Magmatic systems play a crucial role in enriching the crust with volatiles and elements that reside primarily within the Earth's mantle, including economically important metals like nickel, copper ...and platinum-group elements. However, transport of these metals within silicate magmas primarily occurs within dense sulfide liquids, which tend to coalesce, settle and not be efficiently transported in ascending magmas. Here we show textural observations, backed up with carbon and oxygen isotope data, which indicate an intimate association between mantle-derived carbonates and sulfides in some mafic-ultramafic magmatic systems emplaced at the base of the continental crust. We propose that carbon, as a buoyant supercritical CO
fluid, might be a covert agent aiding and promoting the physical transport of sulfides across the mantle-crust transition. This may be a common but cryptic mechanism that facilitates cycling of volatiles and metals from the mantle to the lower-to-mid continental crust, which leaves little footprint behind by the time magmas reach the Earth's surface.
Magmatic arcs are terrestrial environments where lithospheric cycling and recycling of metals and volatiles is enhanced. However, the first-order mechanism permitting the episodic fluxing of these ...elements from the mantle through to the outer Earth's spheres has been elusive. To address this knowledge gap, we focus on the textural and minero-chemical characteristics of metal-rich magmatic sulfides hosted in amphibole-olivine-pyroxene cumulates in the lowermost crust. We show that in cumulates that were subject to increasing temperature due to prolonged mafic magmatism, which only occurs episodically during the complex evolution of any magmatic arc, Cu-Au-rich sulfide can exist as liquid while Ni-Fe rich sulfide occurs as a solid phase. This scenario occurs within a 'Goldilocks' temperature zone at ~1100-1200 °C, typical of the base of the crust in arcs, which permits episodic fractionation and mobilisation of Cu-Au-rich sulfide liquid into permeable melt networks that may ascend through the lithosphere providing metals for porphyry and epithermal ore deposits.
Ore deposits are loci on Earth where energy and mass flux are greatly enhanced and focussed, acting as magnifying lenses into metal transport, fractionation and concentration mechanisms through the ...lithosphere. Here we show that the metallogenic architecture of the lithosphere is illuminated by the geochemical signatures of metasomatised mantle rocks and post-subduction magmatic-hydrothermal mineral systems. Our data reveal that anomalously gold and tellurium rich magmatic sulfides in mantle-derived magmas emplaced in the lower crust share a common metallogenic signature with upper crustal porphyry-epithermal ore systems. We propose that a trans-lithospheric continuum exists whereby post-subduction magmas transporting metal-rich sulfide cargoes play a fundamental role in fluxing metals into the crust from metasomatised lithospheric mantle. Therefore, ore deposits are not merely associated with isolated zones where serendipitous happenstance has produced mineralisation. Rather, they are depositional points along the mantle-to-upper crust pathway of magmas and hydrothermal fluids, synthesising the concentrated metallogenic budget available.
Display omitted
•Hydrothermal alteration of magmatic pyrrhotite-pentlandite-chalcopyrite quantified.•Alteration to pyrite-millerite-chalcopyrite involves large mass losses up to 90%.•Fe, S lost to ...fluid first, then Ni, Cu and Pd all mobilised.•Fluids produced may be a source of metals for enigmatic hydrothermal Ni, PGE deposits.•Implicationd for sulfide transformation and metal transfer in ore systems.
Magmatic Ni-Cu-PGE sulfide assemblages are almost ubiquitously comprised of pyrrhotite-pentlandite-chalcopyrite(-pyrite). Sulfide alteration is common during syn- or post-magmatic fluid interaction, usually replacing sulfides with amphiboles or serpentine. However, some are altered to a low temperature (<200°C) hydrothermal assemblage of pyrite-millerite-chalcopyrite (PMC). An example is the Ni-Cu-PGE mineralisation in the Grasvally-Norite-Pyroxenite-Anorthosite (GNPA) Member, northern Bushveld Complex, which displays a continuum of mineralogical styles formed through progressive alteration: Style 1 primary pyrrhotite-pentlandite-chalcopyrite; which is altered to Style 2 pyrrhotite-pyrite-pentlandite-chalcopyrite; Style 3 pyrite-pentlandite-chalcopyrite; Style 4 pyrite-pentlandite-millerite-chalcopyrite; and Style 5 pyrite-millerite-chalcopyrite-cubanite. Modelling using CHILLER confirms this mineralogical sequence is thermodynamically possible at ∼200°C. Quantitative characterisation using automated Energy-Dispersive X-ray spectroscopy mapping alongside in situ laser ablation analyses determined mineral proportions, major and trace element concentrations and deportments in each style. The early loss of pyrrhotite removes over half of the bulk Fe and S during the initial stages of PMC alteration, increasing Cu, Ni and PGE tenors of the remaining sulfides significantly. As water–rock interaction progresses, pyrrhotite is replaced by pyrite and pentlandite by millerite, with concurrent losses in Fe, S and Ni. Copper is lost throughout the alteration, and is most pronounced in the more advanced stages. The fluids responsible were most likely acidic and oxidised, with metals mobilised as chloride complexes. Using Rh as an immobile normalising element, the overall mass loss in the most altered samples is calculated to be up to 90%, consistent with textural relationships that indicate 40–90% volume loss from Styles 2–5, with sulfides replaced by secondary silicates, including phlogopite, quartz, chlorite, pyroxenes and minor amphiboles. Magnetite is not a significant alteration product and thus Fe is mobilised, or incorporated into silicates. Most trace elements present in the magmatic sulfide (the IPGE, Rh and Bi) remain in the sulfide phases, and are effectively transferred to pyrite during PMC alteration, except Pd, which remains in pentlandite, and is liberated from the sulfide assemblage when pentlandite disappears. Selenium tenors increase slightly with alteration, demonstrating that alteration decreases S/Se ratios. The significant mobilisation of Ni, Cu and Pd during PMC alteration produces fluids enriched in these elements that may represent a metal source for a number of enigmatic hydrothermal Ni deposits such as Avebury, Enterprise and Talvivaara, whose metal sources remain speculative. The PMC alteration of the GNPA Member may be specifically a source for the nearby Waterberg hydrothermal Pt deposit. Furthermore, this study has implications not only for magmatic ore deposits, but also for the general implications of sulfide transformation and metal transfer in ore systems in general.
Magmatic Ni-Cu-PGE sulfide mineralisation is mostly confined to tholeiitic to komatiitic mafic-ultramafic intrusions, yet there have been an increasing number of occurrences recorded in ...alkaline-ultramafic, post-collisional magmatic systems, particularly in the lower and middle crust that generally display a characteristic Cu-Au-Te enrichment over more conventional Ni-Cu(-PGE) mineralisation. The Mordor Alkaline Igneous Complex, Australia, is a mid-crustal, zoned alkaline complex comprised of a syenite body with an alkaline mafic-ultramafic subcomplex containing dunites, wehrlites and shonkinites. Sulfide mineralisation is present either in thin, PGE-enriched stratiform ‘reefs’ within layered ultramafics in the centre of the subcomplex, or in thicker zones of Cu(-Au-PGE-Te) sulfide hosted by phlogopite-rich shonkinites towards the intrusion margins. This latter style comprises blebs of pyrite, chalcopyrite and minor millerite and PGE tellurides formed from the cooling of a Cu-dominant sulfide liquid. Primary igneous calcite is present in intimate association with the sulfide. We note that the circular nature of the complex, with a dunite core and shonkinite rim with chalcophile element mineralisation, is comparable to the pipe-like, intracratonic, alkaline-ultramafic Aldan Shield intrusions in Russia. As such, Mordor may have an intracratonic rather than post-collisional affinity. Nevertheless, sulfide mineralisation is typical of other alkaline-hosted occurrences, with a Cu-Au-Te-rich signature, low Ni contents and textural association with calcite, supporting models of chalcophile metal and S fluxing alongside carbonate in alkaline systems derived from low degrees of partial melting of hydrous and carbonated mantle sources. Mordor illustrates that alkaline igneous rocks are prospective for magmatic Cu-Au-PGE-Ni sulfide mineralisation, and the classic ‘marginal base metal– and sulfide-rich’ and ‘stratiform PGE-rich and sulfide-poor’ mineralisation styles may both be found in such intrusions.
The Platinova Reef, in the Skaergaard Intrusion, east Greenland, is an example of a magmatic Cu–PGE–Au sulfide deposit formed in the latter stages of magmatic differentiation. As is characteristic ...with such deposits, it contains a low volume of sulfide, displays peak metal offsets and is Cu rich but Ni poor. However, even for such deposits, the Platinova Reef contains extremely low volumes of sulfide and the highest Pd and Au tenor sulfides of any magmatic ore deposit. Here, we present the first LA-ICP-MS analyses of sulfide microdroplets from the Platinova Reef, which show that they have the highest Se concentrations (up to 1200 ppm) and lowest S/Se ratios (190–700) of any known magmatic sulfide deposit and have significant Te enrichment. In addition, where sulfide volume increases, there is a change from high Pd-tenor microdroplets trapped in situ to larger, low tenor sulfides. The transition between these two sulfide regimes is marked by sharp peaks in Au, and then Te concentration, followed by a wider peak in Se, which gradually decreases with height. Mineralogical evidence implies that there is no significant post-magmatic hydrothermal S loss and that the metal profiles are essentially a function of magmatic processes. We propose that to generate these extreme precious and semimetal contents, the sulfides must have formed from an anomalously metal-rich package of magma, possibly formed via the dissolution of a previously PGE-enriched sulfide. Other processes such as kinetic diffusion may have also occurred alongside this to produce the ultra-high tenors. The characteristic metal offset pattern observed is largely controlled by partitioning effects, producing offset peaks in the order Pt+Pd>Au>Te>Se>Cu that are entirely consistent with published D values. This study confirms that extreme enrichment in sulfide droplets can occur in closed-system layered intrusions in situ, but this will characteristically form ore deposits that are so low in sulfide that they do not conform to conventional deposit models for Cu–Ni–PGE sulfides which require very high R factors, and settling of sulfide liquids.
Display omitted
•Gold and many sulphides and tellurides dissolved by oxidation in DES ionic liquids.•An optical profiler allowed rapid measurement of leach rates.•Oxidation rates at low temperature ...were favourable for an industrial process.•Pyrite and ditellurides were insoluble by oxidation at the same conditions.•Electrolysis of ditelluride occured, suggesting ways to separate gold from pyrite.
The processing of ore by hydrometallurgy or pyrometallurgy typically has a high energy demand, and associated release of carbon dioxide. Thus there is a need to develop more energy-efficient and environmentally-compatible processes. This article demonstrates that deep eutectic solvent (DES) ionic liquids provide one such method since they can be used to selectively dissolve and recover native gold and tellurium, sulphides and tellurides.
Ionic liquids are anhydrous salts that are liquid at low temperature. They are powerful solvents and electrolytes with potential for high selectivity in both dissolution and recovery. Deep eutectic solvents are a form of ionic liquid that are mixtures of salts such as choline chloride with hydrogen-bond donors such as urea. DESs are environmentally benign, yet chemically stable and, furthermore, the components are already produced in large quantities at comparable costs to conventional reagents.
Electrum, galena and chalcopyrite, as well as tellurobismuthite (Bi2Te3), were soluble in DES through an oxidative leach at 45–50°C. Leaching rates determined by a novel technique employing an optical profiler were very favourable in comparison to the current industrial process of cyanidation. Pyrite was notably insoluble by an oxidative leach. However, pyrite, and indeed any other sulphide, could be selectively dissolved by electrolysis in a DES, thus suggesting a protocol whereby target inclusions could be liberated by electrolysis and then dissolved by subsequent oxidation.
Ionometallurgy could thus offer a new set of environmentally-benign process for metallurgy.
Magmatic Ni–sulfide ore deposits are generally associated with basaltic to komatiitic igneous rocks that originate by partial melting of the mantle, which is usually modelled as a uniform four-phase ...peridotite. Existing models accept that the key metal contributors to mantle melts are olivine (Ni) and sulfide (Cu, platinum group elements (PGEs) and minor Ni). However, melting in the mantle commonly begins in volumetrically minor mantle assemblages such as hydrous pyroxenites that occur as veins in the peridotite mantle, which are rich in the hydrous minerals phlogopite, amphibole and apatite. The contribution of hydrous pyroxenites to the metal endowment of mantle melts may have been underestimated or overlooked in the past, partly because evidence of their input is partially erased as melting intensifies to involve peridotite.
Here, we compile new results from experiments and natural rocks which demonstrate that the hydrous minerals such as phlogopite, amphiboles and apatite all have high partition coefficients for Ni (3–20) and may be important repositories for Ni in mantle sources of igneous rocks. This implies that hydrous minerals hosted in metasomatic mantle lithologies such as hydrous pyroxenites may be important contributors to some magmatic Ni–sulfide ore systems. Hydrous pyroxenites contain hydrous minerals in large modal abundances up to 30–40 vol% in addition to clinopyroxene and a few vol% of oxide phases, such as rutile and ilmenite. These mantle lithologies are commonly associated with cratonic and continental regions, where low-temperature, low-degree volatile-rich melts commonly modify lithospheric peridotite mantle, depositing variable hydrous pyroxenites.
The lower melting temperatures of hydrous minerals in hydrous pyroxenite lithologies also means that the generation of magmatic ore deposits may not require a major thermal perturbation such as a plume, as the melting temperatures of hydrous pyroxenites lie around 300–350 °C lower than dry peridotites. Partial melts of hydrous pyroxenite are more voluminous at low temperatures than melts of peridotite would be. Furthermore, it is argued in the following that they would contain similar or even higher concentrations of Ni. Thus, predictive exploration models should consider domains of the lithospheric mantle where hydrous pyroxenites may be localised and concentrated, as they may have been episodically melted throughout the long-lived geological evolution of cratonic blocks, yielding Ni-rich melts that may be hosted in conduits of varying size and geometry at various crustal levels.
Display omitted
•Chemistry of Te and Se in pyrite as an indicator for key ore-forming processes.•Solubility limit for Te as a function of As in pyrite, similar to that for Au.•Mobilisation and ...transport of Te in high pH fluids, precipitation controlled by fO2.•Se in pyrite varies due to changes in fluid temperature, irrespective of pH and fO2.•Economic potential of Te and Se in pyrite from Carlin-type and epithermal deposits.
Pyrite is one of the most common minerals in many precious and base metal hydrothermal ore deposits and is an important host to a range of trace elements including Au and Co and the semi-metals As, Se, Sb, Te and Bi. As such, in many hydrothermal ore deposits, where pyrite is the dominant sulphide phase, it can represent a major repository for these elements. Furthermore, the concentrations and ratios of Au, As and Co in pyrite have been used to infer key ore-forming processes. However, the mechanisms controlling the distribution of Te and Se in pyrite are less well understood. Here we compare the Te and Se contents of pyrite from a global dataset of Carlin-type, orogenic Au, and porphyry-epithermal deposits to investigate: (1) the potential of pyrite to be a major repository for these elements; and (2) whether Te and Se provide insights into key ore-forming processes. Pyrite from Carlin-type, low-sulphidation and alkaline igneous rock-hosted epithermal systems is enriched in Te (and Se) compared to pyrite from high-sulphidation epithermal and porphyry Cu deposits. Orogenic Au pyrite is characterised by intermediate Te and Se contents. There is an upper solubility limit for Te as a function of As in pyrite, similar to that established for Au by Reich et al. (2005); and this can be used to identify Te present as telluride inclusions, which are common in some epithermal-porphyry and orogenic Au deposits. Physicochemical fluid parameters, such as pH, redox and temperature, as well as crystal-chemistry control the incorporation and concentration of Se and Te in pyrite. Neutral to alkaline fluids have the ability to effectively mobilise and transport Te. Fluid boiling in porphyry-epithermal systems, as well as wall rock sulphidation and oxidation in Carlin-type (and orogenic Au) deposits can effectively precipitate Te in association with pyrite and Au. In contrast, Se concentrations in pyrite apparently vary systematically in response to changes in fluid temperature, irrespective of pH and fO2. Hence, we propose that the Se contents of pyrite may be used asa new geo-thermometer for hydrothermal ore deposits. Furthermore, the comparison of bulk ore and pyrite chemistry indicates that pyrite represents the major host for Te and Se in Carlin-type and some epithermal systems, and thus pyrite can be considered to be of economic interest asa potential source for these elements.
PDF
