James E. Mungall

Roasting the mantle: Slab melting and the genesis of major Au and Au-rich Cu deposits

The generation of large deposits of Au and Cu in suprasubduction-zone settings depends upon a combination of factors, including availability of the chalcophile elements to arc magmas in their mantle source regions, and the operation of suitable hydrothermal systems in the upper crust where the deposits eventually form. The removal of chalcophile elements from the mantle wedge into arc magmas can only occur if sulfide is absent from the melted source rock, requiring oxidation of the mantle wedge to values of log f O 2 > FMQ + 2, where f O 2 is oxygen fugacity and FMQ is the fayalite-magnetite-quartz oxygen buffer. The only agent capable of effecting this change is ferric iron, carried in solution by slab-derived partial melts or supercritical fluids. Arc magmas with high potential to generate Au and Cu deposits will have certain geochemical characteristics; they will have f O 2 more than two log units above FMQ and they will have either adakitic, sodic-alkaline, or potassic-ultrapotassic affinities. Favorable tectonic settings include subduction of very young lithosphere or very slow or oblique convergence, flat subduction, and the cessation of subduction.

Empirical models relating viscosity and tracer diffusion in magmatic silicate melts

The Adam-Gibbs equations describing relaxation in silicate melts are applied to diffusion of trace components of multicomponent liquids. The Adam-Gibbs theory is used as a starting point to derive an explicit relation between viscosity and diffusion including non-Arrhenian temperature dependence. The general form of the equation is Diη = Aiexp{Δ(scEi)/TSc}, where D is diffusivity, η is melt viscosity, T is absolute temperature, Δ(scEi) is the difference between the products of activation energies and local configurational entropies for viscous and diffusive relaxation, Ai is a constant that depends on the characteristics of the diffusing solute particles, and Sc is configurational entropy of the melt. The general equation will be impractical for most predictive purposes due to the paucity of configurational entropy data for silicate melts. Under most magmatic conditions the proposed non-Arrhenian behaviour can be neglected, allowing the general equation to be simplified to a generalized form of the Eyring equation to describe diffusion of solutes that interact weakly with the melt structure: Diη/T = Qiexp{ΔEi/RT}, where Qi and ΔEi depend on the characteristics of the solute and the melt structure. If the diffusing solute interacts strongly with the melt structure or is a network-forming cation itself, then ΔEi = 0, and the relation between viscosity and diffusion has the functional form of the classic Eyring and Stokes-Einstein equations; Diη/T = Qi. If the diffusing solute can make diffusive jumps without requiring cooperative rearrangement of the melt structure, the diffusivity is entirely decoupled from melt viscosity and should be Arrhenian, i.e., Di = Qiexp{Bi/T}. A dataset of 594 published diffusivities in melts ranging from the system CAS through diopside, basalt, andesite, anhydrous rhyolite, hydrous rhyolite, and peralkaline rhyolite to albite, orthoclase, and jadeite is compared with the model equations. Alkali diffusion is completely decoupled from melt viscosity but is related to melt structure. Network-modifying cations with field strength Zi2/r between 1 and 10 interact weakly with the melt network and can be modelled with the extended form of the Eyring equation. Diffusivities of cations with high field strength have activation energies essentially equal to that of viscous flow and can be modelled with a simple reciprocal Eyring-type dependence on viscosity. The values of Qi, ΔEi and Bi for each cation are different and can be related to the cation charge and radius as well as the composition of the melt through the parameters Zi2/r, M/O, and Al/(Na + K + H). I present empirical fit parameters to the model equations that permit prediction of cation diffusivities given only charge and radius of the cation and temperature, composition and viscosity of the melt, for the entire range of temperatures accessible to magmas near to or above their liquidus, for magmas ranging in composition from basalt through andesite to hydrous or anhydrous rhyolite. Pressure effects are implicitly accounted for by corrections to melt viscosity. Ninety percent of diffusivities predicted by the models are within 0.6 log units of the measured values.

Ore Deposits of the Platinum-Group Elements

The formation of ore deposits of the platinum-group elements (PGE) requires that their concentrations be raised about four orders of magnitude above typical continental crustal abundances. Such extreme enrichment relies principally on the extraction capacity of sulfide liquid, which sequesters the PGE from silicate magmas. Specific aspects of PGE ore formation are still highly controversial, however, including the role of hydrothermal fluids. The majority of the worlds PGE reserves are held in a handful of deposits, most of which occur within the unique Bushveld Complex of South Africa.

Evidence from meimechites and other low-degree mantle melts for redox controls on mantle-crust fractionation of platinum-group elements.

Understanding of the geochemistry of the chalcophile elements [i.e., Os, Ir, Ru, Pt, Pd (platinum-group elements), and Au, Cu, Ni] has been informed for at least 20 years by the common assumption that when crust-forming partial melts are extracted from the upper mantle, sulfide liquid in the restite sequesters chalcophile elements until the extent of partial melting exceeds ≈25% and all of the sulfide has been dissolved in silicate melt [Hamlyn, P. R. & Keays, R. R. (1985) Geochim. Cosmochim. Acta 49, 1797–1811]. Here we document very high, unfractionated, chalcophile element concentrations in small-degree partial melts from the mantle that cannot be reconciled with the canonical residual sulfide assumption. We show that the observed high, unfractionated platinum-group element concentrations in small-degree partial melts can be attained if the melting takes place at moderately high oxygen fugacity, which will reduce the amount of sulfide due to the formation of sulfate and will also destabilize residual monosulfide solid solution by driving sulfide melts into the spinel-liquid divariant field. Magmas formed at high oxygen fugacity by small degrees of mantle melting can be important agents for the transfer of chalcophile elements from the upper mantle to the crust and may be progenitors of significant ore deposits of Pt, Pd, and Au.

Geochemical evidence from the Sudbury structure for crustal redistribution by large bolide impacts

Deformation and melting of the crust during the formation of large impact craters must have been important during the Earths early evolution, but such processes remain poorly understood. The 1.8-billion-year-old Sudbury structure in Ontario, Canada, is greater than 200 km in diameter and preserves a complete impact section, including shocked basement rocks, an impact melt sheet and fallback material. It has generally been thought that the most voluminous impact melts represent the average composition of the continental crust, but here we show that the melt sheet now preserved as the Sudbury Igneous Complex is derived predominantly from the lower crust. We therefore infer that the hypervelocity impact caused a partial inversion of the compositional layering of the continental crust. Using geochemical data, including platinum-group-element abundances, we also show that the matrix of the overlying clast-laden Onaping Formation represents a mixture of the original surficial sedimentary strata, shock-melted lower crust and the impactor itself.

Sulfide-silicate textures in magmatic Ni-Cu-PGE sulfide ore deposits: Disseminated and net-textured ores

Abstract A large proportion of ores in magmatic sulfide deposits consist of mixtures of cumulus silicate minerals, sulfide liquid, and silicate melt, with characteristic textural relationships that provide essential clues to their origin. Within silicate-sulfide cumulates, there is a range of sulfide abundance in magmatic-textured silicate-sulfide ores between ores with up to about five modal percent sulfides, called “disseminated ores,” and “net-textured” (or “matrix”) ores containing about 30 to 70 modal percent sulfide forming continuous networks enclosing cumulus silicates. Disseminated ores in cumulates have various textural types relating to the presence or absence of trapped interstitial silicate melt and (rarely) vapor bubbles. Spherical or oblate spherical globules with smooth menisci, as in the Black Swan disseminated ores, are associated with silicate-filled cavities interpreted as amygdales or segregation vesicles. More irregular globules lacking internal differentiation and having partially facetted margins are interpreted as entrainment of previously segregated, partially solidified sulfide. There is a textural continuum between various types of disseminated and net-textured ores, intermediate types commonly taking the form of “patchy net-textured ores” containing sulfide-rich and sulfide-poor domains at centimeter to decimeter scale. These textures are ascribed primarily to the process of sulfide percolation, itself triggered by the process of competitive wetting whereby the silicate melt preferentially wets silicate crystal surfaces. The process is self-reinforcing as sulfide migration causes sulfide networks to grow by coalescence, with a larger rise height and hence a greater gravitational driving force for percolation and silicate melt displacement. Many of the textural variants catalogued here, including poikilitic or leopard-textured ores, can be explained in these terms. Additional complexity is added by factors such as the presence of oikocrysts and segregation of sulfide liquid during strain-rate dependent thixotropic behavior of partially consolidated cumulates. Integrated textural and geochemical studies are critical to full understanding of ore-forming systems.

Behavior of gold in a magma at sulfide-sulfate transition: Revisited

Abstract We have investigated experimentally the partitioning of Au between solid and liquid sulfide phases and basaltic melts at 200 MPa, at redox conditions close to the sulfide-sulfate transition, over temperatures between 1050 and 1200 °C, which span the monosulfide solid solution (MSS) - sulfide liquid (SuL) solidus. The measured MSS/basalt partition coefficient of Au (DMSS-silAu) is about 100-200, whereas the partition coefficient of sulfide liquid/basalt (DMSS-silAu) is approximately 10 times larger at 2200. Although we find that temperature, pressure, and oxygen fugacity (ƒO₂) exert relatively weak controls on Au partitioning, they exert major indirect influences on Au behavior by controlling the identity of the condensed sulfide phase and by affecting S solubility. These observations have important implications for the behavior of Au in the processes of partial melting in the mantle and magma crystallization in the crust. The occurrence of natural magmas with elevated concentrations of Au and presumably other highly siderophile and chalcophile elements requires predominance of MSS over SuL in the source or/and oxidizing conditions close to or above the sulfide-sulfate transition in the magma.

Naldrettite, Pd2Sb, a new intermetallic mineral from the Mesamax Northwest deposit, Ungava region, Québec, Canada

Abstract Naldrettite, Pd2Sb, is a new intermetallic mineral discovered in the Mesamax Northwest deposit, Cape Smith fold belt, Ungava region, northern Québec. It is associated with monoclinic pyrrhotite, pentlandite, chalcopyrite, galena, sphalerite, cobaltite, clinochlore, magnetite, sudburyite (PdSb), electrum and altaite. Other rarer associated minerals include a second new mineral (ungavaite, Pd4Sb3), sperrylite (PtAs2), michenerite (PdBiTe), petzite (Ag3AuTe4) and hessite (Ag2Te). Naldrettite occurs as anhedral grains, which are commonly attached or moulded to sulphide minerals, and also associated with clinochlore. Grains of naldrettite vary in size (equivalent circle diameter) from ~10 to 239 μm, with an average of 74.4 μm (n = 632). Cleavage was not observed and fracture is irregular. The mineral has a mean micro-indentation hardness of 393 kg/mm2. It is distinctly anisotropic, non- pleochroic, has weak bireflectance, and does not exhibit discernible internal reflections. Some grains display evidence of strain-induced polysynthetic twinning. Naldrettite appears bright creamy white in association with pentlandite, pyrrhotite, clinochlore and chalcopyrite. Reflectance values in air (and in oil) for R1 and R2 are: 49.0, 50.9 (35.9, 37.6) at 470 nm, 53.2, 55.1 (40.3, 42.1) at 546 nm, 55.4, 57.5 (42.5, 44.3) at 589 nm and 58.5, 60.1 (45.4, 47.2) at 650 nm. The average of 69 electron-microprobe analyses on 19 particles gives: Pd 63.49, Fe 0.11, Sb 35.75, As 0.31, and S 0.02, total 99.68 wt.%, corresponding to (Pd1.995Fe0.007)2.002(Sb0.982As0.014S0.002)0.998. The mineral is orthorhombic, space group Cmc21, a 3.3906(1), b 17.5551(5), c 6.957(2) Å , V 414.097(3) Å3, Z = 8. Dcalc is 10.694(1) g/cm3. The six strongest lines in the X-ray powder-diffraction pattern [d in Å (I)(hkl)] are: 2.2454(100)(132), 2.0567(52)(043), 2.0009(40)(152), 1.2842(42)(115), 1.2122(50)(204) and 0.8584(56)(1.17.4).

Role of degassing of the Noril’sk nickel deposits in the Permian–Triassic mass extinction event

Significance The Noril’sk deposits represent one of the most valuable metal concentrations on Earth and are associated with the world’s largest outpouring of mafic magma. Mass release of nickel into the atmosphere during ore formation has been postulated as one of the triggers for the Permian–Triassic Mass Extinction Event, by promoting the activity of the marine Archaea methanosarcina with catastrophic greenhouse climatic effects. The missing link has been understanding how nickel, normally retained at depth in magmatic minerals, could have been mobilized into magmatic gases. The flotation of magmatic sulfides to the surface by gas bubbles was suggested as a possible mechanism. Here, we provide evidence of physically attached nickel-rich sulfide droplets and former gas bubbles, frozen into the Noril’sk ores. The largest mass extinction event in Earths history marks the boundary between the Permian and Triassic Periods at circa 252 Ma and has been linked with the eruption of the basaltic Siberian Traps large igneous province (SLIP). One of the kill mechanisms that has been suggested is a biogenic methane burst triggered by the release of vast amounts of nickel into the atmosphere. A proposed Ni source lies within the huge Noril’sk nickel ore deposits, which formed in magmatic conduits widely believed to have fed the eruption of the SLIP basalts. However, nickel is a nonvolatile element, assumed to be largely sequestered at depth in dense sulfide liquids that formed the orebodies, preventing its release into the atmosphere and oceans. Flotation of sulfide liquid droplets by surface attachment to gas bubbles has been suggested as a mechanism to overcome this problem and allow introduction of Ni into the atmosphere during eruption of the SLIP lavas. Here we use 2D and 3D X-ray imagery on Noril’sk nickel sulfide, combined with simple thermodynamic models, to show that the Noril’sk ores were degassing while they were forming. Consequent “bubble riding” by sulfide droplets, followed by degassing of the shallow, sulfide-saturated, and exceptionally volatile and Cl-rich SLIP lavas, permitted a massive release of nickel-rich volcanic gas and subsequent global dispersal of nickel released from this gas as aerosol particles.

The ratio of B-field and dB/dt time constants from time-domain electromagnetic data: a new tool for estimating size and conductivity of mineral deposits

A discrete conductive sphere model in which current paths are constrained to a single planar orientation (the ‘dipping sphere’) is used to calculate the secondary response from Geotech Ltd’s VTEM airborne time domain electromagnetic (EM) system. In addition to calculating the time constants of the B-field and dB/dt responses, we focus on the time-constant ratio at a late time interval and compare numerical results with several field examples. For very strong conductors with conductivity above a critical value, both the B-field and dB/dt responses show decreasing values as the conductivity increases. Therefore response does not uniquely define conductivity. However, calculation of time constants for the decay removes the ambiguity and allows discrimination of high and low conductivity targets. A further benefit is gained by comparing the time constants of the B-field and dB/dt decays, which co-vary systematically over a wide range of target conductance. An advantage of calculating time constant ratios is that the ratios are insensitive to the dip and the depth of the targets and are stable across the conductor. Therefore we propose to use their ratio rτ = τB/τdB/dt as a tool to estimate the size and conductivity of mineral deposits. Using the VTEM base frequency, the magnitude of rτ reaches a limiting value of 1.32 for the most highly conductive targets. Interpretations become more complicated in the presence of conductive overburden, which appears to cause the limiting value of rτ to increase to 2 or more.