Abstract—
The paper presents new data on the trace-element (REE, Y, and Sr) composition of calcite from stockwork Au–Cu porphyry ores and host rocks of the Kutuevsky occurrence, South Urals. Trace elements were analyzed by LA–ICP–MS in calcite and by ICP-MS in intrusive rocks and ophicalcite. We established that REE amounts and patterns of the calcite significantly varied and depend on the ore mineralization location in the metasomatic aureole. The ores in chlorite–sericite–quartz metasomatites in the central part of the gabbro-diorite and diorite intrusion are dominated by calcite, whose REE amounts and patterns are comparable to those of the intrusive rocks. We suggest that REE in the crystallized calcite were borrowed by fluid mainly from the intrusive rocks. Calcite in the ores hosted by biotite–epidote–chlorite–sericite–quartz metasomatites in the eastern inner-contact zone of the intrusive massif contains abnormally low REE amounts. The most likely REE source for this calcite is assumed to be the carbonate cement of the ophicalcites. REE fractionation was largely controlled by fluid temperature. When the calcite crystallized, the mineral-forming temperature exceeded 250°C, and therefore, Eu2+ dominated in the fluid, and the regime was reducing.
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REFERENCES
A. Abedini, A. A. Calagari, and H. Naseri, “Mineralization and REE geochemistry of hydrothermal quartz and calcite of the Helmesi copper deposit, NW Iran,” N. Jb. Geol. Paläont. Abh. 281/2, 123–134 (2016).
M. Bau and P. Dulski, “Comparative study of yttrium and rare-earth behaviors in fluorine-rich hydrothermal fluids,” Contrib. Mineral. Petrol. 119, 213–223 (1995).
M. Bau and P. Möller, “Rare earth element fractionation in metamorphogenic hydrothermal calcite, magnesite and siderite,” Mineral. Petrol. 45, 231–246 (1992).
F. Castorina and U. Masi, “REE and Nd-isotope evidence for the origin siderite from the Jebel Awam deposit (Central Morocco),” Ore Geol. Rev. 34, 337–342 (2008).
D. R. Cooke, P. Hollings, J. J. Wilkinson, and R. M. Tosdal, “Geoshemistry of porphyry deposits,” Treatise on Geochemistry, Ed. by H. D. Holland and K. K. Turekian, 2nd Ed. (Springer, 2014), Vol. 13, pp. 357–381.
D. Debruyne, N. Hulsbosch, and P. Muchez, “Unraveling rare earth element signatures in hydrothermal carbonate minerals using a source-sink system,” Ore Geol. Rev. 72, 232–252 (2016).
A. I. Grabezhev, “Sr–Nd–C–O–H–S isotope-geochemical characteristics of copper porphyry fluid–magmatic systems of the South Urals: possible sources of matter,” Litosfera, No. 6, 66–89 (2009).
A. I. Grabezhev and Yu. L. Ronkin, “U-Pb age of zircons from ore-bearing granitoids of the copper porphyry deposits of the South Urals,” Litosfera 3, 104–116 (2011).
V. N. Kuleshov, Isotope Composition and Origin of Deep-Seated Carbonates, Moscow: Nauka, 1986 [in Russian].
A. Michard, “Rare earth element systematics in hydrothermal fluids,” Geochim. Cosmochim. Acta. 53, 745–750 (1989).
A. A. Migdisov, A. E. Williams-Jones, and T. Wagner, “An experimental study of the solubility and speciation of the rare earth elements (III) in fluoride- and chloride-bearing aqueous solutions at temperatures up to 300 °C,” Geochim. Cosmochim. Acta. 73, 7087–7109 (2009).
P. Möller and G. Morteani, “On the geochemical fractionation of ram earth elements during the formation of Ca-minerals and its application to problems of the genesis of ore deposits,” The Significance of Trace Elements in Solving Petrogenetic Problems and Controversies, Ed. by S. S. Augusthitis (Theophrastus, Athens, 1983), pp. 747–791.
P. Möller, I. Stober, and P. Dulski, “Seltenerdelement-, yttrium-gehalte und bleiisotope in thermal- und mineralwässern des schwarzwaldes,” Grundwasser 2, 118–132 (1997).
P. Möller, P. Dulski, Y. Savascin, and M. Conrad, “Rare earth elements, yttrium and Pb isotope ratios in thermal spring and well waters of West Anatolia, Turkey: a hydrochemical study of their origin,” Chem. Geol. 206, 97–118 (2004)
H. Ohmoto and M. B. Goldhaber, “Sulfur and carbon isotopes,” Geochemistry of Hydrothermal Ore Deposits (Wiley and Sons, 1997), pp. 517–611.
V. Yu. Prokofiev, N. S. Bortnikov, V. A. Kovalenker, S. F. Vinokurov, L. D. Zorina, A. D. Chernova, S. G. Kryazhev, N. N. Krasnov, and S. A. Gorbacheva, “The Darasun gold deposit, eastern Transbaikal region: chemical composition, REE patterns, and stable carbon and oxygen isotopes of carbonates from ore veins,” Geol. Ore Deposits 52 (2), 91–125 (2010).
J. P. Richards, T. Spell, E. Rameh, A. Razique, and T. Fletcher, “High Sr/Y magmas reflect arc matyrity, high magmatic water content, and porphyry Cu ± Mo ± Au potential: examples from the Tethyan arcs of Central and Eastern Iran and Western Pakistan,” Econ. Geol. 107, 295–332 (2012).
H. R. Rollinson, Using Geochemical Data: Evaluation, Presentation, Interpretation (Longman Scientific and Technical, London, 1993).
G. Schwinn and G. Markl, “REE systematics in hydrothermal fluorite,” Chem. Geol. 216, 225–248 (2005).
R. D. Shannon, “Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides,” Acta Crystallogr. Sect. A. 32, 751–767 (1976).
S. M. F. Sheppard, “Characterization and isotopic variations in natural waters,” Rev. Mineral. 16, 70–78 (1986).
R. H. Sillitoe, “Porphyry Copper Systems,” Econ. Geol. 105, 3–41 (2010).
D. A. Sverjensky, “Europium redox equilibria in aqueous solution,” Earth Planet Sci. Lett. 67, 70–78 (1984).
B. Taylor, “Magmatic volatiles: Isotopic variation of C, H, and S,” In Stable Isotopes in High Temperature Geological Processes, Mineral. Soc. Am., Rev. Mineral., Ed. by J. W. Valley et al., 6, 185–225 (1986).
S. L. Votyakov, D. V. Kiseleva, E. S. Shagalov, N. V. Cherednichenko, L. K. Deryugina, S. A. Denisov, A. P. Chempalov, S. E. Uzkikh, and A. A. Orekhov, “Multielement analysis of geological samples by inductively coupled mass spectrometry on an ELAN 9000,” Yearbook-2005, Tr. Inst. Geol. Geokhim. im. akad. A.N. Zavaritskogo 153, 425–430 (2006).
Y.-F. Zheng, “Oxygen isotope fractionation in carbonate and sulfate minerals,” Geochem. J. 33, 109–126 (1999).
S. E. Znamensky and N. M. Znamenskaya, “Distribution of rare-earth elements and yttrium in calcite from the Au–Cu-porphyry ores and host rocks of the Kutuev occurrence (South Urals),” Geologicheskii vestnik. (1), 98–104 (2021).
S. E. Znamensky, N. N. Ankusheva, and N. M. Znamenskaya, “Conditions of formation of the Au–Cu-porphyry mineralization of the Kutuev occurrence (South Urals),” Geol. Izv. Otd. Nauk o Zemle Prir. Resur. AN RB. 26, 8–13 (2019a).
S. E. Znamensky, A. M. Kosarev, and G. T. Shafigullina, “Facies composition, geochemical features, and geodynamic settings of the formation of Late Emsian island arc complexes of the Main Uralian Fault at the South Urals,” Vestn. Permsk. Univ., Geologiya 18 (1), 1–16 (2019b).
S. E. Znamensky, N. N. Ankusheva, and D. A. Artem’ev, “Conditions of formation, composition, and sources of ore-forming fluids of the Bol’shoi Karan gold porphyry deposit, South Urals,” Litosfera 20 (3), 397–410 (2020).
S. E. Znamensky, N. N. Ankusheva, and A. V. Snachev, “The formation conditions and sources of ore-forming fluids of the Nikolaevskoe gold deposit (South Urals),” Russ. Geol. Geophys. 61 (8), 828–837 (2020).
Funding
This study was conducted under government-financed research projects FMRS-2022-0011 for the Institute of Geology, Ufa Federal Research Center, Russian Academy of Sciences, and AAAA-A19-119061790049-3 for the Institute of Mineralogy, South Urals Federal Research Center of Mineralogy and Geoecology, Ural Branch, Russian Academy of Sciences.
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Znamensky, S.E., Artemyev, D.A. & Ankusheva, N.N. REE in the Calcite of Au–Cu Porphyry Mineralization at the Kutuevsky Occurrence, South Urals: LA–ICP–MS Data. Geochem. Int. 60, 830–840 (2022). https://doi.org/10.1134/S0016702922090105
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DOI: https://doi.org/10.1134/S0016702922090105