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Cu isotope systematics of conduit-type Cu–PGE mineralization in the Eastern Gabbro, Coldwell Complex, Canada

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Abstract

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.

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References

  • Albarède F (2004) The stable isotope geochemistry of copper and zinc. In: Geochemistry of non-traditional stable isotopes. Mineralogical Society of America:409–427

  • Albarède F, Beard B (2004) Analytical methods for non-traditional isotopes. Rev Mineral Geochem 55:113–152

    Google Scholar 

  • Ames DE, Kjarsgaard IM, Good DJ, McDonald AM (2016) Ore mineralogy of Cu-PGE mineralized gabbros, Coldwell Alkaline Complex, Midcontinent rift: supporting databases, scanning electron microscope, and mineral chemistry. Geological Survey of Canada

  • Ames DE, Kjarsgaard IM, McDonald AM, Good DJ (2017) Insights into the extreme PGE enrichment of the W Horizon, Marathon Cu-Pd deposit, Coldwell Alkaline Complex, Canada: platinum-group mineralogy, compositions and genetic implications. Ore Geol Rev 90:723–747

    Google Scholar 

  • Asael D, Matthews A, Bar-Matthews M, Halicz L (2007) Copper isotope fractionation in sedimentary copper mineralization (Timna Valley, Israel). Chem Geol 243:238–254

    Google Scholar 

  • Asael D, Matthews A, Oszczepalski S, Bar-Matthews M, Halicz L (2009) Fluid speciation controls of low temperature copper isotope fractionation applied to the Kupferschiefer and Timna ore deposits. Chem Geol 262:147–158

    Google Scholar 

  • Barnes S-J, Ripley EM (2016) Highly siderophile and strongly chalcophile elements in magmatic ore deposits. Rev Mineral Geochem 81:725–774

    Google Scholar 

  • Barnes S-J, Couture J-F, Sawyer EW, Bouchaib C (1993) Nickel-copper occurrences in the Belleterre-Angliers belt of the Pontiac subprovince and the use of Cu-Pd ratios in interpreting platinum-group element distributions. Econ Geol 88:1402–1418

    Google Scholar 

  • Barnes SJ, Mungall JE, Maier WD (2015) Platinum group elements in mantle melts and mantle samples. Lithos 232:395–417

    Google Scholar 

  • Beard BL, Johnson CM (2004) Fe isotope variations in the modern and ancient Earth and other planetary bodies. In: Geochemistry of non-traditional stable isotopes. Mineralogical Society of America, pp 319–357

  • Bradfield A, Barry J, Brown F, Burga D, Feasby DG, Kuchling K, Mackie B, Pitman P, Puritch E (2020) Technical report, updated mineral resource estimate and preliminary economic assessment of the Marathon deposit, Thunday Bay mining district, northwestern Ontario, Canada 48° 45’ N Latitude, 86° 19’ W Longitude. P&E Mining Consultants Inc.

  • Brzozowski MJ, Samson IM, Gagnon JE, Linnen RL, Good DJ, Ames DE, Flemming R (2018) Controls on the chemistry of minerals in late-stage veins and implications for exploration vectoring tools for mineral deposits: an example from the Marathon Cu-Pd deposit, Ontario, Canada. J Geochem Explor 190:109–129

    Google Scholar 

  • Brzozowski MJ, Samson IM, Gagnon JE, Good DJ, Linnen RL (2020a) On the mechanisms for low-sulfide, high-platinum group element and high-sulfide, low-platinum group element mineralization in the eastern gabbro, Coldwell Complex, Canada: evidence from textural associations, S/Se values, and platinum group element concentrations of base metal sulfides. Econ Geol 115:355–384

    Google Scholar 

  • Brzozowski MJ, Samson IM, Gagnon JE, Linnen RL, Good DJ (2020b) Effects of fluid-induced oxidation on the composition of Fe–Ti oxides in the Eastern Gabbro, Coldwell Complex, Canada: implications for the application of Fe–Ti oxides to petrogenesis and mineral exploration. Miner Deposita. https://doi.org/10.1007/s00126-020-00988-4

  • Brzozowski MJ, Samson IM, Gagnon JE, Good DJ, Linnen RL (2020c) Oxide mineralogy and trace-element chemistry as an index to magma evolution and Marathon-type mineralization in the Eastern Gabbro of the alkaline Coldwell Complex. Canada. Miner Deposita. https://doi.org/10.1007/s00126-020-00985-7

  • Campbell IH, Naldrett AJ (1979) The influence of silicate: sulfide ratios on the geochemistry of magnetic sulfides. Econ Geol 74:1503–1506

    Google Scholar 

  • Cao Y, Linnen R, Good D, Samson I, McBride J (2018) Igneous architecture and implications for diverse Cu-PGE mineralization styles in a conduit system: an example from the Area 41 Cu-PGE occurrence, Coldwell Complex, Canada. Miner Deposita 54:1–18

    Google Scholar 

  • Cao Y, Good DJ, Linnen RL, Samson IM (2019) The role of magma injection and crystal sorting in the formation of early gabbros at the Coldwell Complex, Ontario. Canada. Can J Earth Sci:1–23

  • Chi Fru E, Rodríguez NP, Partin CA, Lalonde SV, Andersson P, Weiss DJ, El Albani A, Rodushkin I, Konhauser KO (2016) Cu isotopes in marine black shales record the Great Oxidation Event. Proc Natl Acad Sci 113:4941–4946

    Google Scholar 

  • Eckstrand OR, Hulbert LJ (1987) Selenium and the source of sulfur in magmatic nickel and platinum deposits. In: Geological Association of Canada-Mineralogical Association of Canada. Saskatoon, Canada

  • Eckstrand OR, Sinclair WD, Thorpe RI (1996) Magmatic nickel-copper-platinum group elements. In: Geology of Canadian mineral deposit types. Geological Survey of Canada, p 583

  • Goh SW, Buckley AN, Lamb RN, Rosenberg RA, Moran D (2006) The oxidation states of copper and iron in mineral sulfides, and the oxides formed on initial exposure of chalcopyrite and bornite to air. 19

  • Good DJ (2010) Applying multistage dissolution upgrading and 3D-GIS to exploration at the Marathon Cu-PGE deposit, Canada. In: 11th international platinum symposium. Sudbury, Ontario, Canada

  • Good DJ, Lightfoot PC (2019) Significance of the metasomatized lithospheric mantle in the formation of early basalts and Cu – platinum group element sulfide mineralization in the Coldwell Complex, Midcontinent Rift, Canada. Can J Earth Sci 56:693–714

    Google Scholar 

  • Good DJ, Epstein R, McLean K, Linnen R, Samson I (2015) Evolution of the main zone at the Marathon Cu-PGE sulfide deposit, Midcontinent Rift, Canada: spatial relationships in a magma conduit setting. Econ Geol 110:983–1008

    Google Scholar 

  • Good DJ, Cabri LJ, Ames DE (2017) PGM facies variations for Cu-PGE deposits in the Coldwell Alkaline Complex, Ontario, Canada. Ore Geol Rev 90:748–771

    Google Scholar 

  • Graham S, Pearson N, Jackson S, Griffin W, O’Reilly SY (2004) Tracing Cu and Fe from source to porphyry: in situ determination of Cu and Fe isotope ratios in sulfides from the Grasberg Cu–Au deposit. Chem Geol 207:147–169

    Google Scholar 

  • Haest M, Muchez P, Petit JCJ, Vanhaecke F (2009) Cu isotope variations in the Dikulushi Cu-Ag deposit, DRC: of primary origin or induced by supergene reworking? Econ Geol 104:1055–1064

    Google Scholar 

  • Holwell DA, McDonald I (2010) A review of the behaviour of platinum group elements within natural magmatic sulfide ore systems. Platin Met Rev 54:26–36

    Google Scholar 

  • Huang J, Liu S-A, Wörner G, Yu H, Xiao Y (2016) Copper isotope behavior during extreme magma differentiation and degassing: a case study on Laacher See phonolite tephra (East Eifel, Germany). Contrib Mineral Petrol 171:1–16

    Google Scholar 

  • Ihlenfeld C, Keays RR (2011) Crustal contamination and PGE mineralization in the Platreef, Bushveld Complex, South Africa: evidence for multiple contamination events and transport of magmatic sulfides. Miner Deposita 46:813–832

    Google Scholar 

  • Kerr A, Leitch AM (2005) Self-destructive sulfide segregation systems and the formation of high-grade magmatic ore deposits. Econ Geol 100:311–332

    Google Scholar 

  • Larson PB, Maher K, Ramos FC, Chang Z, Gaspar M, Meinert LD (2003) Copper isotope ratios in magmatic and hydrothermal ore-forming environments. Chem Geol 201:337–350

    Google Scholar 

  • Lesher CM, Burnham OM (2001) Multicomponent elemental and isotopic mixing in Ni–Cu–(PGE) ores at Kambalda, Western Australia. Can Mineral 39:421–446

    Google Scholar 

  • Li W, Jackson SE, Pearson NJ, Alard O, Chappell BW (2009) The Cu isotopic signature of granites from the Lachlan Fold Belt. SE Australia. Chem Geol 12

  • Li W, Jackson SE, Pearson NJ, Graham S (2010) Copper isotopic zonation in the Northparkes porphyry Cu–Au deposit, SE Australia. Geochim Cosmochim Acta 74:4078–4096

    Google Scholar 

  • Lin J, Liu Y, Yang Y, Hu Z (2016) Calibration and correction of LA-ICP-MS and LA-MC-ICP-MS analyses for element contents and isotopic ratios. Solid Earth Sci 1:5–27

    Google Scholar 

  • Liu S-A, Huang J, Liu J, Wörner G, Yang W, Tang Y-J, Chen Y, Tang L, Zheng J, Li S (2015) Copper isotopic composition of the silicate Earth. Earth Planet Sci Lett 427:95–103

    Google Scholar 

  • Maher KC, Larson PB (2007) Variation in copper isotope ratios and controls on fractionation in hypogene skarn mineralization at Coroccohuayco and Tintaya, Perú. Econ Geol 102:225–237

    Google Scholar 

  • Maier WD (2005) Platinum-group element (PGE) deposits and occurrences: mineralization styles, genetic concepts, and exploration criteria. J Afr Earth Sci 41:165–191

    Google Scholar 

  • Maier WD, Barnes S-J (2010) The Kabanga Ni sulfide deposits, Tanzania: II. Chalcophile and siderophile element geochemistry. Miner Deposita 45:443–460

    Google Scholar 

  • Malitch KN, Latypov RM, Badanina Y, Sluzhenikin SF (2014) Insights into ore genesis of Ni-Cu-PGE sulfide deposits of the Noril’sk Province (Russia): evidence from copper and sulfur isotopes. Lithos 204:172–187

    Google Scholar 

  • Marechal CN, Telouk P, Albarede F (1999) Precise analysis of copper and zinc isotopic compositions by plasma-source mass spectrometry. Chem Geol 156:251–273

    Google Scholar 

  • Markl G, Lahaye Y, Schwinn G (2006) Copper isotopes as monitors of redox processes in hydrothermal mineralization. Geochim Cosmochim Acta 70:4215–4228

    Google Scholar 

  • Mason TFD, Weiss DJ, Chapman JB, Wilkinson JJ, Tessalina SG, Spiro B, Horstwood MSA, Spratt J, Coles BJ (2005) Zn and Cu isotopic variability in the Alexandrinka volcanic-hosted massive sulphide (VHMS) ore deposit, Urals, Russia. Chem Geol 221:170–187

    Google Scholar 

  • Mathur R, Ruiz J, Titley S, Liermann L, Buss H, Brantley S (2005) Cu isotopic fractionation in the supergene environment with and without bacteria. Geochim Cosmochim Acta 69:5233–5246

    Google Scholar 

  • Mathur R, Titley S, Barra F, Brantley S, Wilson M, Phillips A, Munizaga F, Maksaev V, Vervoort J, Hart G (2009) Exploration potential of Cu isotope fractionation in porphyry copper deposits. J Geochem Explor 102:1–6

    Google Scholar 

  • Mathur R, Dendas M, Titley S, Phillips A (2010) Patterns in the copper isotope composition of minerals in porphyry copper deposits in southwestern United States. Econ Geol 105:1457–1467

    Google Scholar 

  • Mavrogenes JA, O’Neill HSC (1999) The relative effects of pressure, temperature and oxygen fugacity on the solubility of sulfide in mafic magmas. Geochim Cosmochim Acta 63:1173–1180

    Google Scholar 

  • McBride J (2015) Assessment report for diamond drilling on the Stillwater Canada Inc. Bermuda Property

  • Moeller K, Schoenberg R, Pedersen R-B, Weiss D, Dong S (2012) Calibration of the new certified reference materials ERM-AE633 and ERM-AE647 for copper and IRMM-3702 for zinc isotope amount ratio determinations. Geostand Geoanalytical Res 36:177–199

    Google Scholar 

  • Mudd GM, Jowitt SM (2014) A detailed assessment of global nickel resource trends and endowments. Econ Geol 109:1813–1841

    Google Scholar 

  • Naldrett AJ (2010) From the mantle to the bank: the life of a Ni-Cu-(PGE) sulfide deposit. South Afr J Geol 113:1–32

    Google Scholar 

  • Palme H, O’Neil HSC (2014) Cosmochemical estimates of mantle composition. In: Holland HD, Turekian KK (eds) Treatise on geochemistry, 2nd edn. Elsevier, pp 1–39

  • Queffurus M, Barnes S-J (2015) A review of sulfur to selenium ratios in magmatic nickel-copper and platinum-group element deposits. Ore Geol Rev 69:301–324

    Google Scholar 

  • Ripley EM, Li C (2003) Sulfur isotope exchange and metal enrichment in the formation of magmatic Cu-Ni-(PGE) deposits. Econ Geol 98:635–641

    Google Scholar 

  • Ripley EM, Li C (2013) Sulfide saturation in mafic magmas: is external sulfur required for magmatic Ni-Cu-(PGE) ore genesis? Econ Geol 108:45–58

    Google Scholar 

  • Ripley EM, Dong S, Li C, Wasylenki LE (2015) Cu isotope variations between conduit and sheet-style Ni–Cu–PGE sulfide mineralization in the Midcontinent Rift System, North America. Chem Geol 414:59–68

    Google Scholar 

  • Robb L (2004) Introduction to ore-forming processes, 1st edn. Wiley-Blackwell

  • Rollinson H (1993) Using geochemical data: evaluation, presentation, interpretation. Longman

  • Rouxel O, Fouquet Y, Ludden JN (2004) Copper isotope systematics of the Lucky Strike, Rainbow, and Logatchev sea-floor hydrothermal fields on the Mid-Atlantic Ridge. Econ Geol 99:585–600

    Google Scholar 

  • Ruthart R (2013) Characterization of high-PGE low-sulphur mineralization at the Marathon PGE-Cu deposit. MSc, University of Waterloo, Ontario

    Google Scholar 

  • Samalens N, Barnes S-J, Sawyer EW (2017) The role of black shales as a source of sulfur and semimetals in magmatic nickel-copper deposits: example from the Partridge River Intrusion, Duluth Complex, Minnesota, USA. Ore Geol Rev 81:173–187

    Google Scholar 

  • Samson IM, Fryer BJ, Gagnon JE (2008) The Marathon Cu-PGE deposit. Ontario: insights from sulphide chemistry and textures. p A820

  • Savage PS, Moynier F, Chen H, Shofner G, Siebert J, Badro J, Puchtel IS (2015) Copper isotope evidence for large-scale sulphide fractionation during Earth’s differentiation. Geochem Perspect Lett:53–64

  • Schauble EA (2004) Applying stable isotope fractionation theory to new systems. Rev Mineral Geochem 55:65–111

    Google Scholar 

  • Shahabi Far M (2016) The magmatic and volatile evolution of gabbros hosting the Marathon PGE-Cu deposit: evolution of a conduit system. University of Windsor, PhD dissertation

    Google Scholar 

  • Shahabi Far M, Samson IM, Gagnon JE, Good DJ, Linnen RL, Layne GD, Wing BA (2018) Identifying externally derived sulfur in conduit-type Cu–platinum-group element deposits: the importance of multiple sulfur isotope studies. Geology 46:235–238

    Google Scholar 

  • Shahabi Far M, Samson IM, Gagnon JE, Good DJ, Linnen RL, Ames D (2019) Evolution of a conduit system at the Marathon PGE–Cu deposit: insights from silicate mineral textures and chemistry. J Petrol 60:1–3

    Google Scholar 

  • Smith JW, Holwell DA, McDonald I, Boyce AJ (2016) The application of S isotopes and S/Se ratios in determining ore-forming processes of magmatic Ni–Cu–PGE sulfide deposits: a cautionary case study from the northern Bushveld Complex. Ore Geol Rev 73:148–174

    Google Scholar 

  • Stanton RL (1972) Ore petrology. McGraw-Hill, New York, N.Y.

    Google Scholar 

  • Walker EC, Sutcliff RH, Shaw CSJ, Shore GT, Penczak RS (1993) Precambrian geology of the Coldwell Alkalic Complex. Ontario Geological Survey

  • Watkinson DH, Ohnenstetter D (1992) Hydrothermal origin of platinum-group mineralization in the Two Duck Lake Intrusion, Coldwell Complex, northwestern Ontario. Can Mineral 30:121–136

    Google Scholar 

  • Wilson SA, Ridley WI, Koenig AE (2002) Development of sulfide calibration standards for the laser ablation inductively-coupled plasma mass spectrometry technique. J Anal At Spectrom 17:406–409

    Google Scholar 

  • Ying X, Kiseeva ES, Wade J, Huang F (2019) The effect of core segregation on the Cu and Zn isotope composition of the silicate Moon. Geochem Perspect Lett

  • Zhao Y, Xue C, Liu S-A, Symons DTA, Zhao X, Yang Y, Ke J (2017) Copper isotope fractionation during sulfide-magma differentiation in the Tulaergen magmatic Ni–Cu deposit, NW China. Lithos 286–287:206–215

    Google Scholar 

  • Zhao Y, Xue C, Liu S-A, Mathur R, Zhao X, Yang Y, Dai J, Man R, Liu X (2019) Redox reactions control Cu and Fe isotope fractionation in a magmatic Ni–Cu mineralization system. Geochim Cosmochim Acta 249:42–58

    Google Scholar 

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Acknowledgments

The authors would like to thank John McBride of Generation Mining Ltd. for permitting the use of the samples. The authors would also like to thank Jiaxin She, Zhiguang Xia, Chuan Liu, Shugao Zhao, and Weihao Yan from the State Key Laboratory for Mineral Deposits Research, Nanjing University for their help in operating instruments. The authors are grateful to two anonymous reviewers, J. Smith, Associate Editor David Banks, and Editor-in-Chief Georges Beaudoin for their constructive comments and revisions that greatly improved the quality of the manuscript.

Funding

This study was financially supported by the Natural Science Foundation of China (No. 41622301 to WL).

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  1. State Key Laboratory for Mineral Deposits Research, School of Earth Sciences and Engineering, Nanjing University, 163 Xianlin Rd, Qixia District, Nanjing, 210023, Jiangsu, China

    Matthew J. Brzozowski, Changzhi Wu & Weiqiang Li

  2. Department of Earth Sciences, Western University, 1151 Richmond St, London, ON, N6A 3K7, Canada

    David J. Good

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Brzozowski, M.J., Good, D.J., Wu, C. et al. Cu isotope systematics of conduit-type Cu–PGE mineralization in the Eastern Gabbro, Coldwell Complex, Canada. Miner Deposita 56, 707–724 (2021). https://doi.org/10.1007/s00126-020-00992-8

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