Skip to main content

Origin of native copper in the Paraná volcanic province, Brazil, integrating Cu stable isotopes in a multi-analytical approach

Mineralium Deposita volume 53, pages 417–434 (2018)Cite this article

Abstract

Different hypotheses exist on the origin of native copper mineralization in the Paraná volcanic province that invoke magmatic, late magmatic, or hydrothermal events. The average copper content in the host basalts is ~200 ppm. Native copper occurs as dendrites in cooling joints, fractures, and cavities within amygdaloidal crusts. Cuprite, tenorite, chrysocolla, malachite, and azurite occur in breccias at the top of the lava flows. Chemical analyses, X-ray diffraction, Raman spectrometry, electron microprobe analyses, LA-ICP-MS, and Cu isotope analyses were used to evaluate the origin of native copper in the volcanic province. Copper contents in magnetite of the host basalt are close to 1 wt.%, whereas clinopyroxene contains up to 0.04 wt.% Cu. Cretaceous hydrothermal alteration of magnetite and clinopyroxene released copper to generate hydrothermal copper mineralization. The isotopic composition of the native copper in the Paraná volcanic province varies from −0.9‰ in the southeastern portion (Rio Grande do Sul state) to 1.9‰ in the central portion (Paraná state) of the province. This study supports a hydrothermal origin followed by supergene enrichment for native copper in the Paraná volcanic province.

This is a preview of subscription content, access via your institution.

Access options

Buy single article

Instant access to the full article PDF.

USD 39.95

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11

References

  • Albarède F (2004) The stable isotope geochemistry of copper and zinc. Rev Mineral Geochem 55:409–427

    Article  Google Scholar 

  • Almeida FFM (1986) Distribuição regional e relações tectônicas do magmatismo pós-paleozóico no Brasil. Rev Bras Geociências 16:325–349

    Google Scholar 

  • Arena KR, Hartmann LA, Baggio SB (2014) Geological controls of copper, gold and silver in the Serra Geral Group, Realeza region, Paraná, Brazil. Ore Geol Rev 63:178–200

    Article  Google Scholar 

  • Arioli EE (2008) Arquitetura faciológica da sequência vulcânica e o significado exploratório das anomalias geoquímicas de elementos do grupo da platina (EGP) e metais associados no sistema magmático Serra Geral, Estado do Paraná, Brasil. PhD Thesis, Universidade Federal do Paraná, Curitiba, Brazil, 262 p.

  • 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

    Article  Google Scholar 

  • Bellieni G, Comin-Chiaramonti P, Marques LS, Melfi AJ, Piccirillo EM, Nardy AJ, Roisenberg A (1984) High- and low-Ti flood basalts from the Paraná Plateau (Brazil): petrology and geochemical aspects bearing on their mantle origin. Neues Jahrb Mineral Abh 150:272–306

    Google Scholar 

  • Bornhorst TJ, Barron RJ (2011) Copper deposits of the western Upper Peninsula of Michigan. Geol Soc Am 24:83–99

    Google Scholar 

  • Butler BS, Burbank WS (1929) The copper deposits of Michigan. U.S. Government printing office, 238pp. Washington

  • Cabral AR, Beaudoin G (2007) Volcanic red-bed copper mineralization related to submarine basalt alteration, Mont Alexandre, Quebec Appalachians, Canada. Mineral Deposita 42:901–912

    Article  Google Scholar 

  • Carr PF, Pemberton JW, Nunan E (1999) Low-grade metamorphism of mafic lavas, upper Permian Broughton Formation, Sydney Basin. Aust J Earth Sci 46:839–849

    Article  Google Scholar 

  • Cornwall HR (1956) A summary of ideas on the origin of native copper deposits. Econ Geol 51:615–631

    Article  Google Scholar 

  • Costa AFU (1982) Geologia aplicada à prospecção de cobre em basaltos na área de Vista Alegre: Frederico Westphalen, RS. Acta Geol Leopold 11:17–36

    Google Scholar 

  • Dekov VM, Rouxel O, Asael D, Hålenius U, Munnik F (2013) Native Cu from the oceanic crust: isotopic insights into native metal origin. Chem Geol 359:136–149

    Article  Google Scholar 

  • Duarte LC, Hartmann LA, Vasconcelos MAS, Medeiros JTN, Theye T (2009) Epigenetic formation of amethyst-bearing geodes from Los Catalanes gemological district, Artigas, Uruguay, southern Paraná Magmatic Province. J Volcanol Geoth Res 184:427–436

    Article  Google Scholar 

  • Duarte LC, Hartmann LA, Ronchi LH, Berner Z, Theye T, Massonne HJ (2011) Stable isotope and mineralogical investigation of the genesis of amethyst geodes in the los Catalanes gemological district, Uruguay, southernmost Paraná volcanic province. Mineral Deposita 46:239–255

    Article  Google Scholar 

  • Frank HT, Gomes MEB, Formoso ML (2009) Review of the areal extent and the volume of the Serra Geral Formation, Paraná Basin, South America. Pesquisas em Geociências UFRGS 36:49–57

    Google Scholar 

  • Gilg HA, Morteani G, Kostitsyn Y, Preinfalk C, Gatter I, Strieder AJ (2003) Genesis of amethyst geodes in basaltic rocks of the rocks of the Serra Geral Formation (Ametista do Sul, Rio Grande do Sul, Brazil): a fluid inclusion, REE, oxygen, carbon and Sr isotope study on basalt, quartz, and calcite. Mineral Deposita 38:1009–1025

    Article  Google Scholar 

  • Gilg HA, Krüger Y, Taubald H, van der Kerkhof AM, Frenz M, Morteani G (2014) Mineralisation of amethyst-bearing geodes in Ametista do Sul (Brazil) from low-temperature sedimentary brines: evidence from monophase liquid inclusions and stable isotopes. Mineral Deposita 49:861–877

    Article  Google Scholar 

  • Gordon Jr M (1947) Classification of the Gondwanic rocks of Paraná, Santa Catarina and Rio Grande do Sul. Rio de Janeiro: DNPM, Divisão de Geologia e Mineralogia, Notas Preliminares e Estudos 38a:1–19

  • Graham S, Pearson N, Jackson S, Griffin W, O’Reilly S (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

    Article  Google Scholar 

  • Greenberger RN, Mustard JF, Kumar PS, Dyar MD, Breves EA, Sklute EC (2012) Low temperature aqueous alteration of basalt: mineral assemblages of Deccan basalts and implication for Mars. J Geophys Res 117:E00J12

    Article  Google Scholar 

  • Hartmann LA (2008) Amethyst geodes formed from hot water in dinosaur times, 1st edn. UFRGS, Porto Alegre 57 pp

    Google Scholar 

  • Hartmann LA, Wildner W, Duarte LC, Duarte SK, Pertille J, Arena KR, Martins LC, Dias N.L (2010) Geochemical and scintillometric characterization and correlation of amethyst-bearing Paraná lavas from the Quaraí and Los Catalanes districts, Brazil and Uruguay. Geol Mag 147:954–970

  • Hartmann LA, Duarte LC, Massonne HJ, Michelin C, Rosenstengel LM, Bergmann M, Theye T, Pertille J, Arena KR, Duarte SK, Pinto VM, Barboza EG, Rosa MLCC, Wildner W (2012a) Sequential opening and filling of cavities forming vesicles, amygdales and giant amethyst geodes in lavas from the southern Paraná volcanic province, Brazil and Uruguay. Int Geol Rev 54:1–14

    Article  Google Scholar 

  • Hartmann LA, Medeiros JTN, Petruzzellis LT (2012b) Numerical simulations of amethyst geode cavity formation by ballooning of altered Paraná volcanic rocks, South America. Geofluids 12:133–141

    Article  Google Scholar 

  • Horn I, von Blanckenburg F (2007) Investigation on elemental and isotopic fractionation during 196 nm femtosecond laser ablation multiple collector inductively coupled plasma mass spectrometry. Spectrochim Acta B 62:410–422

    Article  Google Scholar 

  • Horn I, von Blanckenburg F, Schoenberg R, Steinhoefel G, Markl G (2006) In situ iron isotope ratio determination using UV-femtosecond laser ablation with application to hydrothermal ore formation processes. Geochim Cosmochim Acta 70:3677–3688

    Article  Google Scholar 

  • Hussak E (1906) Ueber das Vorkommen von gediegen Kupfer in den Diabasen von São Paulo. Centralb Mineral, pp 333–335

  • Ikehata K, Hirata T (2012) Copper isotope characteristics of copper-rich minerals from the Horoman peridotite complex, Hokkaido, northern Japan. Econ Geol 107:1489–1497

    Article  Google Scholar 

  • Ikehata K, Notsu K, Hirata T (2011) Copper isotope characteristics of copper-rich minerals from Besshi-type volcanogenic massive sulfide deposits, Japan, determined using a femtosecond LA-MC-ICP-MS. Econ Geol 106:307–316

    Article  Google Scholar 

  • Janasi VA, Freitas VA, Heaman LH (2011) The onset of flood basalt volcanism, Northern Paraná Basin, Brazil: a precise U Pb baddeleyite/zircon age for a Chapecó-type dacite. Earth Planet Sci Lett 302:147–153

    Article  Google Scholar 

  • Juchem PL (2014) Amethyst mineralization in rhyodacites of the Serra Geral Group, Paraná volcanic Province. In: Hartmann LA, Baggio SB (orgs) Metallogeny and mineral exploration in the Serra Geral Group, 1st ed. UFRGS, Porto Alegre, pp 321–334

  • 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

    Article  Google Scholar 

  • Lazarov M, Horn I (2015) Matrix and energy effects during in situ determinations of Cu isotope ratios by UV-femtosecond laser ablation multicollector inductively coupled plasma mass spectrometry. Spectrochim Acta B 111:64–73

    Article  Google Scholar 

  • Le Bas MJ, Le Maitre RW, Streckeisen A, Zanettin B (1986) A chemical classification of volcanic-rocks based on the total alkali sílica diagram. J Petrol 3:745–750

    Article  Google Scholar 

  • Li H, Mao J, Chen Y, Wang D, Zhang C, Xu H (2005) Epigenetic hydrothermal features of the Emeishan basalt copper mineralization in NE Yunnan, SW China. In: Mao J, Bierlein FP (eds) Mineral deposit research: meeting the global challenge. Springer Berlin Heidelberg, Beijing, pp 149–152

    Chapter  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 Sc Lett 427:95–103

    Article  Google Scholar 

  • Livnat A (1983) Metamorphism and copper mineralization of the Portage Lake Lava Series, northern Michigan. PhD Thesis, University of Michigan, Ann Arbor, USA

  • Lore J, Gao H, Aydin A (2000) Viscoelastic thermal stress in cooling basalt flows. J Geophys Res 105:695–709

    Article  Google Scholar 

  • Maher KC (2005) Analysis of copper isotope ratios by multi-collector inductively coupled plasma mass spectrometry and interpretation of copper isotope ratios from copper mineralization. PhD Thesis, Washington State University, USA, 239 pp

  • Mantovani MSM, Marques LS, De Sousa MA, Civetta L, Atalla L, Innocenti F (1985) Trace element and strontium isotope constraints on the origin and evolution of Paraná continental flood basalts of Santa Catarina state (southern Brazil). J Petrol 26:187–209

    Article  Google Scholar 

  • Maréchal C, Sheppard SMF (2002) Isotopic fractionation of Cu and Zn between chloride and nitrate solutions and malachite or smithsonite at 30° and 50° C. Geochim Cosmochim Acta 66:A484

    Google Scholar 

  • Maréchal C, Télouk P, Albarède F (1999) Precise analysis of copper and zinc isotopic compositions by plasma-source mass spectrometry. Chem Geol 156:251–273

    Article  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

    Article  Google Scholar 

  • Massonne HJ, Opitz J, Theye T, Nasir S (2013) Evolution of a very deeply subducted metasediment from As Sifah, northeastern coast of Oman. Lithos 156 – 159:171–185

    Article  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

    Article  Google Scholar 

  • Mathur R, Ruiz J, Casselman MJ, Megaw P, Van Egmond R (2012) Use of Cu isotopes to distinguish primary and secondary Cu mineralization in the Cañarico Norte porphyry copper deposit, Northern Peru. Mineral Deposita 47:755–762

    Article  Google Scholar 

  • Melfi AJ, Piccirillo EM, Nardy AJR (1988) Geological and magmatic aspects of the Paraná Basin an introduction. In: Piccirillo EM, Melfi AJ (eds) The Mesozoic flood volcanism of the Paraná Basin: Petrogenetic and geophysical aspects. IAG, USP, São Paulo, pp 1–13

    Google Scholar 

  • Mello SK (2000) Estudo petrológico da região de Água Perdida no vale do Rio Piquiri – PR: Reconhecimento das mineralizações de cobre e produtos de alteração em rochas básicas da Formação Serra Geral – Bacia do Paraná. PPGeo UNISINOS, São Leopoldo, Brazil

    Google Scholar 

  • Meunier A (2005) Clays. Springer Berlin Heidelberg, New York 472 p

    Google Scholar 

  • Morteani G, Kostitsyn Y, Preinfalk C, Gilg HA (2010) The genesis of the amethyst geodes at Artigas (Uruguay) and the paleohydrology of the Guarani aquifer: structural, geochemical, oxygen, carbon, strontium isotope and fluid inclusion study. Int J Earth Sci 99:927–947

    Article  Google Scholar 

  • Nakamura K, Wildner W, Shibuya A, Masuta K, Murakami T, Romanini S (2003) Mineral exploration of the Cu–Ni PGE deposits in the Paraná Basin, Southern Brazil, phase II. Tokyo, Japan Mining Engineering Center for International Cooperation–JMEC/Geological Survey of Brazil–CPRM, Porto Alegre, Brazil

  • Oeser M, Weyer S, Horn I, Schuth S (2014) High-precision Fe and Mg isotope ratios of silicate reference glasses determined in situ by femtosecond LA-MC-ICP-MS and by solution nebulisation MC-ICP-MS. Geostand Geoanal Res 38:311–328

    Article  Google Scholar 

  • Peate DW (1997) The Paraná-Etendeka Province. In: Mahoney JJ, Coffin MR (eds) Large igneous provinces: continental, oceanic, and planetary flood volcanism, Geophysical Monograph Series, vol vol 100. American Geophysical Union, Washington DC, pp 217–245

    Google Scholar 

  • Peate DW, Hawkesworth CJ, Mantovani MSM (1992) Chemical stratigraphy of the Paraná lavas (South America): classification of magma types and their spatial distribution. Bull Volcanol 55:119–139

    Article  Google Scholar 

  • Peate DW, Hawkesworth CJ, Mantovani MSM, Rogers NW, Turner SP (1999) Petrogenesis and stratigraphy of the high-Ti/Y Urubuci magma type in the Paraná flood basalt province and implications for the nature of ‘Dupal’-type mantle in the south Atlantic region. J Petrol 40:451–473

    Article  Google Scholar 

  • Peck DL, Minakami T (1968) Formation of columnar joints in the upper part of Kilauean lava lakes, Hawaii. Bull Geol Soc Am 79:1151–1166

    Article  Google Scholar 

  • Pinto VM, Hartmann LA (2011) Flow-by-flow chemical stratigraphy and evolution of thirteen Serra Geral Group basalt flows from Vista Alegre, southernmost Brazil. An Acad Bras Ciênc 83:425–440

    Article  Google Scholar 

  • Pinto VM, Hartmann LA, Santos JOS, McNaughton NJ, Wildner W (2011a) Zircon U–Pb geochronology from the Paraná bimodal volcanic province support a brief eruptive cycle at 135 Ma. Chem Geol 281:93–102

    Article  Google Scholar 

  • Pinto VM, Hartmann LA, Wildner W (2011b) Epigenetic hydrothermal origin of native copper and supergene enrichment in the Vista Alegre district, Paraná basaltic province, southernmost Brazil. Int Geol Rev 53:1163–1179

    Article  Google Scholar 

  • Rosenstengel LM, Hartmann LA (2012) Geochemical stratigraphy of lavas and fault-block structures in the Ametista do Sul geode mining district, Paraná volcanic province, southern Brazil. Ore Geol Rev 48:332–348

    Article  Google Scholar 

  • Seo JH, Lee SK, Lee I (2007) Quantum chemical calculations of equilibrium copper (I) isotope fractionations in ore-forming fluids. Chem Geol 243:225–237

    Article  Google Scholar 

  • Sherman DM (2013) Equilibrium isotopic fractionation of copper during oxidation/reduction, aqueous complexation and ore-forming processes: predictions from hybrid density functional theory. Geochim Cosmochim Acta 118:85–97

    Article  Google Scholar 

  • Shields WR, Goldich SS, Garner EL, Murphy TJ (1965) Natural variations in the abundance ratio and the atomic weight of copper. J Geophys Res 70:479–491

    Article  Google Scholar 

  • Szubert EC, Grazia CA, Shintaku I (1979) Projeto Cobre em Itapiranga. CPRM SUREG, Porto Alegre 474 pp

    Google Scholar 

  • Tazaki K, Fyfe WS, Tazaki K, Bischoff J, Rocha BR (1988) Occurrence of copper films in basalt from the Serra Geral formation, Paraná Basin, Brazil. Rev Bras Geoc 18:332–337

    Google Scholar 

  • White C (1908) Relatório Final. Comissão de Estudos das Minas de Carvão de Pedra do Brazil. Imprensa Nacional, Rio de Janeiro. Re-impressão - Edição Comemorativa: 100 anos do Relatório White, CPRM, 2008, Belo Horizonte, 617 pp

  • Wildner W, Hartmann LA, Cunha-Lopes R (2009) A proposed stratigraphy for the Serra Geral Group in the Paraná Basin. In: Milani EJ, Chemale F Jr (eds) Correlation Brazil–Africa. PETROBRAS, Gramado

    Google Scholar 

  • Xu W, Van der Voo R, Peacor DR, Beaubouef RT (1997) Alteration and dissolution of fine-grained magnetite and its effects on magnetization of the ocean floor. Earth Planet Sci Lett 151:279–288

    Article  Google Scholar 

  • Yui TF, Chang SS (1999) Formation conditions of vesicle/fissure-filling smectites in Penghu basalts: a stable-isotope assessment. Clay Miner 34:381–393

    Article  Google Scholar 

  • Zhang D, Zhou T, Yuan F, Fiorentini ML, Said N, Lu Y, Pirajno F (2013) Geochemical and isotopic constraints on the genesis of the Jueluotage native copper mineralized basalt, Eastern Tianshan, Northwest China. J Asian Earth Sci 73:317–333

    Article  Google Scholar 

  • Zhu XK, O’Nions RK, Guo Y, Belshaw NS, Rickard D (2000) Determination of natural Cu-isotope variation by plasma-source mass spectrometry: implications for use as geochemical tracers. Chem Geol 163:139–149

    Article  Google Scholar 

Download references

Acknowledgements

The financial support was provided by Project VALE/CNPq, MCT, and Mineral Sector Fund (CT-Mineral) entitled “Desenvolvimento de metodologia de exploração geológica para geodos de ametista e ágata, cobre e outros bens minerais em ambiente hidrotermal do Grupo Serra Geral, sul-sudeste do Brasil” and project of excellence PRONEX-FAPERGS/CNPq on strategic minerals from southern Brazil, coordinated by Léo A. Hartmann. The authors wish to thank P.C. Soares, A.R. Cabral, three anonymous reviewers and the editors Frank Melcher and Georges Beaudoin for their comments that helped to improve the manuscript.

Author information

Authors and Affiliations

  1. Universidade Federal do Rio Grande do Sul, Porto Alegre, Rio Grande do Sul, Brazil

    Sérgio Benjamin Baggio & Léo Afraneo Hartmann

  2. Leibniz Universität Hannover, Hannover, Germany

    Marina Lazarov

  3. Universität Stuttgart, Stuttgart, Germany

    Hans-Joachim Massonne, Joachim Opitz, Thomas Theye & Tillmann Viefhaus

Authors
  1. Sérgio Benjamin Baggio
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Léo Afraneo Hartmann
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Marina Lazarov
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Hans-Joachim Massonne
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Joachim Opitz
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Thomas Theye
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Tillmann Viefhaus
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Sérgio Benjamin Baggio.

Additional information

Editorial handling: F. Melcher

Electronic supplementary material

ESM 1

(PDF 86 kb)

ESM 2

(PDF 13 kb)

ESM 3

(XLS 35 kb)

ESM 4

(XLS 41 kb)

ESM 5

(XLS 44 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Baggio, S.B., Hartmann, L.A., Lazarov, M. et al. Origin of native copper in the Paraná volcanic province, Brazil, integrating Cu stable isotopes in a multi-analytical approach. Miner Deposita 53, 417–434 (2018). https://doi.org/10.1007/s00126-017-0748-2

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00126-017-0748-2

Keywords

  • Paraná volcanic province
  • Native copper
  • Copper isotopes
  • Hydrothermal mineralization