Genesis of the Jinbaoshan PGE-(Cu)-(Ni) deposit: Distribution of chalcophile elements and platinum-group minerals

ABSTRACT The Jinbaoshan platinum group element-(Cu)-(Ni) deposit in southwest China is a sulfide-poor magmatic platinum-group element deposit that experienced multiple phases of post-magmatic modification. The sulfide assemblages of most magmatic Ni-Cu-platinum-group element deposits in China and elsewhere in the world are dominated by pentlandite-pyrrhotite-chalcopyrite with lesser magnetite and minor platinum-group minerals. However, Jinbaoshan is characterized by (1) hypogene violarite-pyrite 1-millerite-chalcopyrite and (2) supergene violarite-(polydymite)-pyrite 2-chalcopyrite assemblages. The platinum-group minerals are small (0.5–10 μm diameter) and include moncheite Pt(Te,Bi)2, mertieite-I Pd11(Sb,As)4, the atokite Pd3Sn – rustenburgite Pt3Sn solid solution, irarsite IrAsS, and sperrylite PtAs2 hosted mainly by violarite, silicates (primarily serpentine), and millerite. The platinum-group minerals occur in two sulfide assemblages: (1) mertieite-I-dominant (with irarsite, palladium, and Pd-alloy) in the hypogene assemblage and (2) moncheite-dominant (with irarsite, sperrylite, and atokite) in the supergene assemblage. Palladium and intermediate platinum-group elements (Os, Ir, Ru) are concentrated mainly in violarite, polydymite, and pyrite 2. Platinum is seldom hosted by base metal sulfides and occurs mainly as discrete platinum-group minerals, such as moncheite, sperrylite, and merenskyite. Violarite and polydymite in the Jinbaoshan deposit contain more Pb-Ag than pentlandite and pyrrhotite in the Great Dyke and Lac des Iles deposit. The formation of the sulfide assemblages in Jinbaoshan can be interpreted to have occurred in three stages: (1) a magmatic Fe-Ni-Cu sulfide melt crystallized Fe-Ni monosulfide and Cu-rich intermediate solid solutions, which inverted to a primary pyrrhotite-pentlandite-chalcopyrite-magnetite assemblage; (2) an early-secondary hypogene voilarite-millterite-pyrite 1-chalcopyrite assemblage formed by interaction with a lower-temperature magmatic-hydrothermal deuteric fluid; and (3) a late-secondary supergene violarite-polydymite-pyrite 2-chalcopyrite assemblage formed during weathering. Late-magmatic-hydrothermal fluids enriched the mineralization in Pb-Ag-Cd-Zn, which are incompatible in monosulfide solid solution, added Co-Pt into violarite, and expelled Pd to the margins of hypogene violarite and millerite, which caused Pd depletion in the hypogene violarite and the formation of mertieite-I. Supergene violarite inherited Pd and intermediate platinum-group elements from primary pentlandite. Thus, the unusual sulfide assemblages in the Jinbaoshan platinum-group element-(Cu)-(Ni) deposit results from multiple overprinted post-magmatic processes, but they did not significantly change the chalcophile element contents of the mineralization, which is interpreted to have formed at high magma:sulfide ratios (R factors) through interaction of crustally derived sulfide and a hybrid picritic-ferropicritic magma derived from subduction-metasomatized pyroxenitic mantle during impingement of the Emeishan plume on the Paleo-Tethyan oceanic subduction system.

PGE distribution in Merensky wide-reef facies of the Bushveld Complex, South Africa: Evidence for localized hydromagmatic control

ABSTRACT The wide-reef facies of the Merensky Reef in the eastern part of the western lobe of the Bushveld Complex was sampled in order to better resolve otherwise spatially constrained variation in highly siderophile elements across this geological unit. The platinum group element mineralogy and whole-rock highly siderophile element concentrations were measured across two vertical sections in close proximity. In one section, the Merensky Reef unit was bound by top and bottom platinum group elements-enriched horizons (reefs) with a well-developed pegmatoidal phase in the top third of the intrareef pyroxenite, but with neither a top nor a bottom chromitite present. The other drill core section featured a thin (<1 cm thick) chromitite layer associated with the highest platinum group element concentrations of any rock in this study as the bottom reef, but with a chromitite-absent top reef, and very poor development of the pegmatoid. Primitive mantle-normalized profiles of the main lithological units show relatively flat, primitive mantle-like highly siderophile element abundances (Cr, V, Co, Ni, platinum group elements, Au and Cu) in the Merensky pyroxenite, with modest depletion in Ir-affiliated platinum group elements. The platinum group element-rich top and bottom reefs, and the pegmatoidal upper pyroxenites, display characteristic enrichment in the Pt-affiliated platinum group elements and undepleted Ir-affiliated platinum group elements. The leuconoritic hanging wall and footwall rocks show comparable highly siderophile element profiles, distinguished from one another by relative depletion in the Pt-affiliated platinum group elements of the footwall samples. The vertical variation in highly siderophile element abundances through both sections is characterized by low platinum group element abundances through the lower reef pyroxenite, with platinum group element, Au, and Cu ± Ni concentrations increasing through the upper pegmatoidal pyroxenite, and main enrichment peaks at the top and bottom reefs. Significant localized (centimeter-scale) zones of chalcophile metal depletion are present immediately above the top reef and below the bottom reef. In addition, a wider zone of Pt-affiliated platinum group elements (with Pd more depleted than Pt)-depletion was identified within the pegmatoidal pyroxenite around one meter below the top reef. The platinum group element mineralogy of the bottom reef consists mainly of platinum group element sulfides, with minor arsenides and antimonides. In contrast, the platinum group element mineralogy of the top reef, and the small amount of data from the intrareef pyroxenite, mainly consist of Pt-affiliated platinum group elements-Bi-tellurides. The Pt-sulfides are mainly equant, relatively coarse crystals (many grains between 50 to 100 μm2 area), contrasting with the Pt-affiliated platinum group elements-Sb-As and -Bi-Te minerals that tend be high aspect-ratio grains, occurring in veinlets or as rims on earlier-forming platinum group element phases. These Te-As-Bi-Sb compounds are closely associated with chlorite, actinolite, quartz, and chalcopyrite, consistent with secondary deposition at lower temperatures and association with aqueous fluids. A model is proposed involving the emplacement of the Merensky unit as a magma pulse into at least semi-crystallized host rock, followed by aqueous fluid saturation and local migration, combined with concentration of late magmatic fluids around the top and bottom contacts of the magma pulse. Late remobilization of Pt-affiliated platinum group elements from the zones immediately (centimeter-scale) above the top reef, and from the underlying meter or two of pyroxenite, and from the centimeters underlying the bottom reef, have added additional platinum group elements to the reefs as late platinum group elements-Te-As-Bi-Sb minerals, independent of whether or not chromite is present in the reef initially.

Supergene mobilization and redistribution of platinum-group elements in the Merensky Reef, eastern Bushveld Complex, South Africa

ABSTRACT Near-surface supergene ores of the Merensky Reef in the Bushveld Complex, South Africa, contain economic grades of platinum-group elements, however, these are currently uneconomic due to low recovery rates. This is the first study that investigates the variation in platinum-group elements in pristine and supergene samples of the Merensky Reef from five drill cores from the eastern Bushveld. The samples from the Richmond and Twickenham farms show different degrees of weathering. The whole-rock platinum-group element distribution was studied by inductively coupled plasma-mass spectrometry and the platinum-group minerals were investigated by reflected-light microscopy, scanning electron microscopy, and electron microprobe analysis. In pristine (“fresh”) Merensky Reef samples, platinum-group elements occur mainly as discrete platinum-group minerals, such as platinum-group element-sulfides (cooperite–braggite) and laurite as well as subordinate platinum-group element-bismuthotellurides and platinum-group element-arsenides, and also in solid solution in sulfides (especially Pd in pentlandite). During weathering, Pd and S were removed, resulting in a platinum-group mineral mineralogy in the supergene Merensky Reef that mainly consists of relict platinum-group minerals, Pt-Fe alloys, and Pt-oxides/hydroxides. Additional proportions of platinum-group elements are hosted by Fe-hydroxides and secondary hydrosilicates (e.g., serpentine group minerals and chlorite). In supergene ores, only low recovery rates (ca. 40%) are achieved due to the polymodal and complex platinum-group element distribution. To achieve higher recovery rates for the platinum-group elements, hydrometallurgical or pyrometallurgical processing of the bulk ore would be required, which is not economically viable with existing technology.

The effects of post-cumulus alteration on the distribution of chalcophile elements in magmatic sulfide deposits and implications for the formation of low-S-high-PGE zones: The Luanga deposit, Carajás Mineral Province, Brazil

ABSTRACT Most of the World's platinum-group element ore deposits occur as thin stratiform layers within layered intrusions. These layers generally contain disseminated base-metal sulfides or chromite. However, cryptic platinum-group element deposits also occur without chromite or base-metal sulfides in what are known as low-S-high platinum-group element deposits. The origin of these deposits is not clearly understood. The Luanga Complex hosts the largest platinum-group elements resource in South America (i.e., 142 Mt at 1.24 ppm Pt + Pd + Au and 0.11% Ni) and hosts both a platinum-group element deposit containing disseminated base-metal sulfides (style 1) and a low-S-high platinum-group element deposit (style 2). It therefore offers the opportunity to compare the two deposit types in the same overall geological setting and consider how the low-S-high platinum-group element deposit could have formed. The first deposit style is termed the Sulfide zone and consists of a 10–50 meter-thick interval with disseminated base metal sulfides, whereas the second style is named low-S-high-Pt-Pd zone and consists of 2–10 meter-thick discontinuous lenses of 1–5 meter-thick sulfide- and oxide-free harzburgite and orthopyroxenite with discrete platinum-group minerals. Secondary assemblages commonly replace primary igneous minerals to a variable extent throughout the deposit, and thus allow for investigating the effects of post-cumulus alteration on the distribution of a wide range of chalcophile elements in a magmatic sulfide deposit at both whole-rock and mineral scale. This study presents the whole-rock distribution of S, platinum-group elements, and Te, As, Bi, Sb, and Se in both mineralization styles and the concentration of trace elements in base-metal sulfides from the Sulfide zone. The Sulfide zone has Pt/Pd ratios around 0.5 and high concentrations of Te, As, Bi, Sb, and Se, whereas the low-S-high-platinum-group element zone has Pt/Pd ratios greater than 1 and much lower Se, Te, and Bi concentrations, but comparable As and Sb contents. This is reflected in the platinum-group element assemblage, comprising bismuthotellurides in the Sulfide zone and mostly arsenides and antimonides in the low-S, high platinum-group elements zone. Moreover, the base-metal sulfides from the Sulfide zone have anomalously high As contents (50–500 ppm), which suggest that the sulfide liquid segregated from a very As-rich silicate magma, possibly illustrated by an average komatiitic basalt that assimilated a mixture of upper continental crust and black shales. We interpret the low-S-high platinum-group elements zone as a product of S loss from magmatic sulfides during post-cumulus alteration of the Luanga Complex. Selenium, Te, Bi, and Pd were also lost together with S, whereas As and Sb were expelled from base-metal sulfide structures and combined with platinum-group elements to form platinum-group minerals, suggesting they may play a role fixating platinum-group elements during alteration. The remobilization of chalcophile elements from magmatic sulfide deposits located in the Carajás Mineral Province may represent a potential source for hydrothermal deposits found in the region.

High grade ores of the Onverwacht platinum pipe, eastern Bushveld, South Africa

ABSTRACT The platiniferous dunite pipes are discordant orebodies in the Bushveld Complex. The Onverwacht pipe is a large body (>300 m in diameter) of magnesian dunite (Fo80–83) that crosscuts a sequence of cumulates in the Lower Critical Zone of the Bushveld Complex. In a pipe-in-pipe configuration, the main dunite pipe at Onverwacht hosts a carrot-shaped inner pipe of Fe-rich dunite pegmatite (Fo46–62) which comprises the platinum-bearing orebody. The latter was ca. 18 m in diameter and a mining depth of about 320 m was reached. In the present work, a variety of ore samples were studied by whole-rock geochemistry, including analyses of platinum group elements, ore microscopy, and electron probe microanalysis. Olivine of the ore zone displays considerable chemical variation (range 46–62 mol.% Fo) and may represent either a continuum, or different batches of magma, or vertical or horizontal zonation within the ore zone. Chromite is principally regarded to be a consanguineous component of the pipe magma that crystallized in situ and simultaneously with olivine. The Onverwacht mineralization is Pt-dominated (>95% of the platinum group elements) and the ore is virtually devoid of sulfides. Platinum-dominated platinum group minerals predominate, followed by Rh-, Pd-, and Ru-species. Pt-Fe alloys are most frequent, followed by Pt-Rh-Ru-arsenides and -sulfarsenides, platinum group element antimonides, and platinum group element sulfides. Our hypothesis on the genesis of the Onverwacht pipe and its mineralization is as follows: After near-consolidation of the layered series of the Critical Zone, the magnesian dunite pipe of Onverwacht was formed by upward penetration of magmas that replaced the existing cumulates initially by infiltration, followed by the development of a central channel where large volumes of magma flowed through. Fractional crystallization of olivine within the deeper magma chamber and/or during ascent of the melt resulted in the formation of a consanguineous, residual, more iron-rich melt. This melt also contained highly mobile, supercritical, water-bearing fluids and was continuously enriched in platinum group elements and other incompatible elements. In several closing pulses, the platinum group element-enriched residual melts crystallized and sealed the inner ore pipe. Crystallization of the melt resulted in the coeval formation of Fe-rich olivine, chromite, and platinum group minerals. The non-sulfide platinum group element mineralization was introduced in the form of nanoparticles and small droplets of platinum group minerals, which coagulated to form larger grains during evolution of the mineralizing system. The suspended platinum group minerals acted as collectors of other platinum group elements and incompatible elements during generation and ascent of the melt. With decreasing temperature, the platinum group mineral grains annealed and recrystallized, leading to the formation of composite platinum group mineral grains, complex intergrowths, or lamellar exsolution bodies. On further cooling, platinum group minerals overgrowing Pt-Fe alloys formed by reaction of leached elements and ligands like Sb, As, and S mobilized by supercritical magmatic/hydrothermal fluids. Redistribution of platinum group elements/platinum group minerals apparently only occurred on the scale of millimeters to centimeters. Finally, surface weathering led to the local formation of platinum group element oxides/hydroxides by oxidation of reactive precursor platinum group minerals.

Genesis and mechanisms of metal enrichment in the Baimazhai Ni-Cu-(PGE) deposit, Ailaoshan Orogenic Belt, SW China

ABSTRACT The ∼259 Ma Baimazhai Ni-Cu-(platinum-group element) deposit is located in the Ailaoshan-Red River fault zone on the southwest margin of the Yangtze Plate in the Jinping area of southeastern Yunnan Province. The intrusion is lenticular (∼530 m long × 190 m wide × 24–64 m thick) and concentrically zoned (margin to core) from gabbro through pyroxenite to peridotite. It contains ∼50 kt of Ni-Cu-(platinum-group element) mineralization, concentrically zoned (margin to core) from disseminated through net-textured to massive sulfides with an average grade of 1.03 wt.% Ni, 0.81 wt.% Cu, and 0.02∼0.69 ppm Pd+Pt. The sulfide assemblage comprises pyrrhotite, chalcopyrite, and pentlandite, with lesser magnetite, violarite, galena, and cobaltite. The mineralization is enriched in Ni-Cu-Co relative to the platinum-group elements and the host rocks are enriched in highly incompatible lithophile elements relative to moderately incompatible lithophile elements with high Th/Yb and intermediate Nb/Yb ratios. These host rocks, and those at most other Ni-Cu-platinum-group element deposits in the Emeishan Large Igneous Province, have high γOs and intermediate εNd values, indicating that they crystallized from a magma derived from a subduction-modified pyroxenite mantle source and modified by crustal contamination. The initial concentrations of metals in the primary magma are estimated to have been on the order of 200 ppm Ni and 100 ppm Cu, but only 0.4 ppb Pd, 0.2 ppb Pt, 0.005 ppb Rh, 0.02 ppb Ru, and 0.01 ppb Ir. The δ34S values of ores and separated sulfides range from 5.8‰ to 8.6‰, between the ∼10‰ value of sulfides in the metasedimentary country rocks and the 0 ± 0.5‰ value expected for magmas derived from MORB-type mantle, or the –2.5 ± 0.3‰ value expected for subduction-modified mantle, consistent with equilibration at magma:sulfide mass ratios (R factors) of 100–1000. Variations in Ir100 and Pd100 (metals in 100% sulfide) are consistent with 40–60% fractional crystallization of monosulfide solid solution to form Ni-Co-intermediate platinum-group element (Ru, Os, Ir)-rich massive ores and Cu-palladium/platinum-group elements (Pt, Pd, Rh)-Au-rich residual sulfide liquids. This process is also recorded by magnetite: Type I (early magmatic), type II (late magmatic), and type III (secondary) magnetites exhibit progressively lower Cr-Ti-V concentrations. The platinum-group element contents in base-metal minerals are low, and only pentlandite, violarite, and cobaltite contain detectable concentrations of Pd, Rh, and Ru. There is abundant textural evidence for metamorphic-hydrothermal alteration of sulfides in the Baimazhai intrusion, with secondary violarite, chalcopyrite, and pentlandite being enriched (Ag, Sb, Au, Pb) or depleted (Sn) in more mobile chalcophile elements. The different tectonic and petrogenetic settings of the Baimazhai and other deposits in China highlight the potential of Ni-Cu-platinum-group element deposits to occur in subduction or post-subduction settings and demonstrate that the key controls are magma flux and access to crustal S. Exploration potential remains for the Ailaoshan orogenic belt to host additional magmatic Ni-Cu deposits.