Marathonite, Pd25Ge9, and palladogermanide, Pd2Ge, two new platinum-group minerals from the Marathon deposit, Coldwell Complex, Ontario, Canada: Descriptions, crystal-chemical considerations, and genetic implications

ABSTRACT Marathonite, Pd25Ge9, and palladogermanide, Pd2Ge, are two new platinum-group minerals discovered in the Marathon deposit, Coldwell Complex, Ontario, Canada. Marathonite is trigonal, space group P3, with a 7.391(1), c 10.477(2) Å, V 495.6(1) Å3, Z = 1. The six strongest lines of the X-ray powder-diffraction pattern [d in Å (I)(hkl)] are: 2.436(10)(014,104,120,210), 2.374(29)(023,203,121,211), 2.148(100)(114,030), 1.759(10)(025,205,131,311), 1.3605(13)(233,323,036,306), and 1.2395(14)(144,414,330). Associated minerals include: vysotskite, Au-Ag alloy, isoferroplatinum, Ge-bearing keithconnite, majakite, coldwellite, ferhodsite-series minerals (cuprorhodsite-ferhodsite), kotulskite and mertieite-II, the base-metal sulfides, chalcopyrite, bornite, millerite and Rh-bearing pentlandite, oberthürite and torryweiserite, and silicates including a clinoamphibole and a Fe-rich chlorite-group mineral. Rounded, elongated grains of marathonite are up to 33 × 48 μm. Marathonite is white, but pinkish brown compared to palladogermanide and bornite. No streak or microhardness could be measured. The mineral shows no discernible pleochroism, bireflectance, or anisotropy. The reflectance values (%) in air for the standard COM wavelengths are: 40.8 (470 nm), 44.1 (546 nm), 45.3 (589 nm), and 47.4 (650 nm). The calculated density is 10.933 g/cm3, determined using the empirical formula and the unit-cell parameters from the refined crystal structure. The average result (n = 19) using energy-dispersive spectrometry is: Si 0.11, S 0.39, Cu 2.32, Ge 18.46, Pd 77.83, Pt 1.10, total 100.22 wt.%, corresponding to the empirical formula (based on 34 apfu): (Pd23.82Cu1.19Pt0.18)Σ25.19(Ge8.28S0.40Si0.13)∑8.81 and the simplified formula is Pd25Ge9. The name is for the town of Marathon, Ontario, Canada, after which the Marathon deposit (Coldwell complex) is named. Results from electron backscattered diffraction show that palladogermanide is isostructural with synthetic Pd2Ge. Based on this, palladogermanide is considered to be hexagonal, space group , with a 6.712(1), c 3.408(1) Å, V 133.0(1), Z = 3. The seven strongest lines of the X-ray powder-diffraction pattern calculated for the synthetic analogue [d in Å (I)(hkl)] are: 2.392(100)(111), 2.211(58)(201), 2.197(43)(210), 1.937(34)(300), 1.846(16)(211), 1.7037(16)(002), and 1.2418(18)(321). Associated minerals are the same as for marathonite. Palladogermanide occurs as an angular, anhedral grain measuring 29 × 35 μm. It is white, but grayish-white when compared to marathonite, bornite, and chalcopyrite. Compared to zvyagintsevite, palladogermanide is a dull gray. No streak or microhardness could be measured. The mineral shows no discernible pleochroism, bireflectance, or anisotropy. The reflectance values (%) in air for the standard COM wavelengths for Ro and Ro' are: 46.8, 53.4 (470 nm), 49.5, 55.4 (546 nm), 50.1, 55.7 (589 nm), and 51.2, 56.5 (650 nm). The calculated density is 10.74 g/cm3, determined using the empirical formula and the unit-cell parameters from synthetic Pd2Ge. The average result (n = 14) using wavelength-dispersive spectrometry is: Si 0.04, Fe 0.14, Cu 0.06, Ge 25.21, Te 0.30, Pd 73.10, Pt 0.95, Pb 0.08, total 99.88 wt.%, corresponding (based on 3 apfu) to: (Pd1.97Pt0.01Fe0.01)Σ1.99(Ge1.00Te0.01)∑1.01 or ideally, Pd2Ge. The name is for its chemistry and relationship to palladosilicide. The crystal structure of marathonite was solved by single-crystal X-ray diffraction methods (R = 7.55, wR2 = 19.96 %). It is based on two basic modules, one ordered and one disordered, that alternate along [001]. The ordered module, ∼7.6 Å in thickness, is based on a simple Pd4Ge3 unit cross-linked by Pd atoms to form a six-membered trigonal ring that in turn gives rise to a layered module containing fully occupied Pd and Ge sites. This alternates along [001] with a highly disordered module, ∼3 Å in thickness, composed of a number of partially occupied Pd and Ge sites. The combination of sites in the ordered and disordered modules give the stoichiometric formula Pd25Ge9. The observed paragenetic sequence is: bornite → marathonite → palladogermanide. Phase equilibria studies in the Pd-Ge system show Pd25Ge9 (marathonite) to be stable over the range of 550–970 °C and that Pd2Ge (palladogermanide) is stable down to 200 °C. Both minerals are observed in an assemblage of clinoamphibole, a Fe-rich, chlorite-group mineral, and fragmented chalcopyrite, suggesting physical or chemical alteration, possibly both. Palladogermanide is also found associated with a magnetite of near end-member composition, potentially indicating a relative increase in fO2. Both minerals are considered to have developed at temperatures of 500–600 °C, under conditions of low fS2 and fO2, given the requirements needed to fractionate, concentrate, and form minerals with Ge-dominant chemistries.