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Sodic volcano-plutonic terranes in the Archean can be well preserved, but why oxidized S-rich sodic magmas and porphyry-type Cu-Au deposits are so rare remains poorly understood. Here we addressed this issue by measuring the S concentration and S6+/ΣS ratio of primary apatite grains in >2.7 Ga felsic volcanic rocks from the well-characterized Neoarchean Abitibi Greenstone Belt of the Superior Province, Canada. Whereas apatite grains in most samples contain low-S concentrations (<0.01 wt%, n = 24), a few apatite samples are S-rich (0.14 ± 0.03 wt%, 1σ) and have low-S6+/ΣS ratios (0.56 ± 0.17; 1σ, n = 4). Samples with S-poor apatite have variable whole-rock La/Yb ratios (generally <30) and zircon 10 000*(Eu/Eu*)/Yb ratios of 11 ± 8 (1σ), which may be products of plume-driven or over-thickened crustal melting. In contrast, the samples with S-rich apatite have elevated La/Yb ratios of 49 ± 15 (1σ), zircon 10 000*(Eu/EuN*)/Yb ratios of 26 ± 7 (1σ), and zircon δ18O values of 5.8 ± 0.1 ‰ (1σ), consistent with a deep, hydrous and homogeneous mantle-like source for the melts dominated by amphibole ± garnet fractionation that is reminiscent of subduction-like process. These are the first reported results documenting the predominant accommodation of relatively reduced S in S-rich apatite grains crystallized from terrestrial silicate melts, possibly reflecting slight oxidation associated with the hydration of Neoarchean mantle and crystal fractionation over the magma evolution. The more common S-poor apatite data suggest that suppressed oxidation of the parental sodic magmas led to weak S emission from Earth’s interior to its evolving surface, explaining the rarity of porphyry-type Cu deposits in >2.7 Ga Archean sodic volcano-plutonic terranes. 

Titanium (Ti) typically exhibits low mobility in geologic fluids due to the low aqueous solubility of common (Fe-)Ti oxide minerals. Consequently, Ti isotope variations (δ49/47Ti, given as δ49Ti) in geologic systems are primarily attributed to magmatic differentiation. Thus, the potential for fluid-mineral fractionation has received less attention. However, ligand-rich fluids are capable of mobilizing Ti as observed in natural systems and laboratory studies. As hydrothermal ore mineralization is commonly associated with ligand-rich brines capable of transporting significant quantities of metals, Ti isotopes may aid in understanding mineralization and alteration in complex hydrothermal systems. Here we present data from computational modeling of various Ti coordination complexes theorized to exist in geologic systems and/or under relevant experimental conditions as well as computed fractionation factors for various Ti-bearing crystalline phases to investigate the basic mechanics of equilibrium fluid-mineral Ti isotope fractionation. These results indicate that equilibrium fluid-mineral Ti isotope exchange between our modeled Ti complexes and phases with 6-coordinated Ti is predicted to generally lead to enrichment of heavy Ti isotopes in the fluid. Because minerals with 6-coordinated Ti (such as magnetite and ilmenite) are the most important reservoirs of Ti in the solid Earth, Ti isotope equilibration between terrestrial rocks and fluids can be generalized to enrich the fluid in heavy Ti isotopes. We also performed magnetite-ülvospinel leaching experiments to investigate fluid-mineral Ti isotope fractionation in this phase. Mineral leaching experiments varying acid strength, leaching temperature, and reaction time with HCl and HF qualitatively support the prediction that the fluid phase will become enriched in heavy Ti isotopes during fluid-mineral interactions that approach equilibrium with Ti-rich magnetite. Additionally, the leaching data also suggest that the fluid becomes slightly enriched in lighter Ti isotopes when Ti exchange is limited—potentially due to kinetic effects. Therefore, magnetite from natural systems may be depleted in heavy Ti isotopes during regenerative mineral replacement involving equilibration with fluids or may possibly become depleted in light Ti isotopes under a kinetic fractionation regime—leading to mineral δ49Ti values that are insufficiently explained by magmatic differentiation or inter-mineral fractionation. These results are a first look at fluid-mineral interactions that may affect Ti isotope fractionation in hydrothermal mineral systems, and Ti isotopes should be further studied as a potential method of understanding aqueous metal transport and tracing alteration in mineral deposits. 

Electric vehicles (EVs) require substantially more copper and other metals than conventional internal combustion engine (ICE) vehicles. For example, manufacture of an ICE automobile requires 24 kg copper whereas manufacture of an EV requires 60 kg. Many have expressed concern that the lack of critical mineral resources may not allow full electrification of the global vehicle transportation fleet, and the vehicle electrification resource demand is just a small part of that needed for the transition. By displaying both demand and mine production in full historical context we show that copper resources are available, but 100% manufacture of EVs by 2035 requires unprecedented rates of mine production. The 100% EV target not only requires significant extra copper for battery manufacture, but also more copper for grid upgrades to support charging, while hybrid electric vehicles do not require extra grid capacity. Under today’s policy settings for copper mining, it is highly unlikely that there will be sufficient additional new mines to achieve 100% EV by 2035. Policymakers might consider changing the vehicle electrification goal from 100% EV to 100% hybrid manufacture by 2035. This would allow for future output of existing and new copper mines to be used for the developing world to catch up with the developed world in electrification. Life cycle emissions for battery electric vehicles compared with hybrid electric vehicles are comparable with each other. Mining must be recognized as essential, and exploration and responsible copper mine development strongly encouraged. 

Oxidation of the sub-arc mantle driven by slab-derived fluids has been hypothesized to contribute to the formation of gold deposits in magmatic arc environments that host the majority of metal resources on Earth. However, the mechanism by which the infiltration of slab-derived fluids into the mantle wedge changes its oxidation state and affects Au enrichment remains poorly understood. Here, we present the results of a numerical model that demonstrates that slab-derived fluids introduce large amounts of sulfate (S6+) into the overlying mantle wedge that increase its oxygen fugacity by up to 3 to 4 log units relative to the pristine mantle. Our model predicts that as much as 1 wt.% of the total dissolved sulfur in slab-derived fluids reacting with mantle rocks is present as the trisulfur radical ion, S3–. This sulfur ligand stabilizes the aqueous Au(HS)S3– complex, which can transport Au concentrations of several grams per cubic meter of fluid. Such concentrations are more than three orders of magnitude higher than the average abundance of Au in the mantle. Our data thus demonstrate that an aqueous fluid phase can extract 10 to 100 times more Au than in a fluid-absent rock-melt system during mantle partial melting at redox conditions close to the sulfide-sulfate boundary. We conclude that oxidation by slab-derived fluids is the primary cause of Au mobility and enrichment in the mantle wedge and that aqueous fluid-assisted mantle melting is a prerequisite for formation of Au-rich magmatic hydrothermal and orogenic gold systems in subduction zone settings.