oceanic crust, the largest contributor to the subducted sulfur budget, to place constraints on the processes controlling sulfur release. Our analysis of anhydrite stability at high pressures suggests that this mineral should dominantly dissolve into metamorphic fluids released across the transition from blueschist to eclogite facies (~450–650 °C), disappearing at lower temperatures on colder geothermal trajectories. In contrast, we suggest that sulfur release via conversion of pyrite to pyrrhotite occurs at temperatures above 750 °C. This higher temperature stability is indicated by the preservation of pyrite–bornite inclusions in coesite-bearing eclogites from the Sulu Belt in China, which reached temperatures of at least 750 °C.Thus, sulfur may be released from subducting slabs in two separate pulses; (1) varying proportions of SO2, HSO4− and H2S are released via anhydrite breakdown at the blueschist–eclogite transition, promoting oxidation of remaining silicates in some domains, and (2) H2S is released via pyrite breakdown well into the eclogite facies, which may in some circumstances coincide with slab melting or supercritical liquid generation driven by influx of serpentinite-derived fluids. These results imply that the metallogenic potential in the sub-arc mantle above the subducting slab varies as a function of subduction depth, having the greatest potential above the blueschist–eclogite transition given the association between oxidised magmas and porphyry Cu(–Au–Mo) deposits. We speculate that th

Raman spectroscopic and petrographic analyses were performed on samples collected from zones distal and proximal to the Macraes gold deposit in the Otago Schist of New Zealand to characterize the features and possible origins of Carbonaceous Material (CM) and to assess the potential role of CM in the formation of gold deposits. CM is a common component in meta-sedimentary orogenic gold deposits, and it has been proposed that CM contributes to gold mineralization processes, but the details of the mechanisms responsible are not fully understood. Documentation of the origins of the Otago schist CM will improve our understanding of the role of CM in gold deposits. This work has identified four types of CM of varying thermal maturity and origins from prehnite–pumpellyite grade to lower greenschist grade samples. In prehnite–pumpellyite and pumpellyite–actinolite grade rocks, low-maturity CM 1 coexists with framboidal pyrite, indicating an in-situ, sedimentary origin, with a potential association with the source of gold. Low crystallinity CM 2 is also found in low grade samples and is likely to have been deposited from fluids unrelated to gold mobilization. CM 3 is the highest maturity CM recognized. CM 3 is found in samples from the highest metamorphic grades studied (lower greenschist facies), where bands of CM 3 cross cut the foliation, CM 3 is therefore thought to have been transported by fluids, though possibly only at short length scales. CM 4 is less mature than CM 3 and is found in mineralized rocks in association with sulfide minerals and gold. CM 4 is likely to have a depositional origin but its precise role with respect to gold mineralization has not been identified.

Sulfur isotope studies of base metal sulfide deposits have mostly focussed on sulfide minerals, but elemental sulfur and organic sulfur are also potentially significant components of the sulfur cycle during ore deposition. The δ34S of elemental sulfur and organic sulfur isolated from the Paleoproterozoic Here's Your Chance (HYC) Pb/Zn/Ag deposit (McArthur Basin, northern Australia) were measured to be between + 5 and + 8‰, approximately 6 to 7‰ heavier than the median values of first-generation HYC sulfides. Elemental sulfur and organic sulfur are thought to have been formed contemporaneously with the first generation of metal sulfides. The δ34S of organic sulfur showed an increasing trend along the path of the mineralising fluid, as sulfate was progressively 34S-enriched due to Rayleigh distillation. The δ34S data support a model in which bacterial sulfate reduction produced dissolved sulfide with δ34S of 0 to + 5‰. The subsequent oxidation of sulfide produced reactive sulfur species such as polysulfide ions, which were then incorporated into organic matter.

Subduction of sulfur in ocean crust makes a significant but poorly understood contribution to the global sulfur cycle. Part of the uncertainty arises from a lack of knowledge about the metamorphic changes that affect subducted sulfur-bearing minerals, and the ultimate source of sulfur that is subducted to depth. Sulfur δ34S varies both as a function of the original sulfur source, and as a consequence of processes subsequent to sulfide crystallisation such as devolatilisation, redox reactions, and fluid loss. To investigate sulfur liberation during subduction, secondary ion mass spectroscopy (SIMS) was used to measure δ34S in grains of pyrite, chalcopyrite and pyrrhotite in eclogites from the Zermatt–Saas zone in the Western Alps, and the Pouébo terrane of New Caledonia. Trace element mapping on selected sulfide grains was also performed. Sulfides in these rocks are generally associated with greenschist retrogression assemblages, but also occur as inclusions in garnet, associated with glaucophane and omphacite, and as polysulfide grains with typicalmagmaticcombinations of minerals. δ34S varies significantly within individual pyrite grains, with striking correlations, insome cases, between Co zoning and changes in δ34SVCDT. δ34SVCDT is, in many cases, greater than 13‰, consistent with derivation from seawater-derived sulfate. The dataset suggests that sulfur isotopes in pyrite experienced little or no post-crystallisation re-equilibration, that pyrite grew under open system conditions with heterogeneous fluid flow on a thin section scale, and that sulfide growth involved sulfur addition. Prograde subduction processes most likely involved sulfur loss. Sulfide growth occurred in some samples at the very earliest stages of exhumation. Therefore these sulfides provide useful information on the fluids present in slabs at great depths.

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 d34S 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.

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 FeKa 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.

The formation of base metal sulfide deposits requires not only a source of metals but also reduced sulfur. If incoming sulfur is present in ore fluids as sulfate, then a source of electrons is needed to drive the reduction of sulfate to sulfide. The oxidation of organic matter can release electrons that provide the reducing capacity, whether it be in low- or high-temperature settings that are conducive to biological or thermochemical sulfate reduction (BSR or TSR). The amounts of organic matter reacted and sulfide minerals formed can be estimated by mass balance calculations. In this study, an integrated mass balance expression is formulated that takes into account the sulfide mineral content and organic carbon content and H/C ratios of mineralised and non-mineralised rocks. Model calculations based on carbon, sulfur and redox budget balances suggest that the extent of oxidation of the organic matter present at the Here’s Your Chance (HYC) Pb–Zn deposit is insufficient for reduction of the required quantity of sulfate. The results imply that externally derived reducing capacity and/or reduced sulfur is required to form the metal resource. Possible sources include hydrocarbon-rich fluids from deeper parts of the sedimentary sequence or formation of sulfide and organic matter as products of BSR during sedimentation/early diagenesis. However, the observed oxidation of organic matter associated with the deposit suggests that at least some reducing capacity is locally derived. Therefore, our calculations are consistent with genetic models for HYC that have multiple sources of redox budget for sulfate reduction.

Estimates of standard molal Gibbs energy (ΔGf°) and enthalpy (ΔHf°) of formation, entropy (S°), heat capacity (Cp°) and volume (V°) at 25 °C and 1 bar of aqueous phenanthrene (P) and 1-, 2-, 3-, 4- and 9-methylphenanthrene (1-MP, 2-MP, 3-MP, 4-MP, 9-MP) were made by combining reported standard-state properties of the crystalline compounds, solubilities and enthalpies of phenanthrene and 1-MP, and relative Gibbs energies, enthalpies and entropies of aqueous MP isomers from published quantum chemical simulations. The calculated properties are consistent with greater stabilities of the β isomers (2-MP and 3-MP) relative to the α isomers (1-MP and 9-MP) at 25 °C. However, the metastable equilibrium values of the abundance ratios 2-MP/1-MP (MPR) and (2-MP + 3-MP)/(1-MP + 9-MP) (MPI-3) decrease with temperature, becoming <1 at ~375–455 °C. The thermodynamic model is consistent with observations of reversals of these organic maturity parameters at high temperature in hydrothermal and metamorphic settings. Application of the model to data reported for the Paleoproterozoic Here’s Your Chance (HYC) Pb–Zn–Ag ore deposit (McArthur River, Northern Territory, Australia) indicates a likely effect of high-temperature equilibration on reported values of MPR and MPI-3, but this finding is contingent on the location within the deposit. If metastable equilibrium holds, a third aromatic maturity ratio, 1.5 × (2-MP + 3-MP)/(P + 1-MP + 9-MP) (MPI-1), can be used as a proxy for oxidation potential. Values of log aH2(aq) determined from data reported for HYC and for a sequence of deeply buried source rocks are indicative of more reducing conditions at a given temperature than those inferred from data reported for two sets of samples exposed to contact or regional metamorphism. These results are limiting-case scenarios for the modeled systems that do not account for effects of non-ideal mixing or kinetics, or external sources or transport of the organic matter.Nevertheless, quantifying the t

Dunite from New Caledonia displays three types of serpentine-dominated veins. The earliest, type 1 veins are narrow (50–100 μm wide) and rarely extend across more than a single olivine grain. They are lizardite, contain abundant brucite and never contain magnetite. Type 2 veins are 0.01 to 0.1 mm wide, extend across several olivine grains and cut across the type 1 veins. They are lizardite, contain magnetite, often in vein interiors, and contain less brucite than type 1 veins. Type 3 veins are dominantly chrysotile, cm-scale, have a magnetite-rich core, and extend for meters or more. Analyses of two representative samples indicate that the type 1 veins have relatively Fe-rich serpentine (XMg = 0.92) and brucite (XMg = 0.82). These minerals are less magnesian than those in the type 2 veins; serpentine has XMg = 0.93–0.94 and brucite has XMg = 0.84. In the magnetite-rich core to the type 3 vein both serpentine (XMg = 0.94–0.97) and one of the two brucite populations (XMg = 0.94) are Mg-rich. Opx in harzburgite layers in these samples is cut by serpentine veins that are on the order of 0.05 mm wide. The serpentine veins after Opx lack talc or magnetite and, as with veins cutting olivine, the older veins are more Fe rich (XMg = 0.84) than the younger veins (XMg = 0.90). We conclude that the formation of magnetite was accompanied by the extraction of iron from the early-formed serpentine and brucite.Thermodynamic calculations suggest that the type 1 veins formed in a rock-dominated system where the activities of FeO, MgO, and SiO2 were dictated by the compositions of olivine and orthopyroxene. In contrast the type 2 veins were formed in a more fluid-dominated system where the infiltrating fluid was relatively oxidizing and out of equilibrium with the original brucite–serpentine assemblage. Reduction of this fluid was accompanied by reaction of brucite and serpentine to magnetite and hydrogen. By producing magnetite, this reaction extracted iron from brucite and serpentin

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 flow of basinal brines via complex silica and carbonate precipitation/dissolution processes. Such models are challenged by the necessary SiO2 removal. Thermodynamic and mass balance constraints are used to refine 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 infiltration 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.

We present a semi-empirical thermodynamic model with uncertainties that encompasses the full range of compositions in H2O–CO2–NaCl mixtures in the range of 10–380 °C and 1–3500 bars. For binary H2O–CO2 mixtures, the activity–composition model is built from solubility experiments. The parameters describing interactions between H2O and CO2 are independent of the absolute thermodynamic properties of the end-members and vary strongly non-linearly with pressure and temperature. The activity of water remains higher than 0.88 in CO2-saturated solutions across the entire pressure–temperature range. In the H2O–NaCl system, it is shown that the speciation of aqueous components can be accounted for by a thermodynamic formalism where activities are described by interaction parameters varying with intensive properties such as pressure and temperature but not with concentration or ionic strength, ensuring consistency with the Gibbs–Duhem relation.The thermodynamic model reproduces solubility experiments of halite up to 650 °C and 10 kbar, and accounts for ion pairing of aqueous sodium and chloride ions with the use of associated and dissociated aqueous sodium chloride end-members whose relative proportions vary with salinity. In the H2O–CO2–NaCl system, an activity–composition model reproduces the salting-out effect with interactions parameters between aqueous CO2 and the aqueous species created by halite dissolution. The proposed thermodynamic properties are compatible with the THERMOCALC database (Holland and Powell, 2011) and the equations used to retrieve the activity model in H2O–CO2 can be readily applied to other systems, including minerals.

Chemical analyses derived from petroleum exploration wells are notorious for their lack of key solute data and their potential to represent mixtures of reservoir and drilling fluids rather than pristine formation compositions. These drawbacks notwithstanding, they usually pose the only access to the reservoir geochemistry. Two literature protocols were applied to a dataset of incomplete major element analyses from 148 petroleum well samples from a database compilation of the Perth Basin whose deeper aquifers may serve as potential hot sedimentary aquifers for geothermal direct heat applications. The first protocol included a set of quality control criteria that reduced the number of relatively genuine formation well samples from the raw data pool by 71%. The remaining well analyses are invariably NaCl solutions of low to medium alkalinity and an ionic strength only occasionally reaching seawater salinity. The low amount of total dissolved solids indicates the absence of extended evaporites in the North Perth Basin and the prevalence of meteoric water infiltration and circulation at depths.The culled well samples underwent as a second protocol a forced equilibrium treatment to reconstruct in situ reservoir concentrations of missing elements (Si, Al, K), organic acid anions and non-carbonate alkalinity, and pH. The petroleum well samples were modelled to be in equilibrium with chalcedony (and kaolinite, albite, and paragonite) in the reservoir which yielded better convergence than using quartz instead. The derived formation temperatures correspond to geothermal gradients in the majority of cases between 25 and 35°C, in accord with literature findings. Those wells drilled to depth <1600 m returned questionably high geothermal gradients, an indication of incomplete mineral–fluid equilibrium. The measured pH (at ambient temperature) deviated in >90% of the wells from the calculated pH, either due to degassed CO2 or unaccounted acetate alkalinity. The wells were further m

Metasomatic rocks, in which mineralogical change is driven by infiltration of an externally-derived fluid, are challenging for the application of equilibrium thermodynamics because fluid-driven changes in rock bulk composition can be faster than diffusive within-grain re-equilibration. Nevertheless, careful definition of systems in terms of appropriate length scales, an informed choice regarding the controlling variables, and detailed petrological analysis can provide useful results. Thermodynamic calculations using methods that solve for equilibrium between a set of independent end-member reactions produce valid results regardless of the identity of the controlling variables but determination of the relationship between cause and effect in metasomatic rocks is best performed with some knowledge of the parameters that drive the evolution of the system. The correspondence between observations of serpentinised harzburgites from New Caledonia and the results of the application of thermodynamic techniques suggest that equilibrium thermodynamics can be applied to these rocks on appropriate small length scales, varying from micron to cm. The primary drivers for mineralogical change are proposed to be (1) infiltration of a H2O fluid, which is buffered to lower aO2 by the rock with resultant production of H2 and the resulting change in the redox budget of the rocks; and (2) gradients in aSiO2 caused by mm to cm scale variation in Si:(Mg+Fe) inherited from the harzburgite protolith.

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.

Elements that can occur in more than one valence state, such as Fe, C and S, play an important role in Earth's systems at all levels, and can drive planetary evolution as they cycle through the various geochemical reservoirs. Subduction introduces oxidised Fe, C and S in sediments, altered ocean crust, and partially serpentinised lithospheric mantle to the relatively reduced mantle, with short- and long-term consequences for the redox state of the mantle. The distribution of redox-sensitive elements in the mantle controls the redox state of mantle-derived material added to the lithosphere and atmosphere, such as arc volcanic gases and the magmas that form arc-related ore deposits. The extent of mantle oxidation induced by subduction zone cycling can be assessed, albeit with large uncertainties, with redox budget calculations that quantify the inputs and outputs to subduction zones. Literature data are augmented by new measurements of the chemical composition of partially serpentinised lithospheric mantle from New Caledonia and ODP 209. Results indicate that there is a net addition of Fe (55 ± 13 × 10 12 mol year− 1), C (4.6 ± 4.0 × 10 12 mol year− 1), S (2.4 ± 0.9 × 10 12 mol year− 1), and redox budget (5–89 × 10 12 mol year− 1) at subduction zones. Monte Carlo calculations of redox budget fluxes indicate that fluxes are 46 ± 12 × 10 12 mol year− 1 entering subduction zones, if input and output parameters are assumed to be normally distributed, and 46–58 × 1012 mol year− 1 if input and output parameters are assumed to be log-normally distributed.Thus, inputs into subduction zones for Fe, C, S and redox budget are in excess of subduction zone outputs. If MORB and plume-related fluxes are taken into account then Fe, C and S fluxes balance, within error. However, the redox budget does not balance, unless the very lowest estimates for the extent of slab oxidation are taken. Thus it is likely that subduction continuously increases the redox budget of the mantle, that is

Ti site occupancy in zircon (ZrSiO4) is fundamental to thermobarometry because substitution mechanisms control Ti content–temperature relations. Here we describe the results of three independent methods used to demonstrate that Ti substitutes for Si and not Zr in zircon. Zircon grains were synthesized from oxide powders held in a Na2WO4 flux at 1 bar and 1300 °C. Zircon grains equilibrated with rutile + cristobalite show Ti contents (1201 ppm) nearly half that of zircon grains equilibrated with srilankite ((Ti,Zr)O2) + tetragonal zirconia (2640 ppm). The lower Ti content of zircon grains produced at silica-saturated conditions indicates that Ti substitution predominately occurs on the Si site. Moreover, the higher Ti contents of silica-saturated experiments at 1 bar (1201 ppm), relative to those at 1 GPa (457 ppm, Ferry and Watson, 2007), indicates a substantial pressure effect on Ti solubility in zircon. Measured Ti K-a edge X-ray Absorption Near Edge Structure (XANES) spectra of synthetic zircon grains show energies and normalized intensities akin to those seen among tetrahedrally coordinated Ti-bearing standard minerals, strongly suggesting that Ti occupies the Si site. Density functional theory (DFT) calculations confirm that Ti substitution is most likely to occur on the Si site and predict a Ti–O bond length of 1.797 Å (compared to an average of 2.160 Å for substitution on the Zr site), in excellent agreement with X-ray Absorption Fine Structure (EXAFS) spectra of experimentally grown zircon grains which indicate a value of 1.76(1) Å.The software FEFF 8.4 was used to simulate XANES spectra from the defect structures determined by DFT for Ti substituting on both the Si and Zr sites. The predicted spectrum for Ti on the Si site reproduces all the key features of the experimental zircon spectra, whereas Ti on the Zr site is markedly different. All applied methods confirm that Ti substitutes for Si in zircon. Consequently, the Ti content of zircon at a given press

A number of lines of evidence point to a causal link between oxidised slab-derived fluids, oxidised sub-arc mantle, and the formation of economic concentrations of metals such as Cu and Au that require oxidised magmas. However, trace element evidence from some trace element and isotope data suggests that sub-arc mantle is no more oxidised than mantle elsewhere. A simple analytical model is applied to constrain the evolution of sub-arc mantle oxidation state as a function of redox-budget fluxes from the subducting slab. Influential variables include the solubility of Fe3+ and SO42− in slab-derived fluids, the geometry of the infiltration of slab-derived fluids in sub-arc mantle, the coupling between slab-derived and arc-output redox budgets, and the concentration of redox-buffering elements such as Fe and S in the sub-arc mantle. Plausible Archean and Proterozoic redox budget fluxes would not have created oxidised sub-arc mantle without input from ferric iron or sulphate dissolved in non-aqueous fluids such as silicate melts. Aqueous-borne Phanerozoic redox budget fluxes, on the other hand, which are dominated by the sulphate component, could have increased sub-arc fo2 by up to three log10 units. The results are generally consistent with the proposed elevated fo2 for sub-arc mantle, but no resolution was found for the apparent contradiction between high proposed fO2 values derived from iron-based oxybarometry and the lower values inferred from trace element and isotope evidence Increases in sub-arc mantle fO2 are favoured by focussed fluid infiltration and magma generation, weak coupling between slab and arc-output redox budgets, and restricted redox-buffering in the sub-arc mantle.Fertile arc segments for ore deposits associated with oxidised magmas require fluid chemistry and pressure–temperature gradients that enhance Fe3+ and SO42 − solubility in aqueous and silica-rich fluids, tectonic stress regimes that favour focussed transfer of components into the sub-arc m

New Re-Os in molybdenite and U-Pb in titanite and zircon age data have been used to discern several dis- crete alteration, mineralization, and igneous events that occurred in iron oxide-copper-gold (IOCG) deposits in the Selwyn-Mount Dore corridor of the Proterozoic Mount Isa inlier. Two distinct sodic-calcic alteration events that occurred prior to mineralization have been recognized. This suggests that sodic-calcic alteration may be a fundamental precursor to IOCG mineralization as it mobilizes large amounts of metals, including Fe, K, and Cu. Sodic-calcic alteration at Starra was early synmetamorphic (Isan orogeny) at 1594 ± 8 Ma. Some ironstone-hosted mineralization at Starra may have formed during this event, but an Re-Os molybdenite age of 1568 ± 7 Ma suggests that mineralization also occurred during a (late) metamorphic tectonic event. These ages demonstrate that the Starra system is unrelated to igneous activity; a metamorphic fluid source is pro- posed. Titanite from a preore alteration assemblage at Mount Elliott yields a U-Pb age of 1530 ± 11 Ma which is within error of the ~1515 Ma Re-Os molybdenite ages from both Mount Elliott and the adjacent SWAN de- posit. A magmatic-related origin for the Mount Elliott and SWAN deposits is favored given that the titanite and main-stage molybdenite ages are similar to the emplacement ages for the nearby Squirrel Hills Granite. Molyb- denite-bearing calcite veins that crosscut main-stage IOCG mineralization at SWAN have been dated at ~1355 Ma, indicating that this paragenetic stage is unrelated to the Squirrel Hills Granite. U-Pb SHRIMP zircon analyses of volumetrically minor trachyandesitic dikes from Mount Elliott and SWAN reveal relatively young crystallization ages of 1119 ± 15 and 1096 ± 10 Ma, therefore they are not a suitable fluid or metal source for these deposits.Two Re-Os molybdenite analyses from Mount Dore (1503 ± 5 and 1508 ± 5 Ma) are similar to the ~1515 Ma ages from Mount Elliott and SWAN emplacement

A zircon grain in an orthopyroxene-garnet-phlogopite-zircon-rutile-bearing xenolith from Udachnaya, Siberia, preserves a pattern of crystallographic misorientation and subgrain microstructure associated with crystal-plastic deformation. The zircon grain records significant variations in titanium (Ti) from 2.6 to 30 ppm that corresponds to a difference in calculated Ti-in-zircon temperatures of over several hundred degrees Celsius. The highest Ti concentration is measured at subgrain centres (30 ppm), and Ti is variably depleted at low-angle boundaries (down to 2.6 ppm). Variations in cathodoluminescence coincide with the deformation microstructure and indicate localised, differential enrichment of rare earth elements (REE) at low-angle boundaries. Variable enrichment of U and Th and systematic increase of Th/U from 1.61 to 3.52 occurs at low-angle boundaries. Individual SHRIMP-derived U-Pb ages from more deformed zones (mean age of 1799 40, n = 22) are systematically younger than subgrain cores (mean age of 1851 65 Ma, n = 7), and indicate that open system behaviour of Ti-Th-U occurred shortly after zircon growth, prior to the accumulation of significant radiogenic Pb. Modelling of trace-element diffusion distances for geologically reasonable thermal histories indicates that the observed variations are ~ 5 orders of magnitude greater than can be accounted for by volume diffusion. The data are best explained by enhanced diffusion of U, Th and Ti along deformation-related fast-diffusion pathways, such as dislocations and low-angle (<5°) boundaries. These results indicate chemical exchange between zircon and the surrounding matrix and show that Ti-in-zircon thermometry and U-Pb geochronology from deformed zircon may not yield information relating to the conditions and timing of primary crystallisation.