Fluids as primary carriers of sulphur and copper in magmatic assimilation

Magmas readily react with their wall-rocks forming metamorphic contact aureoles. Sulphur and possibly metal mobilization within these contact aureoles is essential in the formation of economic magmatic sulphide deposits. We performed heating and partial melting experiments on a black shale sample from the Paleoproterozoic Virginia Formation, which is the main source of sulphur for the world-class Cu-Ni sulphide deposits of the 1.1 Ga Duluth Complex, Minnesota. These experiments show that an autochthonous devolatilization fluid effectively mobilizes carbon, sulphur, and copper in the black shale within subsolidus conditions (≤ 700 °C). Further mobilization occurs when the black shale melts and droplets of Cu-rich sulphide melt and pyrrhotite form at ∼1000 °C. The sulphide droplets attach to bubbles of devolatilization fluid, which promotes buoyancy-driven transportation in silicate melt. Our study shows that devolatilization fluids can supply large proportions of sulphur and copper in mafic–ultramafic layered intrusion-hosted Cu-Ni sulphide deposits.

Naldrettite (Pd2Sb): A new find in Brazil and comparison with worldwide occurrences

ABSTRACT Naldrettite (Pd2Sb) is a PGM discovered in 2005 in Mesamax Northwest deposit, Ungava region, Quebec, Canada. Before and after its approval, PGM with the naldrettite type composition have been reported from a number of localities worldwide. Most frequently, naldrettite has been documented in magmatic Ni–Cu–PGE sulfide deposits, hydrothermal veins in porphyry coppers of the Cu–Au type, and PGE deposits of Alaskan-type zoned intrusions. Naldrettite has been occasionally found in metasomatic Sb–As sulfide ore, metamorphic Ni–oxide ore, and podiform chromitites, although these occurrences have not been fully constrained by solid chemical analyses or paragenetic reconstruction. In this paper we report the first discovery of naldrettite in Brazil. This new finding occurs in a chromitite sample collected in the Luanga Complex, a Neo-archaean layered intrusion in the Carajás Mineral Province. Paragenetic association with alteration assemblages (ferrianchromite, Fe-hydroxides, chlorite) suggests precipitation of naldrettite from metamorphic hydrothermal fluids. The average composition of the Luanga sample (Pd1.76Pt0.24)Σ2.00(Sb0.57As0.43)Σ1.00 shows major substitution of Pt and As. These elements were derived from the breakdown of primary sperrylite, and were incorporated in naldrettite deposited by percolating fluids, at temperature below 350 °C (maximum temperature registered by the crystallization of associated chlorite). An overview of documented occurrences indicates that naldrettite can form in a variety of igneous rocks (ultramafic, mafic, felsic), even involving minimal concentrations of Pd and Sb. Crystallization of naldrettite generally occurs in the post-magmatic stage due to the activity of hydrothermal fluids containing volatile species Sb, As, Bi, Te, and Pd due to its higher mobility compared with the other PGE. A major issue concerns the origin of fluids that can be: (1) “residual”, after the main crystallization of the host magma, (2) “metamorphic”, during regional metamorphism or serpentinization, and (3) “metasomatic”, emanating from an exotic magma intrusion. The combination of two or three of these factors is the most likely process observed in the naldrettite-bearing complexes.

Palladothallite, Pd3Tl, a new mineral from the Monchetundra layered intrusion, Kola Peninsula, Russia

ABSTRACT Palladothallite, Pd3Tl, is a new mineral discovered in the Monchetundra layered intrusion, Kola Peninsula, Russia. Palladothallite occurs in orthopyroxenite with disseminated Ni-Cu-Fe sulfides and in near-surface oxidized ore of an orthopyroxenite unit. In the holotype specimen, the new mineral forms anhedral grains about 1 to 20 μm in size intergrown with bortnikovite (Pt4Cu3Zn). Palladothallite and bortnikovite form a rim around tulameenite (Pt2FeCu), Pt-Pd-Fe-Cu alloys, and Pt-Pd-Fe-Cu “oxides” in a goethite matrix. In plane-polarized light, palladothallite is white, anisotropy was not observed; it exhibits no internal reflections. Reflectance values of palladothallite in air (R' in %) are: 53.9 at 470 nm, 57.1 at 546 nm, 59.4 at 589 nm and 61.7 at 650 nm. Twelve electron probe microanalyses of palladothallite gave an average composition (in wt.%): Pd 59.99, Cu 1.19, Fe 0.35, Ag 1.1, Tl 35.64, Se 0.34, and S 0.09, total 99.67, corresponding to the empirical formula (Pd2.894Cu0.096Fe0.032Ag0.053)∑3.075(Tl0.895Se0.023S0.008)∑0.926 based on four atoms, with the ideal formula Pd3Tl. The density, calculated on the basis of the empirical formula, is 13.04 g/cm3. Palladothallite crystallizes with the same structure as synthetic Pd3Tl, which was solved by Kurtzemann & Kohlmann (2010) from powder neutron diffraction data. Palladothallite is tetragonal, space group I4/mmm, with a 4.10659(9), c 15.3028(4) Å, V 258.07(1) Å3, and Z = 4. Palladothallite crystallizes in the ZrAl3 structure type. The name corresponds to its chemical composition, palladium and thallium.

Trace precious metals in major sulfide minerals from the Federova Tundra platinum group element deposit in the Fedorova-Pana layered intrusion, central Kola Peninsula, Russia

ABSTRACT Drill-core samples from the basal Cu-Ni-platinum-group element mineralization of the Early Proterozoic Fedorova Tundra intrusion in the Fedorova-Pana layered intrusion, central Kola Peninsula, Russia, were studied in two separate projects in Canada and Russia. In Canada, trace precious metal analyses by laser ablation inductively coupled mass spectrometry of 323 base metal sulfide particles [pentlandite (101), pyrrhotite (98), chalcopyrite (25), and pyrite (99)] show that Pd is highly concentrated in pentlandite. Most of the analyses (71%) were done using two master composite samples of comminuted drill core representative of the West Pit and East Pit mineralization, FWMC and FEMC, respectively. Fewer analyses were made of three other comminuted drill core samples from the West Pit referred to as “lithology” samples: OLFW (olivine-bearing rocks), ANFW (leucocratic rocks), and GNFW (gabbronorite). In Russia, 120 polished sections sliced from drill core from the West and East Pits and from four other Fedorova Tundra intrusion deposits (Kievey, Northern Kamennik, Eastern Chuarvy, and Southern Kievey) were studied mineralogically. Platinum group mineral characterization and trace Pd electron probe microanalyses of pentlandite were done using polished sections from all six locations (n = 95). The trace electron probe microanalysis data for Pd in pentlandite from the West (n = 35) and East (n = 19) Pit samples, though at much higher detection levels, are considered to be comparable to the laser ablation inductively coupled mass spectrometry data. The Eastern Chuarvy samples show particularly high Pd concentrations averaging 0.49 wt.% Pd (n = 11) and as high as 1.64 wt.% Pd. The combined data from these studies guides our estimate that pentlandite accounts for 30 to 50% of the Pd in these ores and that Rh solid solution in sulfides may account for >98% of the total Rh.

Sintering as a key process in the textural evolution of chromitite seams in layered mafic-ultramafic intrusions

ABSTRACT Nearly monomineralic stratiform chromitite seams of variable thickness (millimeters to meters) occur in many of the world's layered mafic-ultramafic intrusions. These seams are often associated with economically significant quantities of platinum group metals, yet the petrogenesis of these societally important materials remains enigmatic. Here we evaluate processes associated with late-magmatic (postcumulus) textural maturation of chromitite seams from four layered mafic-ultramafic intrusions of different ages and sizes. From largest to smallest, these intrusions are the ∼2060 Ma Bushveld Complex (South Africa), the ∼2710 Ma Stillwater Complex (USA), the ∼1270 Ma Muskox Intrusion (Canada), and the ∼60 Ma Rum Eastern Layered Intrusion (Scotland). Three endmember chromitite textures are described, based on chromite grain size and degree of textural equilibration: (1) coarse-grained chromite crystals (>0.40 mm) that occur in the central portions of seams and exhibit high degrees of solid-state textural equilibration; (2) fine-grained chromite crystals (0.11–0.44 mm) at the margins of seams in contact with and disseminated throughout host anorthosite or pyroxenite; and (3) fine-grained chromite crystals (0.005–0.28 mm) hosted within intra-seam orthopyroxene, clinopyroxene, and olivine oikocrysts. Crystal size distribution and spatial distribution pattern analyses are consistent with coarsening occurring through processes of textural maturation, including the sintering of grains by coalescence. We propose that textural maturation initially occurred in the supra-solidus state followed by an important stage of solid-state textural maturation and that these equilibration processes played a major role in the eventual microstructural and compositional homogeneity of the chromitite seams.

Chromite Mineralization in the Sopcheozero Deposit (Monchegorsk Layered Intrusion, Fennoscandian Shield)

In 1990, the Sopcheozero Cr deposit was discovered in the Monchegorsk Paleoproterozoic layered mafic-ultramafic layered intrusion (Monchepluton). This stratiform early-magmatic deposit occurs in the middle part of the Dunite Block, which is a member of the Monchepluton layered series. The Cr2O3 average-weighted content in ordinary and rich ores of the deposit is 16.65 and 38.76 wt.%, respectively, at gradually changing concentrations within the rich, ordinary and poor ore types and ore body in general. The ores of the Sopcheozero deposit, having a ratio of Cr2O3/FeOtotal = 0.9–1.7, can serve as raw materials for the refractory and chemical industries. The ore Cr-spinel (magnochromite and magnoalumochromite) is associated with highly magnesian olivine (96–98 Fo) rich in Ni (0.4–1.1 wt.%). It confirms a low S content in the melt and complies with the low oxygen fugacity. The coexisting Cr-spinel-olivine pairs crystallized at temperatures from 1258 to 1163 °C, with accessory Cr-spinel crystallizing at relatively low, while ore Cr-spinel at higher temperatures. The host rock and ore distinguish with widespread plastic deformations of olivine at the postcrystallization phase under conditions of high temperature (above 400 °C) and pressure (5 kbar). At the post magmatic Svecofennian stage (1.84 Ga), the deposit, jointly with the Monchepluton, was subject to diverse tectonic deformations.