Search

The komatiitic Raglan Horizon in northern Quebec hosts one of the largest komatiite-associated magmatic sulfide deposits in the world. Several studies have suggested that the sulfide ores were formed by melting and transporting sedimentary sulfides from upstream after the komatiite melt had assimilated a large amount of S-rich country rocks. In this study, we report new compositional data of the sulfide ores in Zones 5-8 and 13-14 along with the legacy assay database to investigate variability of the ore-forming processes at Raglan at the camp scale. More than 90,000 drill core samples were selected, and the rocks are categorized into disseminated, net-textured, and massive sulfide based on their sulfide abundance. We demonstrate that the majority of the compositional variability of the sulfide-bearing rocks can be attributed to the difference in the mass ratio between silicate and sulfide melts (R factor), by applying thermodynamic modeling of silicate and sulfide magma evolution. The massive sulfides display depletions in Cu, Pd, and Pt that are best explained by sulfide liquid fractionation, which differentiates the residual Cu-, Pd-, and Pt-rich sulfide liquid from the Ni-rich monosulfide solid solution (MSS) cumulate now preserved within the massive sulfide ores. A small population of sulfide-bearing samples that is strongly depleted in all the economically important metals has been interpreted to represent externally derived xenomelts that were poorly equilibrated with the metal-rich host magma due to low residence time. A portion of massive sulfides has been found to be depleted in Pd and Cu but not Pt. This decoupling of these metals can be well explained by a postmagmatic process that persisted to temperatures as low as 300°–350°C. Similar depletions of Pd have also been observed in the Expo Intrusive Suite immediately to the south. The regional variations in the compositions of individual orebodies suggest that they occurred in highly localized environments that record only local magmatic conditions and that the sulfide mineralization did not reach equilibrium with a single regionally continuous silicate magma system. Each zone preserves a unique signature of assimilation, sulfide segregation, and sulfide crystallization; hence, they likely represent separate magmatic pulses within the larger Raglan system. Lastly, based on the spatial locations of the low tenor sulfides, we tentatively suggest that Zone 2 and the Katinniq zone are more proximal to the as-yet-unidentified eruption site of the Raglan komatiite lava flow field.

Genesis of magmatic Ni-Cu-(PGE) deposits involves many interconnected and multiple-scale processes in the fields of thermodynamics, kinetics and fluid dynamics. The main focus of quantitative work on magmatic sulfide ore genesis has been on equilibrium thermodynamics since the initial studies over 50 years ago, while the significance of kinetics and dynamics to sulfide mineralization in dynamic magmatic systems has received little attention. Taking the komatiite-hosted Ni-Cu-(PGE) deposits of the Raglan area as an example, we have developed a quantitative model for assimilation of sulfidic substrates during lava emplacement through the consideration of these three fields. We show that the dominant control on the composition of externally derived sulfide xenomelts throughout their residence within the flowing magma is exerted by relative rates of diffusion of sulfur and metals. In rapid channelized flow of komatiites, the kinetically-controlled extraction of chalcophile elements from silicate melt into externally-derived sulfide droplets released from underlying sediments is the quickest way to produce orebodies with economic value, without the necessity of reaching either sulfide saturation throughout the mass of magma or indeed compositional equilibrium in the magmatic system as our long-held understanding would suggest. The kinetic upgrading of initially metal-poor sulfide xenomelts is enhanced for sulfide droplets of smaller size and increasing downstream distance from the source, approaching to equilibrium mass distribution for the fast-diffusing elements such as Cu during prolonged or especially vigorous processes (e.g., chaotic magma mixing). In this kinetically-driven process, differences in diffusivities between Pt and Pd may account for the anomalous excess Pd/Pt ratios (~2) of disseminated ores from many komatiite-related deposits compared with the compositions of the parental magmas. Sedimentation of sulfide on the bottom of the flowing magma terminates this kinetically-controlled process, while the number density of droplets imposes a restriction on sulfide compositions due to mass conservation. Therefore, sulfide mineralization in komatiite-associated deposits is mostly controlled by diffusion kinetics with additional interactions and restrictions from the dynamics of transport and settling of sulfide droplets. By analogy, multiple cycles of dynamic processes predominate in the conduit-type magmatic deposits. A quantitative grasp of the relative importance of these three fundamental mechanisms, i.e., thermodynamic driving forces, kinetics of diffusive equilibration, and fluid dynamics of transport and deposition, is of great value in understanding ore genesis in complex mineral systems and even the origin of igneous rocks in general.

The highest grade Pd-Pt deposit on Earth, the J-M Reef, is hosted in coarse-grained to pegmatoidal cumulates called the Reef Package. Decades of mine development of the J-M Reef have revealed that a distinct discontinuity in rock fabric marks the top of the rock unit that hosts economic-grade sulfide mineralization. Mine geologists refer to this discontinuity as the hanging wall contact. This contact is the top of the Reef Package and is always locatable—either by the change in rock fabric or by distinctive hanging wall textures of silicate minerals—even when the reef sulfide mineralization is absent. This rather subtle textural feature is used reliably by mine geologists to follow the Reef during exploration and mine development. Although some high tenor sulfides (>1000 ppm Pd in 100% sulfide) are found sporadically in the hanging wall cumulates, these accumulations are too small to be economically viable. We present quantitative rock fabric data for four Reef Package and hanging wall intersections collected by electron back-scattered diffraction (EBSD). Plagioclase fabrics in the hanging wall are characterized by low variance in grain sizes and a strong point maximum concentration of (010) and a perpendicular girdle distribution of [100] consistent with an axial B-type fabric. These fabrics are indicative of either compaction of the crystal mush or crystal settling of nucleated crystals, the bulk magma in a chamber. Conversely, the fabrics of the Reef Package show higher variance grain in size distributions and weak to undeveloped preferred orientation of plagioclase crystals that did not undergo significant alignment or textural equilibration of plagioclase grains. The absence of foliation in the Reef Package stands in contrast both to hanging wall fabrics and to other reported EBSD datasets of plagioclase crystals orientations from the Bushveld Complex, the Skaergaard Intrusion, and the Rum Intrusion. Furthermore, plagioclase crystal size distributions for the Reef Package show flatter slopes and convex profiles with fewer crystals at small size fractions indicating the dissolution of small crystals during partial melting and textural coarsening (i.e. Ostwald ripening) and crystal growth. Crystal growth was favored over the nucleation of new crystals during prolonged interaction with a hot infiltrating melt into the resident mush resulting in the coarse-grained textures of the Reef Package cumulates. The hanging wall contact represents a boundary between partially remelted crystal mush of the Reef Package, where sulfide mineralization formed and accumulated, and an overlying essentially barren cumulate pile. The hanging wall cumulates formed following the cessation of footwall erosion and the resumption of crystal accumulation by normal magma chamber processes.

In this contribution, we analyze 30 years of mine development data and quantitatively identify the processes that control the grade and tenor of the mineralized rock. An assay database of more than 60,000 samples was used to examine variations in ore grade and tenor of the sulfide mineralization in the J-M reef horizon of the Stillwater Complex along the strike and down the dip of the deposit in the area of the Stillwater mine. We compare these results with data from the East Boulder mine and whole-rock lithogeochemistry of samples collected along the entire strike length of the complex. We find significant variation in the composition of the reef sulfides in different spatial domains of the Stillwater mine area and between the Stillwater and East Boulder mines. Most of the variation in the grade and tenor can be explained by a variation in the mass of silicate magma with which the sulfide liquid equilibrated (i.e., R factor); however, geochemical and textural evidence suggests that parts of the reef may have experienced significant S loss following initial sulfide melt segregation. Some variability in the reef tenor and grade can be attributed to variable amounts of sulfur loss due to low-temperature hydrothermal fluids and the overestimation or underestimation of metal concentrations in reef assays due to the nugget effect. Furthermore, we address the Pd/Pt ratio of the reef samples and suggest that the lower solubility of Pt in the parental silicate melt may have caused the crystallization and removal of Pt alloys at some point before the melt reached sulfide saturation and Pt could partition into the sulfide liquid. This disparity between the prior evolution of Pt and Pd in the silicate melt resulted in the observed Pd/Pt ratio of ~3.65 across all areas of the reef—a value significantly larger than anticipated for primitive mantle-derived magmas.

There has been vigorous debate for several decades about whether the extreme enrichments of platinum group elements (PGEs) in some magmatic sulfide deposits could have resulted from simple equilibration of sulfide liquid with silicate melt. Key examples include the Ni-Cu-Pd mineralization in the Norilsk mining camp, the UG2 and Merensky reef Pt-Pd deposits in the Bushveld Complex, the Pd-rich J-M reef of the Stillwater Complex, and the Skaergaard Pd-Au mineralization. It was argued historically that the observed PGE tenors in these latter deposits are too high to be consistent with simple equilibration of sulfide and silicate melt. A commonly cited mechanism for increasing PGE tenor in magmatic sulfide is the upgrading of initially low tenor sulfide by allowing a small volume of sulfide to react with successive batches of fresh, previously undepleted silicate magma. Here we review several previous models for sulfide upgrading in light of recent changes in accepted values of the partition coefficients governing PGE exchange between sulfide and silicate, and we critically examine the physical scenarios implicit in each previous model. We show that, although sulfide upgrading may occur in natural settings such as fractional melting of the mantle, during the formation of sulfide accumulations from magmas it is unlikely to have effects that can be distinguished from simple one-stage batch equilibration. Even the most PGE-rich deposits currently known have compositions that can easily be accounted for by the simple one-stage batch process, with the possible exception of the Skaergaard Pd mineralization. It is generally not possible to use the measured composition of accumulations of magmatic sulfide to infer that sulfide upgrading has or has not occurred.

A close relationship between Ni–Cu–(PGE) sulfide deposits and magmatic conduit systems has been widely accepted, but our present understanding still rests on empirical inductions that sulfide liquids are entrained during magma ascent and aggregated at hydrodynamic traps such as the opening of a conduit into a larger magma body. In this contribution, a preliminary quantitative model for the dynamics of mm-scale sulfide droplets in a vertical magmatic conduit is developed, examining such limiting parameters as the size, transport velocity and the magmas’ maximum carrying capacity for sulfide droplets. Addition of numerous dense sulfide droplets significantly reduces magma buoyancy and rapidly increases the bulk viscosity, and the resulting pressure gradient in the propagating conduit dyke restricts the maximum volume fraction of droplets that can be carried by ascending magma. For sulfide droplets alone, the maximum carrying capacity is low, but it will be improved dramatically by the addition of volatiles which reduces the density and viscosity of silicate melt. Potential volatile degassing during decompression further facilitates sulfide entrainment by reducing bulk magma density, and the formation of buoyant compound vapour-sulfide liquid bubble drops also greatly enhances the carrying capacity. The breakdown of compound drops by detachment of parts of the vapour bubble or sulfide droplet may occur at low pressure, which liberates sulfide liquids from rising compound drops, potentially to collect in traps in the conduit system. When sulfide-laden magma flows through a widening conduit, many droplets can be captured by the re-circulation flow just downstream of the expanding section, followed by sulfide liquid accumulation and enhanced chemical interaction via diffusive exchange with the recirculating magma, potentially resulting in an economic, high-tonnage ore body. We apply our models to the emplacement of sulfide-rich magmatic suspensions at Noril’sk and show that the disseminated mineralization in intrusions could have formed when magmas carrying re-suspended sulfide liquid entrained from pre-existing sulfide accumulations in the conduit system reached their limiting sulfide carrying capacity as dictated by buoyancy and were deflected into blind sills flanking the principal conduit for flood basalt volcanism.

The Moon accreted meteoritic material towards the end of Solar System formation. Quantification of this late accretion requires an estimation of the abundance of highly siderophile, or iron-loving, elements in the lunar mantle. As lunar mantle samples are not available, estimates are derived from lunar basalt compositions, but the melting phase relations needed to derive the mantle composition are poorly constrained. Here we present sulfur solubility measurements from laboratory experiments, combined with thermodynamic calculations, which show that the lunar basalt source is likely to be saturated in a sulfur-poor, iron-rich sulfide melt that concentrates some highly siderophile elements more than others. We found that the observed range in the ratios of highly siderophile elements in primitive lunar basalts is much smaller than expected from residual sulfide control alone. Instead, the elemental ratios are consistent with mixing between primary sulfide-saturated melts and minute (

The platinum-group element (PGE) contents of komatiites have been used to estimate the PGE contents of their mantle sources and investigate temporal variations in the PGE systematics of the mantle throughout Earth history. However, the use of mantle melts to investigate source characteristics is critically dependent on understanding the fractionation of the elements in question between mantle sources and their derived magmas. We present new PGE and Re abundance data, together with Re-Os isotope data for the pristine 1.9 Ga Winnipegosis komatiites, Canada. Whole rock Re-Os isotope data define a 1865 ± 40 Ma isochron, consistent with previous age estimates, with initial γOs of +0.9 ± 1.4. The PGE and Re variations in these komatiites were controlled by fractionation of olivine, chromite, Os-Ir alloys, a Ru-Os rich phase (possibly laurite) from the komatiite melt. The calculated parental melt composition at 23.6 ± 1.6 wt% MgO has 1.1 ± 0.1 ppb Os, 0.91 ± 0.08 ppb Ir, 4.0 ± 0.5 ppb Ru, 7.0 ± 0.8 ppb Pt, 7.2 ± 0.7 ppb Pd, and 0.53 ± 0.06 ppb Re. The calculated PGE contents are low relative to many komatiites; using existing methods for calculating the PGE contents of mantle sources suggests the Winnipegosis source had PGE contents from 25 ± 19 wt% to 57 ± 7 wt% of primitive mantle values. This surprising finding substantiates a growing ‘PGE paradox’, where almost all komatiites appear to have formed from PGE-depleted mantle sources. We suggest the simplest resolution to this paradox is that current methods systematically underestimate mantle source PGE contents. We test the assumptions implicit in these methods by comparing detailed models of PGE behaviour during mantle melting to a large database of parental melt compositions of high degree melts. Ruthenium behaviour in high degree melts can be adequately modelled using our current understanding of Ru partitioning. However, the Ru contents of high degree mantle melts are strongly dependent on the degree of melting, as Ru-rich melts formed after sulphide exhaustion are increasingly mixed into early-formed Ru-poor melts. Platinum and Pd behaviour during mantle melting cannot be successfully modelled under the widespread assumption that they are strongly incompatible following sulphide exhaustion, suggesting that these elements cannot be used to estimate PGE contents of the mantle sources of high degree melts. Parental melt Pt and Pd in many high degree lavas are correlated with Al2O3/TiO2, suggesting a pressure control on their partitioning. We attribute the relatively low PGE contents of the Winnipegosis komatiites to their moderate degrees and depth of melting compared to other komatiites, rather than invoking a PGE-depleted mantle source. More broadly, the complex controls (T, P, fO2, S content, prior depletion) on the PGE contents of komatiites mean that most komatiites can be reconciled with being derived from sources with primitive mantle-like PGE contents, and few komatiites can be confidently asserted to come from PGE-depleted mantle sources. Pending a better understanding of PGE behaviour during mantle melting, we recommend caution when using komatiite PGE systematics to infer the highly siderophile element evolution and accretionary history of Earth’s mantle.

To better constrain the origin of the chromitites associated with the Esker Intrusive Complex (EIC) of the Ring of Fire Intrusive Suite (RoFIS), a total of 50 chromite-bearing samples from the Black Thor, Big Daddy, Blackbird, and Black Label chromite deposits have been analysed for major and trace elements. The samples represent three textural groups, as defined by the relative abundance of cumulate silicate phases and chromite. To provide deposit-specific partition coefficients for modeling, we also report on the results of laboratory experiments to measure olivine- and chromite-melt partitioning of V and Ga, which are two elements readily detectable in the chromites analysed. Comparison of the Cr/Cr+Al and Fe/Fe+Mg of the EIC chromites and compositions from previous experimental studies indicates overlap in Cr/Cr+Al between the natural samples and experiments done at >1400oC, but significant offset of the natural samples to higher Fe/Fe+Mg. This is interpreted to be the result of subsolidus Fe-Mg exchange between chromite and the silicate matrix. However, little change in Cr/Cr+Al from magmatic values, owing to the lack of an exchangeable reservoir for these elements. A comparison of the composition of the EIC chromites and a subset of samples from other tectonic settings reveals a strong similarity to chromites from the similarly-aged Munro Township komatiites. Partition coefficients for V and Ga are consistent with past results in that both elements are compatible in chromite (DV = 2-4; DGa ~ 3), and incompatible in olivine (DV = 0.01-0.14; DGa ~ 0.02), with values for V increasing with decreasing fO2. Simple fractional crystallization models that use these partition coefficients are developed that monitor the change in element behaviour based on the relative proportions of olivine to chromite in the crystallizing assemblage; from 'normal' cotectic proportions involving predominantly olivine, to chromite-only crystallization. Comparison of models to the natural chromite V-Ga array suggests that the overall positive correlation between these two elements is consistent with chromite formed from a Munro Township-like komatiitic magma crystallizing olivine and chromite in 'normal' cotectic proportions, with no evidence of the strong depletion in these elements expected for chromite-only crystallization. The V-Ga array can be explained if the initial magma responsible for chromite formation is slightly reduced with respect to the FMQ oxygen buffer (~FMQ- 0.5), and has assimilated up to ~20% of wall-rock banded iron formation or granodiorite. Despite the evidence for contamination, results indicate that the EIC chromitites crystallized from 'normal' cotectic proportions of olivine to chromite, and therefore no specific causative link is made between contamination and chromitite formation. Instead, the development of near- monomineralic chromite layers likely involves the preferential removal of olivine relative to chromite by physical segregation during magma flow. As suggested for some other chromitite-forming systems, the specific fluid dynamic regime during magma emplacement may therefore be responsible for crystal sorting and chromite accumulation.

The Rustenburg Layered Suite (RLS) of the Bushveld Complex of South Africa is a vast layered accumulation of mafic and ultramafic rocks. The layers are widely assumed to result from fractional crystallization from a melt-dominated magma chamber. We derive compositions of all units of the RLS with thermodynamic models of assimilation of crust by a komatiitic parent magma. Ultramafic U-type cumulate layers represent crystal mush produced by single stages of assimilation-batch crystallization (ABC). Anorthositic (A-type) magma mushes emerged by a second stage of batch crystallization during ascent of melts supernatant to mid-crustal U-type cumulates. Only the ferrobasaltic magma of the Upper and Upper Main Zone formed via classical assimilation-fractional crystallization (AFC) and ponded in a melt-dominated magma chamber that subsequently evolved by fractional crystallization. Mineral deposits associated with reversals between mafic and ultramafic layers, hitherto attributed to magma chamber processes, might form in small intrusions entirely lacking melt-dominated magma chambers.

High-pressure phase relations for much of the Cu–Fe–S system have not previously been determined experimentally. Experimental studies have concentrated on low-pressure phase relations and cannot explain high-pressure sulfide mineral inclusion assemblages in some natural blueschists and eclogites. In particular, the coexistence of pyrite + covellite at 1·0 GPa, and pyrite + bornite at 1·9 GPa, observed in New Caledonian rocks, is precluded by tie-lines between S and bornite, and S and the intermediate solid solution (iss), in the published low-pressure experimental topologies at corresponding temperatures. In addition, the Cu content (up to ∼10 at%) of pyrrhotite in eclogite exceeds the experimentally determined maximum for Cu in solid solution with pyrrhotite at low pressures and at corresponding temperatures. We have performed six experiments in which natural chalcopyrite starting material was equilibrated at conditions ranging from 1·0 to 1·7 GPa and 500 to 650 °C. At 1 GPa chalcopyrite is replaced by iss. The iss phase undergoes a terminal breakdown reaction between 1·0 and 1·7 GPa, being replaced by a new assemblage of bornite, pyrite, and pyrrhotite. Our experimental results confirm predictions from the SUPCRT thermodynamic database (Johnson et al., 1992; Computers & Geosciences 18, 899–947) but not that of Robie & Hemingway (1995; US Geological Survey Bulletin 2131). The former database is therefore recommended for calculation of high-pressure sulfide phase relations. Chalcopyrite and its high-temperature, low-fS2 equivalent, iss are not stable at pressures corresponding to much of blueschist–eclogite-facies metamorphism. These results are also applicable to sulfide assemblages in the lithospheric mantle along both oceanic and continental geotherms; the subsolidus Cu-rich mineral in the lithosphere at depths of 30 to >65 km must be bornite–digenite solid solution (bn-ss) rather than iss as is commonly assumed.

Most of the world's major deposits of nickel and copper were formed as accumulations of magmatic sulfide liquid within small mafic-ultramafic intrusions. Ore-hosting intrusions exhibit a variety of forms but typically show greater horizontal than vertical extents, occurring as tube-shaped chonoliths, narrow elongate sills, boatshaped bodies, or sword blade-shaped dikes with originally horizontal principal axes. Sulfide accumulation at the downward termination of blade-shaped dikes is noted in a number of deposits worldwide. Based on evidence from continental dike swarms, Icelandic fissure eruptions, and active shield volcanoes, we suggest that these blade-shaped bodies formed by magma migration within vertical fractures that propagated laterally rather than vertically. Some examples, notably the bladed dikes of the South Raglan trend, have contact relationships indicating processes of active erosion, assimilation, and replacement of country rock. Where such dikes are injected into mixed volcanic-sedimentary sequences, thermal modeling of interaction with nonrefractory country rock predicts repeated formation and collapse of transient chilled margins against narrow zones of partially molten wall rock. Where the wall rock is sulfide-rich sediment, this generates a slurry of sulfide liquid, country-rock xenoliths, and chilled margin fragments that flows down the wall to accumulate at the bottom edge of the dike. This type of mixture is commonly seen as "sulfide-matrix ore breccias" in intrusion-hosted deposits. Widening of the conduit along zones of easily eroded country rock may result in a transition from a dike-like to a tubular chonolith geometry. Multiple magma pulses within the same magma conduit may give rise to complex superimpositions of ore zones, further complicated by formation of sulfide-silicate melting-infiltration fronts. Hence we argue that the bladed-dike geometry is an end-member type that commonly serves as a precursor form to a range of eventual geometric forms; recognition of this basic geometry provides general insights into the origins of other important deposits.

The origin and parental magma for layered cumulates in the Lower Banded series (LBS) and the J-M Reef Pd-Pt deposit of the Stillwater Complex remains poorly constrained. We present whole-rock lithogeochemistry and mineral chemistry from LBS rocks collected from drill holes and surface samples from the Mountain View area of the complex that in total span nearly the entirety of the LBS stratigraphy. Excess S, Pt, and Pd in the noritic and gabbronoritic cumulates of the LBS indicate that small amounts of high tenor sulfide liquid generated at very low degrees of sulfide oversaturation were ubiquitous parts of the cumulate assemblage. We show that a simple two-stage thermodynamic model of assimilation-batch crystallization of a komatiitic parental magma in the lower crust, produces a close match to a common suite of fine-grained gabbronorite dikes and sills that intrude both the complex and its footwall. After fractionating ultramafic cumulates in the lower crust, the model contaminated komatiitic liquid produces upper crustal cumulates by batch crystallization en route to or at the level of the intrusion. The modeled rocks have compositions and mineral assemblages closely resembling pyroxenite of the Bronzitite zone and both norite and gabbronorite cumulates in the lower LBS. The trends from the Bronzitite zone through Norite zone I and Gabbronorite zone I can be understood as the result of deposition of crystals from successive batches of the same contaminated parental magma, with an upward trend toward greater amounts of cooling before the separation of crystals from liquid. The olivine-bearing suite of Olivine-bearing zone I, which includes the J-M Reef, can be modeled by partial remelting of the same norite and gabbronorite cumulates due to a temporarily increased flux of hot, moderately less contaminated LBS parental magma that infiltrated partially molten cumulates because its density exceeded that of the interstitial liquid. This model suggests that infiltration of hot Mg-rich parental liquid into moderately PGE-enriched footwall cumulates may be fundamental to the formation of the extremely high tenor sulfide mineralization in the J-M Reef ore zone, and perhaps other reef-type deposits worldwide. The same metal tenors that would require silicate/sulfide mass ratios (i.e., R-factors) of 105 to 106 in a single stage of equilibration would be attained during this second stage of interaction by the incremental infiltration and passage of LBS parental magma through previously sulfide saturated cumulate mush.

The origins of apparently magmatic Fe-P-O deposits like those of the El Laco volcanic complex, Chile, with masses on the order of 1 Gt remain contentious. Previous attention has been focused largely on the high-tonnage massive magnetite bodies that form the economic mineral deposits. Extensive occurrences of unconsolidated granular Fe-P-oxide materials or their apparent metamorphic equivalents have received relatively little attention. Here we report textures and compositions of unconsolidated Fe-P-oxide materials from Laco Sur, El Laco. Unconsolidated tephra at El Laco is dominated by hematite along with subsidiary Fe-phosphates, monazite, and silica. A porous hematite bomb contains menisci of two coexisting materials. One is hydrous shoshonitic glass with perlitic texture, and the other comprises finegrained intergrowths of Fe-P-REE (rare earth element) oxides having the bulk composition of the eutectic in the system FePO4-Fe2O3 with minor S, Cl, and other components. We show by experiment that very similar compositions would have coexisted as immiscible silicate and oxide liquids at 900 °C and 1 GPa in the presence of carbonic vapor, magnetite, and quartz; both will also form anhydrous liquids at 1080 °C and 101 kPa. We infer the former existence of a phosphatic Fe-oxide magma rich in volatiles that underwent explosive degassing and consequent rapid compositional undercooling to produce the observed assemblage of Fe-oxide tephra containing small amounts of Fe-P-REE phosphates and silicate glass.

The Brazilian Pilar and Tres Buracos Paleoproterozoic mid-tier gold deposits are located in the south western Pilar de Goias greenstone belt, containing 61,688 kg and 7,144 kg of gold, respectively, in addition to approximately 30,000 kg of past production (1736–2018). This research aimed to assess the hypothesis that the mobility of alkali elements may be used to facilitate the discovery of new gold deposits in hydrothermal systems by creating geochemical vectors based on alkali element mobility. The hypothesis was first proposed for the mafic rocks in the West Australian Goldfields and has been adopted in other deposits worldwide (E.g., Andorinhas greenstone belt, Brazil, Pataz gold field, Peru, and Rio das Velhas gold deposit, Brazil). The procedures consisted in the analysis of metasedimentary and mafic rock types from two drill holes from the Pilar de Goias greenstone belt, central Brazil. These drill holes have intercepted mineralized and barren rock types. The petrographic and energy dispersive spectrometric results indicated that the host rocks around the orebodies present intense sericitization, albitization, and sulfidation. The chemical results reveal that the mobile elements Cs, Rb and Ba tend to be enriched in gold-bearing rock units and depleted in barren rock units. These elements are carried by fluids and can replace K in the structure of the newly formed hydrothermal phyllosilicates forming a halo of alkali-rich elements of up to 50 m around the orebodies. The upper continental crust normalized ratio ((Cs + Rb)/Th)UCC was adopted as an alteration index to evaluate and distinguish possible mineralized zones, with ((Cs + Rb)/Th)UCC > 3, from barren zones, with ((Cs + Rb)/Th)UCC 3 indicating high prospectivity.

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.

The largest mass extinction event in Earth's 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 Superior craton is bordered on its northern and eastern sides by the approximately coeval Cape Smith fold belt and the Labrador Trough, two major Paleoproterozoic volcano-sedimentary belts that record broadly similar tectonic evolution but which show some distinctive characteristics and have notably different mineral resource endowments. The Roberts Lake Syncline, situated directly between the Cape Smith and Labrador Trough, hosts two Paleoproterozoic mafic volcanic sequences and has uncertain tectonic affinities to its neighboring fold belts. It was previously linked to Labrador Trough magmatism but re-interpretation of the regional geology suggests a closer resemblance to the successions of the Cape Smith belt. We present new lithogeochemistry that shows that the Roberts Lake Syncline comprises two distinct magmatic events rather than the single event previously interpreted. The lower and more voluminous suite of the Roberts Lake Syncline lavas comprises multiply-saturated basalts characterized by normalized trace element patterns similar to E-type mid-ocean ridge basalts (E-MORB). The upper suite of the Roberts Lake Syncline stratigraphy is composed of volcanic rocks with depleted, N-MORB-like trace element signatures rocks spanning a range from komatiites and picrites with near-primary compositions to high-Mg basalts with flat normalized trace element patterns. Both suites were apparently undersaturated with sulfide liquid in their mantle source. The E-MORB magmas were affected by a sulphide-saturation event, leading to widespread and variable degrees of depletion of chalcophile elements, despite showing no significant crustal contamination. The N-MORB magmas also underwent saturation with sulfide melt, generating minor occurrences of magmatic sulfide mineralization hosted by ultramafic intrusions within the older volcanic suite and small but significant depletions in chalcophile elements in the erupted picritic basalts. The geochemistry of the lower E-MORB suite is similar to that of the 2170 Ma Biscotasing dike swarm that occurs in and near the Labrador Trough and the 1998 Ma Minto-Povungnituk large igneous province (LIP) of the Cape Smith belt, whereas the upper N-MORB-like suite in the Roberts Lake Syncline has compositions resembling those of the 1880 Ma Circum-Superior LIP. Our detailed geochemical comparison suggests a close resemblance to the chemical stratigraphy observed within the Cape Smith belt, leading us to consider the Roberts Lake Syncline as the southeasternmost portion of the Ungava Orogen rather than the northernmost part of the Labrador Trough. These insights contribute to a revised LIP and plume centre map for this NE portion of the Superior craton and help to constrain the large-scale tectonic architecture of the margins of the Superior Province.

The motion of dense Fe-rich immiscible sulphide liquids is generally supposed to be dominated by gravitational settling in crustal magma chambers, however they may become buoyant by attachment to low-density vapour bubbles to form compound drops, possibly contributing to the upward transfer of sulphur and transition metals in degassing magma bodies. Here, using numerical models, we consider constraints on the flotation of compound drops, and find a wide range of morphologies that would be expected to be capable of migrating through magmatic systems, including both melt- and mush-dominated domains, but also some situations where the compound drops will spontaneously separate to allow the vapour to rise while the sulphide phase is sequestered in the mush. The stability of compound drops is empirically related to a function f ( B o ) = | σ M V − σ M S | σ M S ⋅ 1 / B o S + | σ V S − σ M S | σ M S ⋅ 1 / B o V , where M, V, and S denote silicate melt, vapour, and sulphide liquid, σ is surface tension (N⋅m−1), and Bo is the Bond number. Over a range of plausible conditions in magmas, f(Bo) must exceed values of 3 to 4 for capillary forces to overcome buoyancy forces tending to pull them apart. Using published thermodynamic models for vapour and sulphide solubility in silicate melts, we show that in many magmas the second boiling of vapour occurs synchronously with the saturation of sulphide liquid, increasing the potential for coupling of vapour and sulphide droplets. Diffusive coarsening produces mm-sized bubbles within 100-500 years, generating enough buoyancy to trigger the migration of compound drops. During compaction-driven expulsion of interstitial melt, compound drops can pass through constrictions between crystals in mush. The flotation of sulphide-vapour aggregates is likely to occur in crustal magma reservoirs and provides a feasible mechanism for the removal of sulphide liquid from crystal mushes, promoting its ability to participate in the generation of magmatic sulphide and porphyry copper deposits, emissions of the metals during volcanic eruptions, and even the remobilization of chalcophile metals sequestered in deep arc cumulates to generate porphyry Cu-(Au) deposits.

Transport of coexisting sulfide and silicate melts in partially molten peridotite contributes to the redistribution of chalcophile elements within the upper mantle as well as the genesis of magmatic Ni-Cu sulfide deposits, but has not been investigated systematically. Using laboratory experiments, theoretical calculations, and X-ray synchrotron microtomography, this study documents the topology and considers controls on the extraction of two immiscible liquids during partial melting of mantle peridotite. Under hydrostatic conditions, the measured dihedral angle at silicate melt-mineral-mineral junctions is 13.7–21.3°. Silicate melt is distributed along grain edges forming incompletely interconnected melt channels that disconnected by some dead ends at melt fractions ∼7–9 vol%. Application of theoretically predicted permeability ( k ∼ 10 − 14 –10−16 m2) permits estimation of the extraction velocity of silicate melt of 0.7-11.1 μm/day within a single interconnected melt channel. In the absence of silicate melt, isolated sulfide droplets (3.77 vol%) show a sulfide-olivine-olivine dihedral angle of 91.5–101.3°. However, in the presence of silicate melt, sulfide droplets (average size ∼2.53 ± 2.14 μm, 1σ) are partially surrounded by silicate melt and stranded in triple junctions or melt pockets due to the limitation of the smallest dimension (0.3 μm) of melt channels. Thus, the extraction of sulfide liquid is highly restricted by these dead ends and the smallest dimension of melt channels during porous flow of silicate melt. In contrast, during large-strain shear deformation (strain ∼1.6–2.5), initially stranded sulfide droplets were elongated and extracted with silicate melt into liquid-rich sheets with a length of several hundred microns, constantly oriented at 14.3 ± 4.5° to the shear plane and antithetic to the shear direction. The angle is lower than that (18–30°) of those sheets containing sulfide liquid only, indicating that silicate melt dominates liquid-rich sheets. Driven by stress, silicate melt-dominated liquid-rich sheets open the appropriately oriented grain boundaries between silicate minerals, thus providing an efficient pathway for the extraction of sulfide liquid during deformation. When such sheet-like channels remain open, sulfide droplets (> millimeter-scale) can be potentially mobile through high strain domains of the upper mantle, contributing to the addition of chalcophile elements and the fertilization of the lithospheric mantle.

Conventional models of the genesis of the Rustenburg Layered Suite (RLS) of the Bushveld Complex postulate that it is the product of a single multiply-replenished magma chamber that cooled as a single massive unit, i.e., a monolithic magma chamber. This concept has been challenged by alternative hypotheses involving out-of-sequence emplacement of some of its major layers as sills. Both scenarios have partial support from high-precision U-Pb geochronological data. To test these contradictory hypotheses, new zircon geothermometric data and compositional data for plagioclase from the Upper Critical Zone are presented and the available geochronological data are tested against the predictions of the thermal evolution of the entire RLS for both emplacement and cooling scenarios. Crystallization temperatures of zircon within units of the Upper Critical Zone were estimated using Ti-in-zircon thermometry and range between 799 ± 45 °C and 865 ± 64 °C. The data are used in conjunction with a detailed numerical model of heat flow in the Bushveld Complex that is used to approximate the duration and extent of thermal perturbations felt throughout the system and delimit the time intervals during which zircon crystals could have grown at the measured crystallization temperatures. The results show that prolonged cooling histories (>1 Myr), that would be experienced near the centre of a large, slowly cooled, plutonic magma chamber, would erase signs of plagioclase zoning at 4 kbar and moderate f H 2 O ; however, plagioclase crystals with zoning profiles spanning at least 10 mole% An are common in the Upper Critical Zone. In contrast, emplacement of the major units of the RLS at widely separated intervals, as recorded by the existing high-precision U-Pb dataset, would impose transient thermal effects on the system against a backdrop of generally much lower ambient temperatures throughout its evolution. In this scenario, apparent ages of zircon crystals would record the time of cooling through temperatures near the water-saturated biotite granite solidus, corresponding to the final intercumulus mineral assemblage in both mafic and ultramafic macrolayers. Subsequent reheating of these rocks would be unable to reset primary zircon crystallization dates but might, in some examples, result in some amount of remelting or regrowth of zircon. Comparison of the evolving temperature fields of the two types of emplacement and cooling histories shows that the existing geochronological data and preservation of plagioclase zoning are consistent with out-of-sequence emplacement and rapid cooling of individual ultramafic sills into previously solidified lithologies of the RLS but not with the conventional view of a single monolithic magma body.

The Tootoo and Mequillon Ni-Cu-Pt-Pd deposits in the South Raglan Trend of the New Quebec orogen host significant but as yet unexploited nickel-copper-platinum group element (PGE) mineralization within the mafic-ultramafic rocks of the Expo Intrusive Suite. The olivine melagabbronorite host rocks have been pervasively altered to hydrous mineral assemblages dominated by chlorite, tremolite-actinolite, and relict late-magmatic hornblende, characteristic of greenschist facies metamorphism. In greenschist-altered rocks, the PGE are spatially associated with intercumulus blebs and networks of pyrrhotite, chalcopyrite, and pentlandite after primary magmatic sulfides. Palladium is significantly enriched in the vicinity of veins associated with local replacement of the early hydrous silicate mineral assemblage by talc, calcite, dolomite, and minor serpentine and disseminated magnetite. The varieties of platinum group minerals (PGM) are similar in samples both with and without carbonate alteration, with platinum hosted exclusively in discrete sperrylite grains, and palladium dominantly hosted by the Pd-Sb intermetallic phases of sudburyite, ungavaite, and naldrettite, as well as merenskyite, kotulskite, and michenerite. Palladium minerals commonly form composite grains with hessite, altaite, and other PGM. Most of the PGM are hosted by silicate minerals, but some also occur attached to sulfide minerals, and a few PGM grains are completely enclosed within sulfides. In samples disturbed by carbonate alteration, the PGM are present in greater abundance and larger size. We suggest that palladium was transferred from massive ores to the net-textured ores via an oxidizing, CO2-bearing, neutral to mildly alkaline fluid capable of mobilizing the semimetals such as antimony as hydroxide complexes. Upon reaching zones where oxygen fugacity was buffered to lower values by an assemblage containing pyrrhotite but not magnetite, antimony in the fluid was reduced to its metallic state, causing coprecipitation of palladium in intermetallic phases. This process appears to have been localized at a reaction front near the outer edges of moderately oxidized carbonate-altered domains surrounding carbonate veins. This reaction front has high Pd/Pt whereas lower Pd/Pt ratios are observed in magnetite-bearing, carbonate-altered samples closer to the carbonate veins. PGE grades in the vicinity of carbonate alteration attain levels of potential economic significance, possibly meriting attention as PGE resources distinct from the Ni-Cu-PGE sulfide assemblage extracted by current beneficiation practices in nearby deposits. If the magnetite-free, carbonate-altered lithofacies can be confirmed by further study to show consistently elevated Pd grades, then it may be possible to improve Pd recoveries.

Cratonic lithospheric mantle is composed of predominantly refractory materials that formed at higher mantle potential temperatures ( T P) than recorded in non-cratonic peridotites. It also shows stronger depletion and fractionation of Pd and Pt from Ru, Os and Ir than oceanic, supra-subduction zone or off-cratonic lithospheric mantle, as well as some of the lowest Se and Te contents. The varied response of the highly siderophile elements (HSE: Os, Ir, Ru, Rh, Pt, Pd, Re, Au), and their embedded radioactive decay systems, to changes in oxygen fugacity ( f O2), sulfur fugacity ( f S2) and pressure ( P )—in particular through the impact of these parameters on the stability of the main HSE-bearing sulfide and alloy phases makes them potentially powerful tracers of their melting environment. Therefore, investigation of the HSE systematics of cratonic mantle peridotites, in combination with information from Re–Os isotopes on time-integrated enrichment or depletion, can help us to understand processes leading to mantle differentiation and continental lithosphere formation in the Archean, which are controversial subjects despite decades of research. The longevity of the cratonic lithosphere implies that there was ample opportunity for secondary overprint, obscuring our view of earlier processes. For example, destabilization of platinum-group element (PGE: Os, Ir, Ru, Rh, Pt, Pd) alloy leading to depletions in the compatible PGE, and perhaps Pt, in some cratonic mantle samples may occur in an oxidizing mantle wedge or through interaction with oxidizing small-volume, volatile-rich melts that typically invade cratonic roots. Such melts may eventually deposit S, Pd, Pt and Re and also capture remaining PGE alloys, consistent with the anomalous S-rich character of many kimberlite-borne xenoliths. Their basalt-borne counterparts show additional late effects of subaerial degassing that can deplete volatile elements (S, Re, Os). Basaltic melts can also scavenge PGE alloys at depth, while still sulfide-undersaturated. Such melts, may, …

A large data compilation has been assembled of platinum group element (PGE) analyses in mantle melts and mantle rocks, the latter including an assortment of xenoliths and obducted mantle massifs. The degree of correlation has been investigated among the PGEs and with other major element variables such as Al2O3, TiO2 and Mg number, and the results are considered in the context of the current paradigm for the behaviour of highly siderophile elements in the silicate Earth. Primitive mantle melts have a wide range of PGE contents. Komatiites have the highest abundances of all the PGEs, show the strongest correlations between Pt and Rh, Pt and Pd and between the iridium-group PGEs Ir, Ru and Os (IPGEs). Most basalts of all affinities have lower levels of Pt and Pd and much lower levels of Ir, Ru and Os than komatiites. Within the basalt grouping Rh has stronger affinities with the IPGEs. Picrites and Archaean basalts are intermediate between these two groups. MORBs and a small proportion of continental LIP basalts show strong depletions in all PGEs attributable to retention of sulfide in their mantle source rocks, or sulfide liquid fractionation on ascent. The degree of PGE depletion in other basalts is probably attributable to equilibration with sulfide, but is less than would be expected under conventional models of sulfide extraction, and is instead attributed to mixing of magmas generated at variable depths incorporating both sulfide-saturated and undersaturated components. Basalts with Pt and Pd contents higher than typical komatiites are rare, a notable example being B1-type parent magmas to the Bushveld Complex, which have komatiite-like relative PGE abundances and Pt, Pd and Rh abundances up to a factor of two higher than komatiites for comparable Ti contents. The mantle composition array as a whole is characterized by variable degrees of depletion of Pt, Pd and Rh in Al-poor, melt-depleted harzburgite/dunite lithologies; lack of depletion in these elements in Al-bearing lherzolites; and a lack of systematic variation in IPGEs across this range. Strongest correlations across the entire set are observed between Ir, Ru and Os; and between Pt and Rh. Melt-depleted cratonic mantle samples are notably more deficient in Pd than in Pt, but comparable Pd-enriched components are not represented in the available data from continental environments. The only group of mantle melts that systematically record high Pd/Pt ratios are MORBs; if these are indeed the complement of the depleted cratonic mantle suite then the melt depletion recorded by the cratonic mantle suite occurred at low pressure prior to tectonic underplating of the depleted lithosphere beneath the cratons. A filtered subset of orogenic peridotite compositions that are thought not to have been affected by significant extents of melt extraction or metasomatic refertilization have median concentrations of 3.9 ppb Os, 2.9 ppb Ir, 6.3 ppb Ru, 1.0 ppb Rh, 6.2 ppb Pt, 5.4 ppb Pd, and Cu/Pd ratio of 5500, which we consider to be representative of the modern convecting mantle. The convecting mantle has PGE proportions closely resembling those of lunar impact breccias, diverging considerably from chondritic proportions and attributable to the presence of a late veneer-derived, predominantly sulfide-hosted component. The compositions of mantle peridotites show considerable scatter attributable to the combined effects of measurement error and a strong covariance due to a heterogeneous distribution of sulfide in the small samples typically chosen for pulverization. The intensity of the covariance between all of the PGE due to sampling error gives a false impression of a genetic trend toward highly enriched PGE in some samples which could be mistaken for the effects of metasomatism; however no plausible metasomatic process would be expected to retain the tight interelement correlations shown.

The formation of platinum-group minerals (PGM) during magma differentiation has been suggested to be an important process in primitive magma evolution, but decisive textural evidence is difficult to obtain because PGM tend to be very small and very rare. We have investigated Cr-spinel phenocrysts from two oxidized magmas (Siberian meimechite and Vanuatu [Ambae Island] arc picrite) and one reduced magma (Uralian [Russia] ankaramite) for PGM inclusions and their platinum-group element (PGE) contents. We observed Os-Ir and Pt-Fe alloys entrapped as inclusions in Cr-spinel in all three suites of lava. The alloys may occur in association with PGE-bearing sulfides and co-trapped silicate melt. Cr-spinel crystals also contain measurable amounts of Os, Ir, Ru, and Rh, which are at concentrations 2×–100× higher than mantle values. Thermodynamic models indicate that the arc picrite and ankaramite melts were probably both saturated with the observed PGM phases, whereas the Os-Ir alloy grain observed in the meimechite is not in equilibrium with the "bulk" melt. Our results demonstrate that PGM (alloys and sulfides) occur as liquidus phases in primitive (unfractionated) melts at high temperature and at a variety of redox conditions, and that Cr-spinel is a significant host of PGE, either in the crystal structure or as PGM inclusions.

Fluid and melt inclusions trapped in igneous rocks below the platinum-group element (PGE)-rich J-M reef in the Stillwater Complex, Montana provide a physiochemical record of a continuum of high P-T magmatic-hydrothermal and low P-T metamorphic events. Magmatic-hydrothermal volatiles ranged from NaCl-dominated halide melts (>82 wt % NaClequiv) to more complex Na-Ca-K-Fe-Mn-Ba-Si-Al-Cl brines (28-79 wt % NaClequiv) that were trapped simultaneously with a moderate density carbonic fluid (CO2 ± CH4). Early primary inclusions containing immiscible brine and carbonic fluid were trapped in the granophyric albite-quartz core of a zoned pegmatite body in the Gabbronorite I unit at T of ∼ 700-715°C, and P between 4·3 and 5·6 kbar. The pegmatitic body crystallized from a fluid-saturated residual silicate liquid that was channeled through the cooling igneous stratigraphy. Approximately 500 m stratigraphically below the pegmatite, in the Ultramafic Series, early halide melt inclusions representing samples of formerly molten NaCl were trapped in unaltered primary olivine over a minimum range in temperature of 660-800°C. In the same olivine that hosts the halide melt inclusions, secondary brine inclusions with a composition similar to brines in the pegmatite were trapped over a minimum temperature range of 480-640°C. As hydrothermal activity continued during post-solidus cooling of the intrusion, quartz precipitation in the vuggy core of the pegmatite body trapped post-magmatic, immiscible brine and carbonic fluid inclusion assemblages that record a progressive decrease in fluid salinity, T and confining P from lithostatic to near-hydrostatic conditions. Late secondary inclusions containing regional metamorphic fluids were trapped in quartz in the pegmatite after cooling to zeolite-facies conditions. The late metamorphic fluids were low to moderate salinity, CaCl2-MgCl2-H2O solutions. Hydrous salt melts, magmatic brines, and non aqueous (carbonic) fluids may have coexisted and interacted throughout much of the late crystallization and post-magmatic history of the Stillwater Complex. Hence, the potential for interaction between exsolved magmatic volatiles and grain boundary-hosted sulfide minerals below the J-M reef at near-solidus temperatures, and the post-magmatic modification of the J-M reef PGE ore compositions by hydrothermal fluids are strongly indicated

The partitioning of platinum-group elements (PGE; Os, Ir, Ru, Rh, Pt, and Pd) and Au between sulfide melt and silicate melt (i.e., D PGE sul ) exerts a critical control on the PGE composition of the Earth’s crust and mantle, but previous estimates have been plagued by experimental uncertainties and vary through several orders of magnitude. Here we present direct experimental measurements of D PGE sul , based on in situ microanalysis of the sulfide and silicate melt, with values ranging from ∼4 × 105 (Ru) to ∼2–3 × 106 (Ir, Pt). Our measurements of D PGE sul are >100 times larger than previous results but smaller than anticipated based on comparison of alloy solubilities in sulfide melts and S-free silicate melts. The presence of S in the silicate melt greatly increases alloy solubility. We use our new set of partition coefficients to develop a fully constrained model of PGE behavior during melting which accurately predicts the abundances of PGE in mantle-derived magmas and their restites, including mid-ocean ridge basalts, continental picrites, and the parental magmas of the Bushveld Complex of South Africa. Our model constrains mid-ocean ridge basalt (MORB) to be the products of pooled low and high degree fractional melts. Within-plate picrites are pooled products of larger degrees of fractional melting in columnar melting regimes. A significant control on PGE fractionation in mantle-derived magmas is exerted by residual alloy or platinum group minerals in their source. At low pressures (e.g., MORB genesis) the mantle residual to partial melting retains primitive mantle inter-element ratios and abundances of PGE until sulfide has been completely dissolved but then evolves to extremely high Pt/Pd and low Pd/Ir because Pt and Ir alloys form in the restite. During melting at high pressure to form picrites or komatiites Ir alloy appears as a restite phase but Pt alloy is not stable due to the large effect of pressure on fS2, and of temperature on fO2 along an internal oxygen buffer, which causes large increases in alloy solubility. The magmas parental to the Bushveld Complex of South Africa appear, at least in part, to be partial melts of mantle that has previously been melted to the point of total sulfide exhaustion at low pressure, closely resembling mantle xenoliths of the Kaapvaal craton. Using the new extremely large D PGE sul the world-class Merensky Reef and UG2 Pt deposits of the Bushveld Complex can readily be modeled as the result of sulfide saturation due to mixing of magmas with unremarkable PGE contents, obviating the need to postulate anomalously PGE-rich parent magmas or hydrothermal inputs to the 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 t...

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 ( D AuMSS-sil) is about 100–200, whereas the partition coefficient of sulfide liquid/basalt ( D AuSuL-sil) is approximately 10 times larger at 2200. Although we find that temperature, pressure, and oxygen fugacity ( f O2) 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.

The migration of dense Fe-rich immiscible liquids through partially molten silicates is of critical importance to several issues including the formation of magmatic sulfide ore deposits and the formation of metallic cores in terrestrial planets. The migration of immiscible dense liquids can be considered to occur in three distinct regimes dictated by the relative sizes of the dense liquid droplets and the crystals making up the silicate crystal mush or partially melted silicate rock. If dense microdroplets are smaller than the diameter of the narrowest portions of pore throats between silicate crystals then downward motion is possible. The maximum rate of downward settling in loosely packed crystal mushes occurs when the droplet size is approximately one tenth the crystal size. As long as the silicate melt between crystals remains, microdroplets are capable of migrating distances of hundreds to thousands of meters vertically through crystal mushes contained in cooling dikes with typical grain sizes. Stranding of larger droplets similar in size to the crystals results from capillary forces preventing droplet deformation as they attempt to pass into pore throats narrower than themselves. Only in very coarse-grained mushes with grain sizes greater than about 2 cm can droplets the size of intergranular pores migrate downwards. On the other hand, coalescence of many microdroplets into pre-existing stranded droplets may generate connected net-textured domains of the dense liquid that are many times larger than the grain size of the mush. When the vertical height of the connected domain is great enough, the pressure gradient inside the dense phase exceeds the capillary force impeding downward motion through narrow pore throats and the immiscible phase is able to move down along vertically-oriented networks. These networks should not suffer stranding until they reach a solid layer or the base of the intrusion. We suggest that, in most cases, sulfide droplets formed by fractional segregation in large magma bodies should come to rest at the top of the crystal pile, whereas sulfides introduced to magmas by assimilation of fine-grained sulfidic sediments should be capable of passing downward through crystal mushes to form massive or net-textured accumulations at the bottom of the partially molten zone.

The Oligocene Yao’an syenite porphyry, associated with gold mineralisation, and the Machangqing alkali granite porphyry–monzonite porphyry, associated with Cu mineralisation, belong to the Red River–Jinshajiang alkaline igneous belt that formed in a continental setting in southwestern China. A study of the mineral chemistry of major silicate minerals in these two mineralised intrusions provides insights into their overall crystallisation conditions. The temperature and pressure conditions, derived from amphibole–plagioclase and perthite–plagioclase geothermometry and Al-in-amphibole barometry, suggest that the Yao’an intrusion crystallised at around 820 ± 50°C and 0.9–1.3 kbar, whereas the Machangqing intrusion crystallised at around 730 ± 50°C and 2.2–2.8 kbar. The higher temperature and lower pressure of crystallisation for the Yao’an intrusion relative to the Machangqing intrusion indicates that it was emplaced at a shallower crustal level. Based on biotite composition, the two intrusions formed under imposed oxygen fugacities above the Ni–NiO buffer (NNO), and the Yao’an intrusion crystallised under more oxidising conditions than the Machangqing intrusion. The results show that the intrusions associated with Cu–Au mineralisation in the Red River–Jinshajiang alkaline igneous belt were emplaced at a relatively high fO2, which, together with the weakly fractionated magma, favoured Au enrichment relative to Cu in the belt.

Chromite is widely recognized to act as a collector for platinum group elements (PGE), which tend to be observed as discrete grains of platinum group minerals included within magmatic chromite grains. In the course of experiments involving the re-equilibration or growth of chromite and Cr-spinel in molten silicate, we observe that platinum group minerals (PGM; including metal alloys and laurite) form at the mineral^melt interface. The formation of PGM to the extent observed requires a mechanism involving sustained transport of PGE from a source within the experiment to the site of deposition. We propose that the driving force for this process is a redox gradient developed in response to mineral growth or re-equilibration with the surrounding melt. The mechanism is local reduction within the mineral^melt interfacial region as a consequence of the selective uptake of trivalent Cr and Fe from the melt by spinel relative to the divalent species.We have modeled the transient perturbation of fO2 in a compositional boundary layer melt around spinel for both crystal growth and diffusive re-equilibration of mineral and melt.We find that metal solubilities decrease by several per cent in the silicate melt at the melt^crystal interface during crystal growth, providing the driving force for PGM formation. In magmas that are saturated with PGM, as a result of falling temperature and oxygen fugacity during spinel crystallization, nucleation of PGM will be impeded by interfacial tension everywhere except in the reduced boundary layer around spinel crystals. The resulting concentration and trapping of alloy particles in the growing chromite crystals can produce apparent bulk chromite/melt partition coefficients exceeding 20 even if there is no solid solution of PGE in the chromite.The introduction of spinel grains, initially equilibrated with a mafic magma, into a more primitive magma, with higher Cr/Al, would lead to disequilibrium between chromite and melt. The perturbation of fO2 in the compositional boundary layer surrounding a chromite xenocryst would exceed 0 1 log unit, leading to local reduction of alloy solubility of the order of 13^18%. A small number of spinel xenocrysts could serve as collection sites for all of the excess PGE in the magma, leading to the eventual observation that a few chromite crystals contain many PGM inclusions, whereas the rest of the chromite population may be relatively free of PGM.

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 world's PGE reserves are held in a handful of deposits, most of which occur within the unique Bushveld Complex of South Africa.

Layered intrusions represent part of the plumbing systems that deliver vast quantities of magma through the Earth's crust during the formation of large igneous provinces, which disrupt global ecosystems and host most of the Earth's endowment of Pt, Ni and Cr deposits. The Rustenburg Layered Suite of the enormous Bushveld Igneous Complex of South Africa has been presumed to have formed by deposition of crystals at the floor of a subterranean sea of magma several km deep and hundreds of km wide called a magma chamber. Here we show, using U–Pb isotopic dating of zircon and baddeleyite, that individual chromitite layers of the Rustenburg Layered Suite formed within a stack of discrete sheet-like intrusions emplaced and solidified as separate bodies beneath older layers. Our U–Pb ages and modelling necessitate reassessment of the genesis of layered intrusions and their ore deposits, and challenge even the venerable concept of the magma chamber itself., Large igneous intrusions layering is thought to represent an upward-aggrading crystal pile. However, Mungall et al. show that the Rustenburg Layered Suite of the Bushveld Complex, South Africa was created by the injection of a series of thin sheet-like intrusions that cooled and solidified as separate bodies.

I present an empirical parameterization of low-pressure melting relations of monosulfide solid solution in the system Ni–Cu–Fe–S–O and use it to argue that sulfide ores at Sudbury are almost exclusively cumulate in origin. In the model the solid is considered to be composed of four components NiS, CuS, FeS, and S, where S represents substitution of a vacancy for a cation. The liquid solution is considered to be a mixture of cations Ni, Fe, and Cu and anions S and O. The exchange of metals and sulfur between solid and melt is treated as a series of reactions of the form Ml + Sl = MSs, where subscripts l and s denote liquid and solid, respectively, allowing the definition of an exchange coefficient K D = X s MS / ( X l M × X l S ) where X denotes mole fraction. I have fitted equations of the form log KD = a/T + bXlS + c to the existing database for coexisting sulfide liquid–monosulfide solid solution for each of the liquid components Ni, Cu, and S. The fitted KD expressions have been implemented in a Matlab program to estimate the compositions of coexisting solid and liquid sulfide phases in the system Ni–Cu–Fe–S–O, using the liquidus temperature approximation of Fleet and Pan [Fleet M. E. and Pan Y. (1994) Fractional crystallization of anhydrous sulfide liquid in the system Fe–Ni–Cu–S, with application to magmatic sulfide deposits. Geochim. Cosmochim. Acta 58, 3369–3377], and using a crude approximation to the liquidus surface of magnetite. Ni is found to be incompatible with mss over most of the range of conditions of crystallization of natural sulfide magmas, becoming compatible only at the lowest temperatures and highest Ni and Cu contents attained. Comparison with compositions of sulfide ores from Sudbury demonstrates that many ore compositions are distributed along mixing lines between primary mss and intermediate solid solution (iss) or between high pentlandite (heazlewoodite solid solution; hzss) and iss. The mss–iss trend can be modeled as a mixing line between mss and residual sulfide liquid or between mss and iss cumulates. In the former case, the Ni-rich composition of the mss must reflect continuous equilibration of solids and liquids during cooling to low temperatures close to the sulfide solidus. In the latter case, a significant mass of highly Ni- and Cu-enriched residual sulfide liquid must be interpreted to have left the mss–iss cumulates behind during a late-stage migration process at temperatures well below the solidus temperature of the enclosing silicate rocks. Subsequent crystallization of hzss–iss cumulates from Ni- and Cu-rich residual sulfide liquids produced the second trend between the compositions of pentlandite and chalcopyrite. The balance of evidence favors the hypothesis that most sulfide ores represent cumulate mixtures of iss and mss or of iss and hzss rather than residual Cu-rich sulfide liquids.

The Proterozoic Expo Intrusive Suite comprises a series of mafic to ultramafic intrusions crosscutting the Povungnituk Group of the Cape Smith Fold Belt in New Quebec. The intrusions are mainly in the form of blade-shaped dikes that penetrate a sediment-rich horizon in the middle of the Beauparlant Formation and terminate downward against massive basalts of the lower Beauparlant Formation. Significant accumulations of magmatic sulfide occur at the basal terminations of the dikes. At stratigraphic levels above the Beauparlant Formation the intrusions appear as broad dikes or sills within the Nuvilik Formation, below the mineralized lava flows and subvolcanic intrusions of the Raglan Formation.The Expo Intrusive Suite and the mineralized bodies of the Raglan Formation are probably coeval and comagmatic with the overlying Chukotat Group. Post-emplacement folding has exposed the Expo Intrusive Suite over about 5 km of structural relief, revealing the basal sulfide concentrations where dike segments terminate on the flanks of anticlines. The parent magma as preserved in chilled margins and narrow dikes was a picrite containing � 17 wt % MgO (i.e. komatiitic basalt) and slightly depleted in Th, U and Nb relative to middle and heavy rare earth elements. The compositions of ultramafic cumulate rocks within the intrusions are strongly enriched inTh, U and Nb relative to heavy rare earth elements, reflecting assimilation of the enclosing basalts and metasediments. Modeling of the assimilation process suggests that the picritic magma was capable of assimilating masses of basalt or sediment up to 50% of the original mass of magma. Assimilation of � 10% of a mixture of basalt and sediment caused the magma to become sulfide-saturated, and was accompanied by the crystallization of masses of ultramafic cumulates approximately equal to the mass of rock assimilated. The presence of dikes whose chilled margins resemble uncontaminated primary magmas but that contain abundant cumulates recording wholesale assimilation of host-rocks indicates that the process of assimilation and fractional crystallization required to produce continental tholeiites from picritic parent magmas may not require the presence of long-lived magma chambers, but can occur during transport along dikes and reaction with wall-rocks.

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.