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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.

Oberthürite, Rh3(Ni,Fe)32S32, and torryweiserite, Rh5Ni10S16, are two new platinum-group minerals discovered in a heavy-mineral concentrate from the Marathon deposit, Coldwell Complex, Ontario, Canada. Oberthürite is cubic, space group , with a 10.066(5) Å, V 1019.9(1) Å3, Z = 1. The six strongest lines of the X-ray powder-diffraction pattern [d in Å (I)(hkl)] are: 3.06(100)(311), 2.929(18)(222), 1.9518(39)(115,333), 1.7921(74)(440), 1.3184(15)(137,355) and 1.0312(30)(448). Associated minerals include: vysotskite, Au-Ag alloy, isoferroplatinum, Ge-bearing keithconnite, majakite, coldwellite, ferhodsite-series minerals (cuprorhodsite–ferhodsite), kotulskite, and mertieite-II, and the base-metal sulfides, chalcopyrite, bornite, millerite, and Rh-bearing pentlandite. Grains of oberthürite are up to 100 × 100 μm and the mineral commonly develops in larger composites with coldwellite, isoferroplatinum, zvyagintsevite, Rh-bearing pentlandite, and torryweiserite. The mineral is creamy brown compared to coldwellite and bornite, white when compared to torryweiserite, and gray when compared chalcopyrite and millerite. 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: 36.2 (470 nm), 39.1 (546 nm), 40.5 (589 nm), and 42.3 (650 nm). The calculated density is 5.195 g/cm3, determined using the empirical formula and the unit-cell parameter from the refined crystal structure. The average result (n = 11) using energy-dispersive spectrometry is: Rh 10.22, Ni 38.83, Fe 16.54, Co 4.12, Cu 0.23 S 32.36, total 100.30 wt.%, which corresponds to (Rh2Ni0.67Fe0.33)Σ3.00(Ni19.30Fe9.09Co2.22Rh1.16Cu0.12)∑31.89S32.11, based on 67 apfu and crystallochemical considerations, or ideally, Rh3Ni32S32. The name is for Dr. Thomas Oberthür, a well-known researcher on alluvial platinum-group minerals, notably those found in deposits related to the Great Dyke (Zimbabwe) and the Bushveld complex (Republic of South Africa).Torryweiserite is rhombohedral, space group , with a 7.060(1), c 34.271(7) Å, V 1479.3(1), Z = 3. The six strongest lines of the X-ray powder-diffraction pattern [d in Å (I)(hkl)] are: 3.080(33)(021), 3.029(58)(116,0110), 1.9329(30)(036,1115,1210), 1.7797(100)(220,0216), 1.2512(49)(0416), and 1.0226(35)(060,2416,0232). Associated minerals are the same as for oberthürite. The mineral is slightly bluish compared to oberthürite, gray when compared to chalcopyrite, zvyagintsevite, and keithconnite, and pale creamy brown when compared to bornite and coldwellite. 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: 34.7 (470 nm), 34.4 (546 nm), 33.8 (589 nm), and 33.8 (650 nm). The calculated density is 5.555 g/cm3, determined using the empirical formula and the unit-cell parameters from the refined crystal structure. The average result (n = 10) using wavelength-dispersive spectrometry is: Rh 28.02, Pt 2.56, Ir 1.98, Ru 0.10, Os 0.10, Ni 17.09, Fe 9.76, Cu 7.38, Co 1.77 S 30.97, total 99.73 wt.%, which corresponds to (Rh4.50Pt0.22Ir0.17Ni0.08Ru0.02Os0.01)∑5.00(Ni4.73Fe2.89Cu1.92Co0.50)Σ10.04S15.96, based on 31 apfu and crystallochemical considerations, or ideally Rh5Ni10S16. The name is for Dr. Thorolf (‘Torry') W. Weiser, a well-known researcher on platinum-group minerals, notably those found in deposits related to the Great Dyke (Zimbabwe) and the Bushveld complex (Republic of South Africa).Both minerals have crystal structures similar to those of pentlandite and related minerals: oberthürite has two metal sites that are split relative to that in pentlandite, and torryweiserite has a layered structure, comparable, but distinct, to that developed along [111] in pentlandite. Oberthürite and torryweiserite are thought to develop at ∼ 500 °C under conditions of moderate fS2, through ordering of Rh-Ni-S nanoparticles in precursor Rh-bearing pentlandite during cooling. The paragenetic sequence of the associated Rh-bearing minerals is: Rh-bearing pentlandite → oberthürite → torryweiserite → ferhodsite-series minerals, reflecting a relative increase in Rh concentration with time. The final step, involving the formation of rhodsite-series minerals, was driven via by the oxidation of Fe2+ → Fe3+ and subsequent preferential removal of Fe3+, similar to the process involved in the conversion of pentlandite to violarite. Summary comments are made on the occurrence and distribution of Rh, minerals known to have Rh-dominant chemistries, the potential existence of both Rh3+ and Rh2+, and the crystallochemical factors influencing accommodation of Rh in minerals.

The Geordie Lake Cu-Pd deposit is associated with troctolite at the base of the Geordie Lake intrusion, located near the center of the Coldwell Complex (1106.5 + 1.2 Ma). It is the only platinum group element deposit in the Midcontinent Rift associated with alkaline rocks. This study focuses on the long-standing questions regarding genetic relationships among the Geordie Lake gabbros, the Wolfcamp basalt, and the various syenites that make up the east-central portion of the Coldwell Complex. Primitive mantle-normalized trace-element patterns for the Geordie Lake intrusion are nearly flat from Th to Ce and show negative Sr, Eu, and Zr anomalies. Characteristic ratios for the Geordie Lake gabbro and troctolite include Th/Nb (0.12), La/Nb (1.1), La/Lu (150), La/Sm (6.9), Zr/Sm (18), and Gd/Yb (2.8). Trace-element patterns that are useful for determining petrogenesis for gabbros are similar to the Wolfcamp basalt and augite syenite with some key exceptions, notably the middle rare earth element and Zr abundances. Affects due to metasomatism or crustal contamination in Wolfcamp basalt and Geordie Lake gabbros and syenites are negligible. Results of Rayleigh fractionation modeling show (1) the Geordie Lake intrusion and Wolfcamp basalt are very similar but not directly related by crystallization, (2) the gabbros and basalt are not related to the syenites, (3) the lower augite syenite can be related to the upper augite syenite and amphibole quartz syenite by fractionation of a hypothetical crystal cumulate composed of orthoclase (78%), clinopyroxene (15%), olivine (1%), and titanomagnetite (6%). We conclude that the Geordie Lake intrusion, Wolfcamp basalt, and saturated syenites in the Coldwell were derived by separate partial melting events in a common mantle source. The origin of the sulfide mineralization is enigmatic because it exhibits characteristics of both magmatic and hydrothermal processes. The sulfide assemblage changes from disseminated bornite and chalcopyrite in the basal zone to pyrrhotite plus chalcopyrite in the upper zones. Sulfides occur as coarse blebs interstitial to fresh or partly altered silicates, or as very fine grains intergrown with clusters of biotite and actinolite. Primitive mantle-normalized platinum group element patterns exhibit a W-shape for Pd-Pt-Rh-Ir-Ni, indicating a relative depletion of Pt and Ir. The Cu/Pd ratios in the mineralized zones are within the range of mantle values (1000–10,000), Pd/Pt is 14–19, Pd/Rh is 91 + 37, and Pd/Ir >16,000. The Pd/Pt, Pd/Rh, and Pd/Ir are considerably higher than in the Wolfcamp basalt (

Mafic intrusions in the Coldwell Complex have previously been interpreted as forming from a metasomatized mantle source. To build upon our understanding of this metasomatism, the Mg–Fe isotope compositions of these rocks have been determined, and variations are assessed with respect to the magmatic processes that could have occurred at different stages of their formation. The mineralized Marathon Series (δ26Mg = −0.28‰ to −0.19‰), associated metabasalt (δ26Mg = −0.24‰ to −0.23‰), and the Geordie Lake gabbro (δ26Mg = −0.31‰ to −0.22‰) are characterized by δ26Mg values that are within the range of mantle values, whereas the unmineralized Layered Series (δ26Mg = −0.2‰ to −0.05‰) is heavier than mantle. In contrast, the δ56Fe values of all the Coldwell basaltic–gabbroic rocks (δ56Fe = 0.07 ± 0.08‰) are heavier than mantle but within the range of terrestrial basalts and mafic–ultramafic layered intrusions. We propose that the Mg–Fe isotope compositions of these rocks was not significantly modified by processes such as partial melting or garnet retention/fractionation in the mantle, fractional crystallization, or contamination during ascent through the crust, as the isotope values do not correlate with proxies for these processes (e.g. La/Sm and La/Yb, Gd/Yb, MgO–CaO–TiO2, and Th/Nb and Th/La, respectively). Their isotope compositions are, therefore, proposed to reflect the compositions of their metasomatized mantle sources. We conclude that metasomatism was not caused by a carbonate melt, subduction-altered oceanic crust and sediments, or an evolved silicate melt, as these processes generate light δ26Mg, variably fractionated δ56Fe, and heavy δ56Fe values, respectively, which are not observed in our dataset for the Coldwell Complex. The agent that metasomatized the mantle beneath the Coldwell Complex was likely slab-derived fluids characterized by isotopically heavy δ26Mg and basaltic δ56Fe values. This scenario can account for the lack of Fe isotope fractionation from basaltic values in all of the Coldwell rocks. The variably heavier δ26Mg of the Layered Series (−0.20 ± 0.01‰ to −0.05 ± 0.05‰) relative to the mantle (−0.25 ± 0.07‰) suggests that the magmas for the Coldwell rocks were derived by tapping of an isotopically heterogeneous mantle source that had undergone variable degrees of metasomatism. The distinctive geochemistry of mafic sequences in the Coldwell and numerous mafic dykes located in the northeast shoulder of the Midcontinent Rift suggests the presence of a variably metasomatized mantle source beneath a large area of the rift.

The W Horizon is a thin continuous zone of low sulfide-high-grade platinum group element (PGE) mineralization in the Two Duck Lake gabbro at the Marathon Cu-PGE deposit, Coldwell Complex, Canada, that resembles reef-type PGE deposits found in much larger intrusions. The Marathon deposit was previously shown to have grown by accretion of syn-magmatic, sulfide-bearing sill-like intrusions that formed each of the W Horizon, Main Zone, and Lower Zone mineralization. Each zone can be distinguished by features such as sulfide mineral or platinum group mineral assemblages, or by Cu/Pd, Pd/Se, and Pd/Au values. For example, the W Horizon is defined by the presence of bornite, very high PGE values, low Cu/Pd ( 95% of the original sulfide liquid. In some samples, metal and S abundances indicate that PGE were transported as TABS-PGE phases. This work describes an example of thin PGE-rich sill-like injections that could be of importance to PGE exploration elsewhere.

Chalcopyrite from the Cu–PGE sulfide deposits in the Eastern Gabbro, Coldwell Complex, Canada, exhibit a > 2‰ variation in δ65Cu. In the Marathon deposit, the δ65Cu of chalcopyrite increases from the lower Footwall Zone (− 1.49 to − 0.75‰), to the Main Zone (− 1.04 to 0.08‰), to the upper W Horizon (− 0.35 to 1.07‰). In the northern deposits, chalcopyrite at Four Dams and Sally have δ65Cu that range from − 0.08 to 0.47‰ and − 0.59 to − 0.05‰, respectively. Notably, samples from the Marathon deposit with lower chalcopyrite δ65Cu values tend to have higher S/Se and Cu/Pd ratios. Integrated geological and geochemical evidence suggests that secondary hydrothermal alteration and redox processes are unlikely to have been the primary causes of the observed Cu isotope variation. Numerical modeling of δ65Cu–Cu/Pd–S/Se of mineralization in the Eastern Gabbro illustrates three key aspects of Cu isotope behavior in magmatic Ni–Cu–PGE systems. First, R factors less than ~ 10,000 can exhibit significant control on the δ65Cu of sulfides. Second, sulfide liquid–silicate melt fractionation factors for Cu (Δ65Cusul–sil) greater than − 0.5‰ are applicable to Ni–Cu–PGE systems. Third, sulfide segregation exhibits no measurable control on the δ65Cu of sulfides at degrees of fractionation typical of Ni–Cu–PGE systems (< 0.3%). In the Marathon deposit, the range of δ65Cu–S/Se–Cu/Pd is attributed to the addition of Archean sedimentary Cu to a pool of sulfide liquid located at depth, followed by progressive dilution of the contaminated δ65Cu–S/Se signature and decrease in Cu/Pd ratio by influxes of uncontaminated pulses of magma (i.e., increasing R factor), some of which had Cu isotope compositions heavier than the mantle. Variably contaminated and enriched, with respect to Pd, sulfides from this pool were entrained by magma pulses and emplaced to form the Marathon deposit. This contribution demonstrates that Cu isotopes can fractionate at high temperatures and, when combined with other geochemical proxies, can be valuable in characterizing magmatic–post-magmatic processes in Ni–Cu–PGE sulfide deposits and for identifying PGE-rich sulfide deposits.

The Eastern Gabbro of the alkaline Coldwell Complex, Canada, represents a Ni-poor conduit-type system that comprises two rock series, the Layered Series and Marathon Series, which intruded into a metabasalt package. Based on distinct variations in magnetite compatible (e.g., Ni, Cr) and incompatible (e.g., Sn, Nb) elements in Fe–Ti oxide intergrowths, the metabasalts, Layered Series, and Marathon Series must have crystallized from magmas that originated from compositionally distinct sources. Of these rock units, the metabasalts crystallized from a more primitive melt than the Layered Series as Fe–Ti oxides in the former have higher concentrations of magnetite-compatible elements. Unlike the metabasalts and Layered Series, the Marathon Series crystallized from multiple, compositionally distinct magmas as Fe–Ti oxides in this series exhibit large variations in both magnetite compatible and incompatible elements. Accordingly, the various rock types of the Marathon Series cannot be related by fractional crystallization of a single batch of magma. Rather, the magmas from which the rock types crystallized had to have interacted to variable degrees with a late input of more primitive melt. The degree of this magma interaction was likely controlled by the geometry of the conduit and the location of emplacement given that Fe–Ti oxides in the oxide-rich rocks occur in pod-like bodies and exhibit no compositional evidence for magma mixing. Mirrored variations in magnetite compatible and incompatible elements in Fe–Ti oxides in the Footwall Zone, Main Zone, and W Horizon of the Marathon Cu–PGE deposit indicate that these zones could not have formed from a single, evolving magma, but rather multiple batches of compositionally distinct magmas. Fe–Ti oxides exhibit no compositional difference between those hosted by barren and mineralized rock. This is likely because sulfide liquated at depth in all of the magmas from which the Marathon Series crystallized. The composition of Fe–Ti oxides in the Eastern Gabbro fall outside of the compositional fields for Ni–Cu mineralization defined by Dupuis and Beaudoin (Mineral Deposita 46:319–335, 2011) and Ward et al. (J Geochem Explor 188:172–184, 2018) demonstrating that their discrimination diagrams can distinguish between Ni-rich and Ni-poor systems that contain disseminated and massive sulfides.

Magnetite (mag)–ilmenite (ilm) intergrowths are more common than mag–ulvospinel (usp) intergrowths in mafic–ultramafic Ni–Cu–PGE systems, yet the former has no known solid solution. The most accepted model for the formation of mag–ilm intergrowths in terrestrial environments is fluid-induced oxidation of mag–usp assemblages by oxygen in water. In this study, we re-examine this model in light of the fact that crustal fluids have very low pO2 and that mag–ilm intergrowths commonly occur in rocks that show little or no evidence of hydrothermal alteration. We also characterize the chemical changes that occurred during the formation of mag–ilm intergrowths and how they affect the use of Fe–Ti oxide chemistry for petrogenesis and mineral exploration. In the Eastern Gabbro, Coldwell Complex, a continuum of Fe–Ti oxide intergrowths occur ranging from cloth (mag–usp) to trellis (mag–ilm) types. Trellis-textured intergrowths have higher bulk Fe3+:Fe2+ ratios and are predominantly enriched not only in some multivalent (Ge, Mo, W, Sn) elements, but also in Cu and Ga, consistent with their formation via oxidation by a metal-rich fluid. These compositional changes are significant relative to typical elemental abundances in Fe–Ti oxides and could potentially lead to erroneous interpretations regarding primary magmatic processes if they are not taken into consideration. The irregular distribution of the intergrowths throughout the Eastern Gabbro suggests that different rock series and mineralized zones experienced variable degrees of fluid-induced oxidation. It is proposed that C in CO2 rather than O2 in water could potentially be an important oxidizing agent in mafic systems: $$ 9{\mathrm{Fe}}_2^{2+}\mathrm{Ti}{\mathrm{O}}_4+0.75{\mathrm{CO}}_2+1.5{\mathrm{H}}_2\mathrm{O}\leftrightharpoons 9{\mathrm{Fe}}^{2+}\mathrm{Ti}{\mathrm{O}}_3+3{\mathrm{Fe}}_2^{3+}{\mathrm{Fe}}^{2+}{\mathrm{O}}_4+0.75\mathrm{C}{\mathrm{H}}_4 $$ The applicability of this model is supported by the common occurrence of CO2 and CH4 in fluid inclusions in mafic rocks.

The Eastern Gabbro, Coldwell Complex, hosts several geochemically and mineralogically distinct Cu-platinum group element (PGE) deposits, including the high-grade W Horizon (>100 ppm Pd-Pt-Au over 2 m). Several magmatic and/or hydrothermal models have previously been proposed to explain the range of enrichment in PGEs observed in the Marathon deposit, but no work has integrated textural and compositional variations in sulfides to elucidate which of these models is most suitable. Additionally, comparatively little work has been done to characterize the genesis of Cu-PGE mineralization that occurs to the northwest of the Marathon deposit in the Eastern Gabbro. Through integration of base metal sulfide (BMS) mineralogy, texture, and trace element chemistry, a wide range of magmatic and postmagmatic processes have been characterized that contributed to the formation of these deposits. In all zones of mineralization in the Eastern Gabbro, chalcophile elements were remobilized from primary chalcopyrite by hydrothermal fluids and precipitated as secondary chalcopyrite, which occurs as a replacement of pyrrhotite and as intergrowths with hydrous silicates. BMSs in the mineralized zones in the Marathon deposit (Footwall zone, Main zone, and W Horizon) experienced higher R factors than those deposits located northwest of the Marathon deposit (Four Dams, Area 41, and Redstone), with BMSs in the W Horizon having experienced the highest R factors. The silicate melts from which the Footwall zone crystallized likely experienced some degree of sulfide segregation at depth, albeit to a much lesser degree than the northern deposits. Additionally, the melts from which the mineralized zones in the Marathon deposit crystallized were likely contaminated by high-S/Se Archean sedimentary rocks, whereas the northern deposits were likely contaminated by low-S/Se igneous and/or metamorphic rocks. BMSs in a chalcopyrite-rich pod located within the vicinity of the Coldwell Complex experienced both high R factors and high degrees of contamination (cf. W Horizon and Footwall zone, respectively). This study illustrates the complexity of processes that generate and modify mineralization in conduit-type Ni-Cu-PGE systems.

The Marathon platinum group element (PGE)–Cu deposit is hosted by the Two Duck Lake Gabbro of the Mesoproterozoic Coldwell Complex, Canada, and comprises three zones of mineralization, which have different textural, mineralogical and geochemical characteristics. The Footwall Zone occurs at the base of the Two Duck Lake Gabbro, at the contact with the Archean country rocks. The Main Zone occurs within the Two Duck Lake Gabbro, above the Footwall Zone. The W Horizon is an extraordinarily PGE-enriched zone that is characterized by very low Cu/Pd values, less pyrrhotite, and appreciably more bornite than the Footwall and Main zones. It occurs above Main Zone-equivalent mineralization in the southern half of the Two Duck Lake intrusion. Silicate mineral textures and chemistry reveal that the Marathon deposit formed in a dynamic magma conduit system with a complex magma evolution history. The deposit developed into three zones as a result of the multiple pulses of compositionally different magmas. Plagioclase commonly shows resorption surfaces with overgrowths and the anorthite content and concentrations of trace elements such as Fe, Sr, Ba, and rare earth elements in plagioclase change significantly across these surfaces. In rocks that contain sulfide minerals, plagioclase crystals have been partly resorbed and the resorbed rims are Ca-enriched and intergrown with sulfide mineral inclusions. These rims contain higher base-metal and sulfur contents and are light rare earth element-enriched compared with the primary plagioclase. These characteristics indicate input of a separate sulfide-enriched melt with a different composition compared with that from which the primary plagioclase crystallized. Additional evidence for the involvement of slightly different magmas during evolution of the three mineralized zones is derived from variations in pyroxene chemistry (e.g. higher Fe, lower Mg, V, and Sc) between the Footwall Zone and the other two zones and the absence of inverted pigeonite from the W Horizon. The PGE enrichment occurred at depth prior to intrusion and late-stage PGE-rich sulfide-bearing magmas intruded and formed the W Horizon. Therefore, the W Horizon is a zone of mineralization that formed late in the evolution of the Two Duck Lake Gabbro.

A diverse suite of tholeiitic to alkaline basalt and gabbroic intrusions located in the Coldwell Complex on the northern margin of the Midcontinent Rift exhibit unusual trace element signatures that show enriched large ion lithophile elements and light rare earth elements with negative Nb and Zr anomalies. These features are not typical of magmas derived by partial melting within or above a rising mantle plume, as might be expected in an early Midcontinent Rift magmatic event. In this paper, we provide a detailed geochemical study of a 500 m thick sequence of metabasalt that represents the earliest stage of magmatism in the Coldwell Complex. We show that contamination or crystallization processes or subsequent metasomatism cannot explain the trace element variations. Instead, we propose partial melting in a metasomatized Subcontinental Lithospheric Mantle source to explain the decoupled behavior of large ion lithophile elements from light rare earth elements and heavy rare earth elements and rare earth elements from high field strength elements and the enriched Nd isotope signature of metabasalt. Similar features occur in unit 5b of the Mamainse Point Volcanic Group located at the northern margin of the Rift. An objective of this paper is to relate Two Duck Lake gabbro, host rock for low-sulfur, high precious metal sulfide mineralization at the Marathon deposit, to the metabasalt sequence. The excellent match of trace element abundances in Two Duck Lake gabbro to metabasalt unit 3 confirms an early Coldwell Complex age for metabasalt and a Subcontinental Lithospheric Mantle source for Cu – platinum group element mineralized gabbros.

The Layered Series of the Midcontinent Rift related Coldwell Complex comprises thick sections of gabbro, without any known associated ultramafic rocks. It represents a major early intrusive unit of the Coldwell Complex and consists of thick accumulations of olivine gabbro and oxide augite melatroctolite. This study combines petrography, mineral chemistry, and lithogeochemistry to constrain the magma composition and petrogenesis of the Layered Series. The presence of cumulus orthoclase together with the observation that the Layered Series rocks plot in the alkaline field on a total alkali–silica diagram indicate that the Layered Series magma has an alkaline parentage. The stratigraphy of the Layered Series cannot be fully correlated between different areas using lithogeochemistry and mineral chemistry. This together with observed normal and reverse trends for mineral chemical compositions in different areas suggest that the processes related to magma emplacement and crystallization were different in different locations. The whole-rock concentrations of incompatible elements and the compositions of major minerals of the olivine gabbro and oxide augite melatroctolite units are chemically similar. However, major element lithogeochemistry is variable, dominantly due to differences in the abundances of olivine, clinopyroxene, plagioclase, and magnetite. An additional observation is that olivine and clinopyroxene are not in chemical equilibrium. Together, these observations are interpreted to reflect a combination of multiple injections of magma and crystal sorting in an open system.

Mafic intrusions on the NE shoulder of the Midcontinent Rift (Keweenawan LIP), including Cu–PGE mineralized gabbros within the Coldwell Complex (CC), and rift parallel or radial dykes outside the CC are correlated based on characteristic trace element patterns. In the Coldwell Complex, mafic rocks are subdivided into four groups: (1) early metabasalt; (2) Marathon Series; (3) Layered Series; (4) Geordie–Wolfcamp Series. The Marathon Series are correlated with the rift radial Abitibi dykes (1140 Ma), and the Geordie–Wolfcamp Series with the rift parallel Pukaskwa and Copper Island dykes. U–Pb ages determined for five gabbros from the Layered and Marathon Series are between 1107·7 and 1106·0 Ma. Radiogenic isotope ratios show near chondritic (CHUR) εNd(1106 Ma) and 87Sr/86Sri values that range from –0·38 to +1·13 and 0·702537 to 0·703944, respectively. Distinctive geochemical properties of the Marathon Series and Abitibi dykes, such as Ba/La (14–37), Th/Nb (0·06–0·12), La/Sm (3·8–7·7), Sr/Nd (21–96) and Zr/Sm (9–19), are very different from those of the Geordie–Wolfcamp Series and a subset of Copper Island and Pukaskwa dykes with Ba/La (8·7–11), Th/Nb (0·12–0·13), La/Sm (6·7–7·9), Sr/Nd (5–7·8) and Zr/Sm (18–24). Each unit exhibits covariation between incompatible element ratios such as Zr/Sm and Nb/La or Gd/Yb, Sr/Nd and Ba/La, and Nb/Y and Zr/Y, which are consistent with mixing relationship between two or more mantle domains. These characteristics are unlike those of intrusions on the NW shoulder of the MCR, but resemble those of mafic rocks occurring in the East Kenya Rift. The results imply that an unusual and long-lived mantle source was present in the NE MCR for at least 34 Myr (spanning the 1140 Ma Abitibi dykes and the 1106 Ma Marathon series) and indicate potential for Cu–PGE mineralization in an area much larger than was previously recognized.

Portable XRF (pXRF) and benchtop scanning electron microscopes equipped with energy dispersive systems (bSEM-EDS) are two real-time analytical techniques that can be combined to collect on-site lithogeochemical and mineral chemical results at dramatically reduced cost and time compared to traditional analytical methods. The Coldwell Complex, northwestern Ontario, is used as a case study on how the combination of these techniques can be applied to mineral exploration. Our results show that whole-rock Ba, V/Ti, Cu/S determined by pXRF, and plagioclase, olivine, and clinopyroxene compositions measured by bSEM-EDS can be applied to exploration for PGE deposits. Cu/S ratios for disseminated sulfides are a proxy for metal tenor, which can be applied as a vector towards higher grade mineralization. Potential magma recharge zones are identified by inspecting down-hole variations in plagioclase, olivine, and clinopyroxene compositions. Fluctuating down-hole variations in these parameters are interpreted to reflect episodic magma recharge. Whether rocks contain PGE mineralization can initially be assessed by documenting the variability of mineral chemistry, i.e., the greater variability of mineral chemistry could be used to vector higher grade PGE mineralization, particularly if the mineralization is conduit-related. Lastly, geochemical mapping of the igneous stratigraphy enables identification of favorable hosts for mineralization. Down-hole whole-rock variations in Ba and V/Ti from pXRF, and mineral chemical profiles from bSEM-EDS are used to discriminate the mineralized Marathon Series from the barren Layered Series throughout the Coldwell Complex. Whole-rock Ba and V/Ti from pXRF and mineral chemical results from bSEM-EDS could prove useful in other settings of the Midcontinent Rift (e.g., the Duluth Complex, Eagle and Eagle East intrusions, Tamarack Intrusive Complex, and the Sonju Lake intrusion) and elsewhere (e.g., the Stillwater Complex) to identify mineralized host rock types. An additional important application is a rapid interpretation of petrogenesis. Down-hole variations in olivine-clinopyroxene Mg-Fe exchange coefficients determined by bSEM-EDS analyses show that olivine-clinopyroxene pairs in the Marathon Series units, particularly for those within PGE mineralized zones, have compositions that are closer to chemical equilibrium (constant) compared to units of the barren Layered Series (highly variable), and thus could be a tool for interpreting petrogenetic processes active in the magma chamber or during the mineralization forming event.

Exploration for mineral deposits is becoming increasingly difficult, requiring the use of novel approaches that are reliable and cost-effective. One such approach is the use of vein-hosted mineral chemistry. A number of studies have described the use of vein-hosted mineral chemistry as an exploration tool, but few have assessed a variety of factors that may have controlled the composition of these minerals. An understanding of why and how the composition of minerals varies, however, is critical to the development of robust exploration tools. This contribution combines detailed mineralogy using energy- and wavelength-dispersive spectroscopy, Raman spectroscopy, and μXRD with high-resolution laser ablation ICP-MS trace element analysis to characterize the controls on the chemistry of vein-hosted minerals, and the implications of these controls for the applicability of these minerals for mineral exploration. In and around the Marathon Cu-Pd deposit, veins consist of a complex mixture of phyllo and chain silicates, including chlorite, serpentine, saponite, and Ca-rich amphibole, whereas disseminated alteration consists predominantly of Ca-rich amphibole with lesser chlorite. The abundance of these veins is inversely correlated with the presence of mineralization. Minerals hosted in veins and patchy alteration crystallized from different fluids during temporally distinct events; the veins formed later than the disseminated alteration and from multiple stages of lower-temperature fluids. There is no correlation between the rock types that the veins are hosted by and the composition of the vein minerals, but on a very local scale, the mineral that a vein is hosted by does exhibit a compositional control. Vein minerals that are hosted by magnetite, and to a lesser extent, pyroxene, are enriched in Ti, V, and Cr compared to those hosted by plagioclase. In vein minerals that are hosted by plagioclase, the concentration of Co, Ni, and Zn increase systematically with distance from mineralization. The concentrations of Co, Ni, and Zn in vein minerals hosted by plagioclase also, however, increase systematically with distance from the contact between the mineralized pluton and the underlying Archean country rocks (i.e., the footwall contact). This suggests that the Co, Ni, and Zn in the fluids were likely derived by progressive leaching from pyroxene, olivine, and magnetite as the fluid migrated upwards through the pluton, rather than from the mineralization. Consequently, the correlation between vein-hosted mineral chemistry and sulfide mineralization are misleading. The only vein characteristic that can be used as an exploration tool at Marathon is the inverse correlation between vein density and zones of sulfide mineralization. This study demonstrates that the application of vein and mineral chemistry to mineral exploration needs to be carried out in the context of a careful assessment of the variations and controls on mineral chemistry from the scale of the deposit and its surrounding rocks down to the grain-scale.

Accurate characterization of the platinum group mineral (PGM) assemblages for Cu-Ni-PGE deposits are typically constrained by sample size and the difficulty of finding statistically significant numbers of grains, which is expected given the low concentrations of platinum group elements ( 75 µm) can account for large fractions of total mass. Despite these limitations, an accurate survey of PGM from different deposit types would have significant value towards developing deposit models and respective exploration strategies. In this study, we present results for a comprehensive evaluation of PGM at four copper-PGE occurrences hosted within separate but co-genetic gabbro or troctolite intrusions in the Coldwell Alkaline Complex and confirm that accurate surveys are possible with sufficient sample material and efficient PGM concentration methods. The PGM concentration methods used include: (1) hydroseparation of sieved size fractions of pulverized material, and (2) panning of grain separates produced by electric pulse disaggregation of drill core specimens. A favourable comparison of the results has verified the reliability of each method and added confidence that the PGM assemblages identified at three of the four locations are fully characterized. Precious metal mineral (PMM) assemblages are determined for the Main zone and W Horizon at the Marathon deposit, and the main zones at each of the Geordie Lake deposit and Area 41 occurrence. A total of 10,824 PMM grains (PGE and Au-Ag) and 68 mineral species, including 16 unknown minerals, were identified, of which 768 grains and 31 species occur at the Main zone, 523 grains and 41 species at Area 41,9485 grains and 43 species at W horizon, and 56 grains and 12 species at Geordie Lake. The PMM are grouped as follows: Pd-Ge, PGE-S-As, Pt-Fe alloy, Pd-Cu-Pb-Au, Pd-Ni-S, Pd-Pt-Sn, Pt-As, Pd-As, Pd-Pt-Sb-As, Pd-Pt-Bi-Te, and Au-Ag. All of the deposits were found to contain similar proportions of Pd-Pt-Sb-As, Pd-Pt-Bi-Te and Au-Ag minerals. But the W Horizon and Area 41 are distinguished from the Marathon Main zone and Geordie Lake deposits by the presence of minerals in the PGE-S-As, Pt-Fe alloy, Pd ± Cu ± Pb ± Au and Pd-Ge groups. Taken together, the PMM assemblages for deposits in the Coldwell exhibit a strong correlation to PGE enrichment relative to the range for mantle Cu/Pd values (1000–10,000). And there is no relationship between the abundances of Pd-Pt-Bi-Te and Pd-Pt-Sb-As minerals that are commonly associated with hydrous phases, and the intensity of hydrothermal alteration. Thus minerals found only at the W Horizon and Area 41, where significant PGE upgrading has occurred, including Pt-Fe alloys, rustenburgite, marathonite, palladogermanide, unknown Rh-Ni-Fe-sulfide, Au-Pd-Cu alloy, braggite, coldwellite, laurite, zvyagintsevite, laflammeite, and unknown phases Pd 5 As 2 , Pd 3 As, Pd 3 (As,Pb,Bi) might be considered as index minerals for PGE enriched types of mineralization in the Coldwell.

The W Horizon, Marathon Cu-Pd deposit in the Mesoproterozoic Midcontinent rift is one of the highest grade PGE repositories in magmatic ore deposits world-wide. The textural relationships and compositions of diverse platinum-group mineral (PGM) and sulfide assemblages in the extremely enriched ores (>100 ppm Pd-Pt-Au over 2 m) of the W Horizon have been investigated in mineral concentrates with ∼10,000 PGM grains and in situ using scanning electron microprobe and microprobe analyses. Here we show, from ore samples with concentrations up to 23.1 Pd ppm, 8.9 Pt ppm, 1.4 Au ppm and 0.73 Rh ppm, the diversity of minerals (n = 52) including several significant unknown minerals and three new mineral species marathonite (Pd25Ge9; McDonald et al., 2016), palladogermanide (Pd2Ge; IMA 2016-086, McDonald et al., 2017), kravtsovite (PdAg2S, IMA No 2016-092, Vymazalova et al., 2017). The PGM are distributed as PG-, sulfides (52 vol%), -arsenides (34 vol%), -intermetallics of Au-Ag-Pd-Cu and Pd-Ge(10 vol%) and -bismuthides and tellurides (4 vol%). The discovery of abundant (>330 grains) large unknown sulfide minerals with Rh allows us to present analyses three significant potentially new minerals (WUK-1, WUK-2, WUK-3) that are all clearly enriched in Rh (averaging 4.2, 8.5 and 28.21 wt% Rh respectively). Several examples of paragenetic sequences and mineral chemical changes for enrichment of Cu, Pd and Rh with time are revealed in the PGM and base-metal sulfides. We suggest this enhanced metal enrichment formed in response to increasing fO2 causing the oxidation of Fe2+ to Fe3+ and to a lesser extent, S. Phase relations in the Ag-Pd-S, Rh-Ni-Fe-S, Pd-Ge, Au-Pd-Cu-Ag, Pd-Ag-Te systems help constrain the crystallization temperatures of the majority of ore minerals in the W Horizon at ∼500 °C or moderate to high subsolidus temperatures (400–600 °C). Local transport by aqueous fluids becomes evident as minerals recrystallize down to

Mineral exploration is increasingly taking advantage of real time techniques that dramatically reduce the costs and time taken to obtain results compared to traditional analytical methods. Portable X-ray fluorescence (pXRF) is now a well-established technique that is used to acquire lithogeochemical data. To date, however, benchtop scanning electron microscopes, equipped with energy dispersive systems (bSEM-EDS) have received little attention as a possible mineral exploration tool. This study examines the utility of combining pXRF and bSEM-EDS to characterize the igneous stratigraphy and its relationship to Cu-Pd mineralization in a drill hole at the Four Dams occurrence, located within the Eastern Gabbro assemblage of the Coldwell Alkaline Complex, Canada. The first part of this study compares field portable and laboratory techniques. Seventy-two powdered samples analysed by pXRF are compared with traditional major elements analysed by inductively coupled atomic emission spectroscopy (ICP-AES) and trace elements by inductively coupled plasma spectrometry (ICP-MS), and the compositions of 128 olivine, clinopyroxene and plagioclase grains analysed by bSEM-EDS are compared with traditional electron microprobe data. Our results show that each portable technique yields results similar to their lab-based counterparts within the analytical capabilities and precisions of the respective instruments. The second part presents a case study for the application of pXRF and bSEM-EDS to resolve questions related to igneous stratigraphy as an aid to mineral exploration in a complicated geological setting. A major problem for Cu-Pd exploration in the Coldwell Complex of NW Ontario is that the oxide-rich units that host Cu-Pd mineralization in the Marathon Series are petrographically similar to the barren oxide-rich units in the Layered Series. However, the mineralized units are geochemically distinctive. Our results show that the mineralized Marathon Series can be distinguished from the barren Layered Series, including oxide-rich units of both, by combinations of P 2 O 5 , Ba, Zr and V/Ti values, determined by pXRF, combined with plagioclase, olivine or clinopyroxene compositions measured by bSEM-EDS. The combination of pXRF and bSEM-EDS thus shows considerable promise as an exploration technique. Supplementary material: Comparisons of pXRF analyses with ICP-AES, ICP-MS and IR analysis are available at http://doi.org/10.6084/m9.figshare.c.3291518

Coldwellite, ideally Pd 3 Ag 2 S, is a new mineral species discovered in a heavy-mineral concentrate from the Marathon deposit, Coldwell Complex, Ontario Canada. It is cubic, crystallizing in space group P 4 3 32 (#212) with a 7.2470(8) A, V 380.61(1) A 3 , Z = 4. The five strongest lines of the X-ray powder-diffraction pattern [ d in A (I)( hkl )] are: 2.427(100)(221), 2.302(38)(310), 2.195(38)(311), 1.4280(44)(510,431), 0.9294(24)(650,643), and 0.9208(20)(732,651). Associated minerals in the discovery sample include Au-Ag alloy, hollingworthite, isoferroplatinum, keithconnite, kotulskite, mertieite-II, michenerite, palladoarsenide, sobolevskite, sperrylite, stillwaterite, vysotskite, Ti- and Cr-rich magnetite and ilmenite, pyrrhotite, chalcopyrite, and pentlandite, with trace amounts of bornite, cobaltite, and galena. Coldwellite is white with a light pinkish brown tint, and it has a metallic luster. No streak or microhardness could be measured. The mineral shows no internal reflections, pleochroism, bireflectance, or anisotropy. The reflectance values (%) in air for the standard COM wavelengths are: 41.9 (470 nm), 44.9 (546 nm), 44.0 (589 nm), and 45.0 (650 nm). The density, 9.90(1) g/cm 3 , was calculated using the empirical formula and the unit-cell parameters from the refined crystal-structure. The average result ( n = 23) of electron-microprobe analyses is: Pd 56.1, Fe 0.16, Ag 38.2, S 5.63, total 100.09 wt.%, which corresponds to (Pd 2.99 Fe 0.02 ) Σ3.01 Ag 2.00 S 0.99 , based on 6 apfu . The name recalls the type locality.

Various ultramafic Ni-Cu-platinum group element (PGE) deposits associated with the North American Midcontinent rift have been attributed to formation in a magma conduit setting, whereby PGE concentration is controlled by various fluid dynamic processes. The Marathon Cu-PGE sulfide deposit located within the Midcontinent rift-related Coldwell Alkaline Complex has been classified as a gabbro-associated contact-type deposit; however, both magmatic and hydrothermal processes have been proposed to account for the significant concentration of PGE. In light of the growing field of evidence for magma conduit-type settings, this study comprised a comprehensive geochemical investigation of the complicated crosscutting gabbroic to ultramafic units in the immediate vicinity of the Marathon deposit; and a thorough three-dimensional investigation of the distribution of Cu and Pd within the Main mineralized zone. The main objectives of this study were to test the applicability of the magma conduit deposit model to the Marathon deposit and to identify key exploration criteria for use elsewhere in the Coldwell Alkaline Complex. Mineralization is hosted by the Two Duck Lake gabbro, a 4-km-long and 250-m-thick unit of the Marathon Series. The Marathon Series is the latest of three magmatic series that make up the 1- to 2-km-thick Eastern Gabbro Suite, which wraps around the eastern and northern margin of the Coldwell Alkaline Complex. The three magmatic series are shown here to have distinct trace element signatures that enable reliable discrimination of potentially sulfide and PGE-bearing units of the Marathon Series from the barren rocks of either the Fine-Grained or Layered Series. At the Marathon deposit, sulfides consist of disseminated chalcopyrite, pyrrhotite, and minor bornite and occur within the Main, Footwall, and Hanging-wall zones and in the PGE-enriched W Horizon. This paper focused on sulfides located within the Main zone, including the keel-shaped feeder channel that continues downdip to over 550-m depth. The spatial distribution of Cu, Pd, and Cu/Pd were examined in relation to a three-dimensional surface model for the footwall contact; in a vertical profile through the Main zone; and in a longitudinal section that cuts the feeder channel. There are three important observations: (1) trends for elevated Cu and Pd are parallel to numerous troughs and ridges in the footwall, (2) Cu, Pd, and Cu/Pd varies up section in a saw-toothed pattern from high to low values, and (3) the proportion of high Cu/Pd sulfides is greatest within the thickest accumulations of sulfides within the feeder channel. Evaluation of interelement relationships between Cu and Pd and between Pd and Ir, Rh, Pt, and Au for mineralization within the Main zone indicate positive associative, but nonlinear behavior for all elements. Briefly, the data show nonlinear correlations between Cu and Pd in which Cu/Pd decreases with increasing Pd; and coherent but nonlinear behavior for Ir, Rh, Pt, and Pd in which Pd/Ir, Pd/Rh, Pd/Pt, and Pd/Au all increase with increasing Pd. The observed variation in Cu/Pd is consistent with a magmatic model calculated by others for deposits in the Duluth Complex, in which sulfides accumulated in a closed system from a melt with mantlelike Cu/Pd and an elevated silicate to sulfide ratio. The observed variations in Pd/Ir, Pd/Rh, and Pd/Pt are consistent with R factor fractionation related to differences in the relative partition coefficients between sulfide and silicate melts, and rule out the possibility that processes such as fractionation of sulfide melt by monosulfide solid solution (mss) or redistribution of metals during hydrothermal alteration played a significant role in the mineralizing event. The Two Duck Lake gabbro and associated sulfides of the Marathon deposit are proposed to have formed by multiple injections of plagioclase crystal mush that carried droplets of sulfide liquid along a conduit system that was controlled by radial and ring fault structures in the Coldwell Alkaline Complex. The accumulation of sulfides was controlled by flow dynamic processes within the magma channels, but Cu/Pd was controlled by local proportions of silicate melt to sulfide liquid. Key characteristics of the deposit that are critical to exploration elsewhere in the Coldwell Alkaline Complex include the following: (1) the recognition that gabbroic to ultramafic intrusions of the Marathon Series are the host for Cu and PGE mineralization, (2) the distribution of Cu/Pd data within sulfide occurrences are useful as vectors toward the feeder channel, (3) topographic lineaments are indicators of potential mineralized feeder zones, and (4) oxide- and apatite-rich, irregularly shaped gabbroic to ultramafic pods are potential indicators of an underlying feeder channel.

PurposeThe purpose of this paper is to determine if transformational leadership has an effect on business‐to‐business salespeople's trust in the organization, whether trust in the organization affects moral judgment and if moral judgment in turn affects salesperson performance, specifically “world‐class” sales performance.Design/methodology/approachThrough the utilization of a national survey of 345 business‐to‐business salespeople, this study explored linkages between transformational leadership, trust in the organization, moral judgment and world class sales performance using structural equation modeling.FindingsResults suggest that transformational leadership can be used to influence sales performance through trust in the organization and salesperson moral judgment.Originality/valueThe paper furthers the understanding of transformational leadership and its impact on salespeople. The interaction of three variables (transformational leadership, trust in the organization, and the moral judgment of the salesperson) and their ability to relate to world class sales performance provide an interesting strategic guide for sales organizations, as well as a meaningful set of managerial tools that can assist in constructing a performance driven sales organization. These constructs have not been simultaneously investigated prior to this research.

PurposeA great deal has been written recently in the practitioner press about the strategic importance and usage of social media. However, as practitioners only release limited information about the internal advantages such a tool provides, research in this emerging field remains extremely limited about its usage in the sales area. In this context, the purpose of this paper is to propose and empirically assess a model of social media usage among business‐to‐business (B2B) salespeople.Design/methodology/approachA survey of 273 B2B salespeople was conducted and then analyzed using structural equation modeling.FindingsResults support the hypothesized model suggesting that age negatively affects social media usage, while social media norms positively affect it. Social media usage positively affects sales performance. Customer‐oriented selling was not found to be positively related to social media usage, but does have a positive effect on sales performance.Research limitations/implicationsThis study was conducted by e‐mail, and as a result, there might be an existing bias towards respondents who already embrace some usage of an online communication method, indicating overall usage, acceptance, and application of social media may be lower than reported. A potential research agenda offers opportunities for both theoretical development and empirical assessment in social media research.Practical implicationsThe findings provide an important foundation to advance academic sales research and demonstrate a needed understanding of how to operationally utilize social media to improve outcome performance.Originality/valueThis is one of the few studies empirically examining social media usage among B2B salespeople.

Despite a growing strategic, operational, and research spotlight on relational building and retention in recent years, practitioners must balance this vision with commonly critical selling practices and needs (i.e., obtain sales quota while building and retaining customer relationships). In such an environment, this paper proposes that marketers can prosper if they more fully understand the connections between sales quotas and other important organizational issues (i.e., trust in the organization, customer-oriented selling, and sales performance). The significance of sales quotas as a directing force has been noted by researchers and practitioners for some time. Yet beyond their obvious influence (e.g., as sales goals), little is understood as to what extent these frequently utilized performance objectives connect and impact other critical organizational issues within the selling group. Using a sample of 345 business-to-business salespeople, this study explores how the application of sales quotas have far...

The purpose of this study was to determine the influence of water vapor sorbed by and dissolved in an amorphous polymer on the formation and thermodynamic stability of cocrystals that are incongruently saturating in water. The conversion of crystalline phases of a hydrophobic drug (carbamazepine) and a hydrophilic coformer (nicotinamide) to cocrystal as a function of moisture sorption (43%, 62% and 75% RH) by an amorphous polymer (polyvinylpyrrolidone, PVP), molecular weight (K12 and K90) and fraction of polymer in ternary mixtures (25 and 50 wt%) was investigated. Moisture uptake and crystallization behavior were studied by gravimetric and dynamic vapor sorption, X-ray powder diffraction, FT-IR, Raman microscopy, and polarized optical microscopy. Results indicate that moisture uptake by PVP can generate cocrystals at moisture contents as low as 3.3% in a ternary mixture corresponding to 13.1% moisture sorbed by PVP. Cocrystal formation rate increased with moisture uptake. The same level of moisture sorption by PVP resulted in higher cocrystal formation rates with lower PVP molecular weight and higher PVP fraction in mixture. This behavior is explained by the increased mobility of water and PVP leading to more effective dissolution of components and higher supersaturation with respect to cocrystal. PVP was also found to change the eutectic point associated with the cocrystal/drug hydrate/solution equilibrium such that the ratio of cocrystal to drug solubility decreases with increasing PVP. Thus, PVP increases the thermodynamic stability of this cocrystal relative to drug.

Sales research often notes the critical role of sales managers in providing interface between the firm and the salesperson while cultivating sales performance in highly competitive marketplaces. In such a stressful environment, reports of unethical behaviors (results, causes, effects, etc.) continue to plague the profession. In this context, the purpose of this study was to examine the role of a chiefly unexplored quality of sales managers, transformational leadership, and its affect on the moral judgment of the sales force. In a study of 345 business-to-business salespeople, it was found that transformational leadership has an indirect effect on moral judgment as well as direct effects on supervisory capability orientation and the trust of the salesperson in the manager. Managerial and research implications are also offered as part of the paper.

For many years, researchers and practitioners have sought out meaningful indicators of sales performance. Yet, as the concept of performance has broadened, the understanding of what makes up a successful seller, has become far more complicated. The complexity of buyer–seller relationships has changed therefore as the definition of sales performance has expanded, cultivating a growing interest in ethical/unethical actions since they could potentially have impacts on sales performance. Given this environment, the purpose of this study is to explore the impact of moral judgment on sales performance and sellers engaging in a customer-oriented selling approach. Specifically, by utilizing a sample of 345 business-to-business salespeople, this study examines the relationships between moral judgment, customer-oriented selling, and outcome and behavior based performance. Results, managerial implications, and opportunities for future research are provided.

Cocrystal eutectic constants (Keu), the ratio of solution concentrations of cocrystal components at the eutectic point, are a fundamental indicator of phase behavior and are shown to be a function of the solubility ratio of cocrystal and drug in pure solvent. Keu is shown to depend on solution chemistry including (i) solvent, (ii) complexation, and (iii) ionization, as does the solubility of cocrystals. More than 40 eutectic constants are presented and shown to provide essential information for cocrystal synthesis, selection, and formulation.

Pharmaceutical cocrystals can improve solubility, dissolution, and bioavailability of poorly water soluble drugs. However, true cocrystal solubility is not readily measured for highly soluble cocrystals because they can transform to the most stable drug form in solution. The objectives of this study are to develop a method to estimate the cocrystal solubility in pure solvent and establish the influence of constituent drug and ligand (i.e., coformer) properties. Cocrystal solubility and solubility product were derived from transition concentration measurements where a solution is in equilibrium with solid drug and cocrystal. Transition concentrations and solubilities are reported for carbamazepine cocrystals in water, ethanol, isopropanol, and ethyl acetate. The aqueous solubility for seven carbamazepine cocrystals was estimated to be 2−152 times greater than the solubility of the stable carbamazepine dihydrate form. Cocrystal solubility is shown to be directly proportional to the solubility of constituent...

Because it is believed sales performance can be enhanced through ethical behaviors, increasingly, emphasis is being placed on understanding unethical behaviors among key customer-contact employees and the environment in which these sales professionals engage clients. In this context, understanding how the direct supervision of the sales force (sales managers) can shape the ethical behavior of salespeople may be a critical controllable key to understanding unethical sales behaviors that offers upper management strategic opportunities to enrich customer relationships. In this framework of understanding unethical sales behaviors, 240 sales managers were surveyed to determine their impact on unethical sales behaviors. The results indicate that although the overall ethical climate influences ethical attitudes of sales managers, importantly, these managerial attitudes impact ethical training and hiring evaluations of the sales force. Further, the positive relationship found between the ethical attitudes of sale...

The purpose of this study is to determine the mechanisms by which moisture can generate cocrystals when solid particles of cocrystal reactants are exposed to deliquescent conditions (when moisture sorption forms an aqueous solution). It is based on the hypothesis that cocrystallization behavior during water uptake can be derived from solution chemistry using models that describe cocrystal solubility and reaction crystallization of molecular complexes. Cocrystal systems were selected with active pharmaceutical ingredients (APIs) that form hydrates and include carbamazepine, caffeine, and theophylline. Moisture uptake and crystallization behavior were studied by gravimetric vapor sorption, X-ray powder diffraction, and on-line Raman spectroscopy. Results indicate that moisture uptake generates cocrystals of carbamazepine-nicotinamide, carbamazepine-saccharin, and caffeine or theophylline with dicarboxylic acid ligands (oxalic acid, maleic acid, glutaric acid, and malonic acid) when solid mixtures with cocrystal reactants deliquesce. Microscopy studies revealed that the transformation mechanism to cocrystal involves (1) moisture uptake, (2) dissolution of reactants, and (3) cocrystal nucleation and growth. Studies of solid blends of reactants in a macro scale show that the rate and extent of cocrystal formation are a function of relative humidity, moisture uptake, deliquescent material, and dissolution rates of reactants. It is shown that the interplay between moisture uptake and dissolution determines the liquid phase composition, supersaturation, and cocrystal formation rates. Differences in the behavior of deliquescent additives (sucrose and fructose) are associated with moisture uptake and composition of the deliquesced solution. Our results show that deliquescence can transform API to cocrystal or reverse the reaction given the right conditions. Key indicators of cocrystal formation and stability are (1) moisture uptake, (2) cocrystal aqueous solubility, (3) solubility and dissolution of cocrystal reactants, and (4) transition concentration.

La ferropicrite de Boston Creek, affleurant pres de Kirkland Lake dans la ceinture de l'Abitibi, en Ontario, est une unite differenciee a niveaux mafiques et ultramafiques d'âge archeen ayant une couche remarquablement epaisse de clinopyroxenite a texture spinifex a son contact superieur, equivalant a environ un tiers de l'epaisseur totale d'environ 100 m. Nous avons echantillonne la section a spinifex a un intervalle d'environ 1 m. Des reliquats du clinopyroxene a spinifex sont presents dans les deux-tiers inferieurs de la couche. Les resultats des analyses avec une microsonde electronique montrent que le clinopyroxene est une augite calcique avec une bordure generalement enrichie en Fe, Ca et Mn par rapport au noyeau. Ces variations sont plus evidentes dans les 10 m a la base de la couche. Un second clinopyroxene en surcroissance et en invaginations montre des variations de coeur a la bordure encore plus marquees, avec des compositions atteingnant le domaine de la diopside et de l'hedenbergite. Les variations en composition du clinopyroxene a texture de spinifex sont attribuees a la reaction entre clinopyroxene et liquide interstitiel piege. Une origine metamorphique semble beaucoup moins probable, compte tenu du manque de signes de tranferts de masse entre les roches encaissantes et la ferropicrite, la probabilite que les reactions d'echange entre pyroxene et liquide piege (presentement la matrice) seraient favorisees par une temperature magmatique, et la teneur elevee en Mn dans les premiers 5 m a la base du niveau a texture spinifex. Les compositions globales temoignent de diminutions marquees en Mg, Ni, Co et Cr dans les premiers 3 m au haut de la couche, et de faibles enrichissements en Ca, Al, K et Ti, signes de l'incompatibilite de ces elements au cours du fractionnement du clinopyroxene. Dans les premiers 10 m a la base de la couche, des inversions distinctes en composition sont evidentes dans les profils de Mg, Al, Cr et Mg# des roches totales. Ces inversions refleteraient un changement important de la composition du magma, peut-etre a cause d'une venue de magma frais au stade de cristallisation du gabbro, et d'un melange consequent entre magma non fractionne et magma residuel. Des variations locales des teneurs en elements du groupe du platine, certains aspects des relations isotopiques entre Re et Os, et les caracteristiques magnetiques a la base de la zone a spinifex et de la partie superieure de la couche gabbroique viennent etayer cette hypothese.

The maxim of managers seems to be what gets measured gets done. However, with multiple measures of marketing effectiveness, which few should be chosen? This paper re-examines the proposed outcome measures of Good (1992) and the marketing literature since that time to suggest an updated view of performance measures.

Sales quotas typically “drive” sales organizations. As such, the ability of the sales organization, both individually (the salesperson) and the group (the total collection of the sales professionals), to accomplish its quota has a significant impact on the performance of the sales and marketing organization, as well as the entire firm. Within the context of this use, quotas represent a critical sales goal, although very little is actually known about their strategic or operational use within marketing organizations. The purpose of this paper is to investigate quotas from a strategic and operational perspective to provide additional insight into understanding sales quotas. Specifically, this manuscript investigates the consequences of failing to achieve quota and the relationship between these consequences and salesperson performance, salesperson income, and the firm’s annual sales revenue. In addition, the relationship between these variables and quota difficulty, and quota performance are explored.

The invariance, by executive position in the organization, of an information technology impacts model is examined. The theoretical model links computer training, end-user previous computer experience, information (provided by the system) quality, ease of system use, customer knowledge in the firm’s industry, and the tasks performed using the system to individual and firm performance impacts through system use and satisfaction. The empirical examination uses data from a national mail survey. The respondents are business executives at four different organizational levels (i.e., owners, senior executives, marketing executives, and middle/operational executives). The quantitative technique used is invariance analysis based on structural equation modeling. The results indicate that the interrelationships among the theoretical constructs in the model are generally invariant across these different organizational positions. The one difference identified is the path from information quality to system use. Examining each executive group individually shows that this path is significant for marketing executives, but no other executive group. Thus, the identified difference appears to be produced by the importance of information quality on marketing executives’ use of computer systems. Managerial implications, conclusions, and suggestions for future research are discussed based upon these results.

The study explores which tasks performed using computer technology improve the performance of the marketing organization. The basis of the study is the need for marketers to improve the output in the marketing organization. The model links using computerization and information technologies to exploit opportunities, solve problems, improved work quality and quantity, and improved communications to improved marketing operations. A national mail survey of marketing executive provided the data. The 122 survey responses were used to analyze the model via structural equation modeling. The results indicate that using these technologies to exploit opportunities and improve work quality and quantity have impacts on improving marketing operations.

The literature is rich with examples that stress the importance of marketers having long‐term customer relationships. Yet, the reality is that while relational attachments can foster benefits, there are many occasions when marketers seek, or are forced, to disband or change the nature of customer relationships. Interestingly however, despite the obviousness of this circumstance, this remains an unexamined strategic condition. In a unique investigation, this article explores the strategic opportunities and conditions that emanate from “relational unrest” in the business‐to‐business marketplace. Consequently, this article notes how sellers can benefit from understanding how to properly manage relational unrest. To address this issue, a strategic framework is proposed, which concludes that when sellers experience relational difficulties, strategic options with positive outcomes and related managerial implications can be associated with this condition.

The value of long‐term relationships has become a widely studied variable in marketing. This article investigates two important characteristics of salespeople (consideration of future sales consequences and customer‐oriented selling) and their effects on the usage of long‐term relationships. In turn, associations between a long‐term relationship orientation, and a preference for long‐term compensation are explored. The findings suggest managerial and research implications for structuring of reward systems and potential tools for recruiting, selection and assignment of salespeople based on these characteristics.

Although chiefly anecdotal, reports that performance is enhanced through technology has encouraged many marketers to adopt computer systems. To examine this issue, 183 industrial marketing executives familiar with computers were surveyed. The results suggest that, properly managed, computer usage enriches individual marketer productivity and, in turn, organizational performance. Because managers can direct this productivity through organizational activities and investments, these findings suggest a number of key implications for marketers and researchers interested in utilizing and/or expanding applications of computer technology.

The academic literature has convincingly noted the growing importance and impact that corporate culture has on the behavior of firms. Correspondingly, industrial sellers are increasingly relying on relationship selling as a key marketing strategy. In conjunction with these two issues, this article demonstrates how capitalizing on an effective understanding of the buyer's corporate culture can be used by sellers to achieve a competitive advantage in developing and maintaining long-term buyer–seller relationships. The implications of this approach are also discussed.

The variables impacting marketers’ motivation to work smarter are examined. These influencing variables are the manager’s venturesomeness, job challenge, effort and skill results, as well as self‐esteem. The model is empirically tested using 273 responses to a questionnaire distributed to marketers using a purchased, national mailing list. The empirical tests were done using a structural equations approach and maximum likelihood estimation. The results indicate that the motivation to work smarter is directly and positively impacted by the manager’s job challenge, effort and skill results, and venturesomeness. The manager’s self‐esteem has positive, indirect impacts on the motivation to work smarter through each of the manager’s venturesomeness, effort and skill results, and job challenge. Based on these results, recommendations on how marketers can be encouraged to work smarter are made.