Next Article in Journal
Fibrous Ferrierite from Northern Italy: Mineralogical Characterization, Surface Properties, and Assessment of Potential Toxicity
Previous Article in Journal
Research on Factors Affecting Mine Wall Stability in Isolated Pillar Mining in Deep Mines
 
 
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Occurrences of Pd–Pt Bismuthotellurides and a Phosphohedyphane-Like Phase in Sulfide Veins of the Monchepluton Layered Complex, Kola Peninsula, Russia

1
Research Laboratory of Industrial and Ore mineralogy, Cherepovets State University, 162600 Cherepovets, Russia
2
Department of Earth and Planetary Sciences, McGill University, Montreal, QC H3A 0E8, Canada
*
Author to whom correspondence should be addressed.
Submission received: 25 April 2022 / Revised: 5 May 2022 / Accepted: 7 May 2022 / Published: 14 May 2022

Abstract

:
We describe occurrences of platinum-group minerals (PGM) and an uncommon mineral enriched in Cl, and provide a brief review of Cl-bearing minerals associated with basic–ultrabasic complexes. An unusual phosphohedyphane-like phase (~30 µm), close to CaPb4(PO4)3Cl, occurs in one of the PGM-bearing veins of massive sulfides in the Monchepluton layered complex, Kola Peninsula, Russia. These veins consist of varying amounts of pyrrhotite, pentlandite, chalcopyrite, pyrite and accessory grains of galena; they are fairly abundant in the heavy-mineral concentrate, as are small (<0.1 mm) grains of PGM: michenerite, sperrylite, Bi-enriched members of the merenskyite–moncheite series and kotulskite, also rich in Bi. The PGE mineralization is attributed to a low-temperature deposition at the hydrothermal stage. The pyromorphite–phosphohedyphane solid solution likely formed as a secondary phase under conditions of a progressive build-up of oxygen fugacity via oxidation reactions of a precursor grain of galena and involving Ca, as an incompatible component of the sulfides, in a medium of residual fluid enriched in Cl.

1. Introduction

A detailed investigation of ore veins sampled at the site of long-abandoned mine adits in the Monchepluton layered basic–ultrabasic complex has led to the discovery of a member of the pyromorphite–phosphohedyphane solid solution among the ore constituents. As a chlorine-bearing member of the apatite supergroup, its presence in a vein of pyrrhotite, pentlandite, chalcopyrite, pyrite, galena and platinum-group minerals (PGM) raises questions about the role of Cl and other volatiles in mineralized ultrabasic suites. Our aims are to describe the occurrence, documented for the first time in a vein of massive Cu–Ni sulfides bearing platinum-group elements (PGE) at Mount Nittis, in the Monchepluton layered mafic–ultramafic complex of Paleoproterozoic (~2.5 Ga) age [1,2]. We explore what is known about the pyromorphite–phosphohedyphane solid-solution series and document the associated PGM. We believe that this phase is significant not only as a new representative of Cl-bearing minerals associated with ore zones, but also as a monitor of a progressive build-up in levels of oxygen fugacity (fO2) during ore formation.

Geological Background

The Monchepluton layered complex belongs to an extensive group of Paleoproterozoic layered intrusions in the Fennoscandian Shield, e.g., [2]. It is located at the boundary of the Imandra–Varzuga zone of the Polmak–Pasvik–Pechenga–Imandra–Varzuga rift of Paleoproterozoic age with the Archean Kola–Norwegian terrane of the Kola Province (Figure 1).
The Monchepluton complex consists of sequences of dunite–harzburgite–orthopyroxenite–gabbronorite [4,5,6,7]. Seven divisions are recognized: the Dunite block, mounts Nittis, Kumuzhya, and Travyanaya along a northeasterly trend, and mounts Sopcha, Nyud, and Poaz on an easterly trend (Figure 2). The Dunite block, which hosts the Sopcheozyorskoe chromite deposit [8], may correspond to the location of the magma-feeder channel [5]. This block represents a podiform or core-like zone of olivine and olivine–chromite cumulates formed close to the nexus of the boomerang-shaped structure [5].

2. Materials and Methods

Our materials consist of ore samples and heavy-mineral concentrates obtained from three samples (10–15 kg each) of Ni–Cu–PGE ores collected at old mine adits (67°55′18.4″ N 32°46′46.6″ E; 67°55′25.1″ N 32°46′27.3″ E; 67°55′31.7″ N 32°46′44.9″ E) known historically and built during the years 1933–1936 (Figure 2). The fragments of ore are dense, massive, and coated by an oxidized rind (Figure 3a,b). They consist of pyrrhotite, pentlandite, chalcopyrite and less-abundant pyrite, in varying proportions. The heavy-mineral concentrates studied consist of ~10 to 100 micrometer-sized fractions of galena, grains of platinum-group minerals (PGM), followed by minor amounts of barite, and remnant grains of base-metal sulfides, mostly pentlandite. By interpolation, the density of our member of the apatite supergroup is approximately 6.5 g/cm3.
The phosphohedyphane-type phase occurs in a single subhedral grain that is small (~30 µm) and cracked due to its brittleness (Figure 4a). It was found in one of the veins sampled (Figure 2). Bismuthotelluride species of Pd and Pt and sperrylite, present in the concentrates, are consistent with the findings of a previous study [9].
We employed scanning-electron microscopy (SEM) and energy-dispersive analysis (EDS) conducted at an accelerating voltage of 20 kV and a beam current of 1.6 nA, with a beam size of ~1 µm, using a MIRA 3 LMU (Tescan Orsay Holding, Brno, Czech Republic) SEM with an attached INCA Energy 450 XMax 80 (Oxford Instruments Nanoanalysis, Wycombe, UK) microanalysis EDS system at the Institute of Geology and Mineralogy (the Analytical Center for Multi-Elemental and Isotope Studies), Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia. The standards used were FeS2 (S), PtAs2 (As), PbTe (Pb and Te), wollastonite (Ca), synthetic GaP (P), NaCl (Cl) and pure metals (Fe, Co, Ni, Cu, Rh, Pd, Pt and Bi). For the analytical signal of S, Fe, Ni, Cu, Ca, P and Cl, the K family of peaks was used, and for the other elements, the L family. The use of the L family for Pt and Bi avoids the mutual overlaps of their M peaks. Minimum detection-limits (3σ criterion) of the elements (wt.%) were found to be 0.1–0.2 for S, Fe, Co, Ni, Cu, Ca and Cl; 0.2–0.4 for As, Pd and Te; and 0.4–0.7 for Pt and Bi. The analytical error for the main components did not exceed 1–2 relative % and satisfied the requirements for a quantitative analysis.

3. Results

The Pyromorphite–Phosphohedyphane Solid Solution

Phosphohedyphane, ideally Ca2Pb3(PO4)3Cl, a member of the apatite supergroup [10], was discovered in the Capitana mine, Atacama Province, Chile, where it is commonly encountered in zones of oxidized Pb-bearing ores [11]. Phosphohedyphane and pyromorphite, ideally Pb5(PO4)3Cl, seem to form a complete solid solution, as demonstrated by a compilation of literature data [11,12]. Values of the ratio 5 × Ca/(Ca + Pb) range from 0 to 2 over that interval, and our specimen has a value of 0.78. Values between 2 and 5, i.e., intermediate compositions between phosphohedyphane and chlorapatite, Ca5(PO4)3Cl, are not found in nature [11]. Although we do not have supporting structural data, we can assume that our phase, (Pb4.13Ca0.76)Σ4.90(PO4)3Cl0.95 (Table 1), (Pb1.13Ca0.76)Σ1.89Pb3(PO4)3Cl0.95 or, in general terms, (Pb,Ca)2Pb3(PO4)3Cl, is a member of the phosphohedyphane–pyromorphite series, in which Pb2+ enters the Ca site in accordance with the formula (Ca,Pb)2Pb3(PO4)3Cl. It displays a characteristic EDS spectrum (Figure 5). A complete solid-solution series probably exists between phosphohedyphane and hedyphane, Pb3Ca2(AsO4)3Cl. Phosphohedyphane is the phosphate analog of hedyphane, i.e., the long-established arsenate [13], and the Cl analog of fluorphosphohedyphane [11]. In an arsenic-bearing system, intermediate members are complex solid solutions involving components of phosphohedyphane, hedyphane and mimetite, Pb5(AsO4)3Cl [14,15,16]. Members of such a series are developed, for example, in the oxidized zone at the Preguiça mine, Portugal [17]. As in that case, the phase found at Monchepluton is a secondary mineral formed by oxidation of primary Pb-rich precursors.

The Platinum-Group Minerals

We have identified five species of PGM in the samples investigated (Table 2). Sperrylite (ideally PtAs2), both S-bearing (up to 0.63 wt.% S) and essentially devoid of S, is relatively common, as well as michenerite (PdBiTe). Members of the moncheite Pt(Te,Bi)2–merenskyite Pd(Te,Bi)2 series are subordinate, and kotulskite Pd(Te,Bi) is rare in our samples.
A relative enrichment in Bi is noteworthy; it is observed in compositions of all species of the Pd–Pt bismuthotellurides (Table 2; Figure 6 and Figure 7). Note that Te occupies almost entirely the Te site, and makes up a substantial portion (up to ~20%) of the Bi site (Figure 6).

4. Discussion

The presence of pyromorphite–phosphohedyphane solid solution in association with zones of massive PGE-bearing Cu–Ni sulfide ore provides a direct indication of the role of Cl at the hydrothermal stage in the Monchepluton cumulates. The abundance of galena, Bi-, Te, and As-enriched species of Pd and Pt is consistent with deposition from hydrothermal fluids late in the crystallization history of the complex. The observed assemblages enriched in Bi imply a relative decrease in temperatures of crystallization of the bismuthotelluride species. Experimental results [18] indicate that michenerite is stable below 500 °C, whereas the melting point of the end member of the merenskyite series (740 °C) decreases to 500–525 °C for the Bi-enriched phases having greater extents of Bi-for-Te substitution. Sperrylite is also known to form at a postmagmatic hydrothermal stage in layered intrusions [19]. We therefore presume that the phosphohedyphane-like phase represents a part of the late Pb–S–Te–Bi–As-enriched assemblages deposited hydrothermally during the formation of the sulfide veins.
In Table 3, we review [6,20,21,22,23,24,25,26,27,28,29,30,31,32,33,34,35,36,37,38,39,40,41,42,43,44,45] the occurrences of Cl-rich minerals known in basic–ultrabasic complexes emplaced in different geological settings worldwide. These phases include hydroxychlorides, such as (Fe,Mn)(OH)Cl and hibbingite (Fe2(OH)3Cl) from the Sudbury complex, Canada, hibbingite in the Duluth layered complex, USA, members of the hibbingite–kempite (Mn2(OH)3Cl) series, djerfisherite (K6(Fe,Cu,Ni)25S26Cl) and thalfenisite, its thallium analog (Tl6(Fe,Ni)25S26Cl), pyrosmalite-(Fe) in the Noril’sk complex of Russia, djerfisherite in the Guli and Yoko-Dovyren complexes, Russia, a penfieldite-type phase (Pb2Cl3(OH)) in the Bushveld complex, South Africa, and unnamed Pd–Bi chlorides from Noril’sk and Sudbury.
On the basis of findings in the reviewed occurrences (Table 3), we infer that Cl-rich compounds typically form at relatively low temperatures as a consequence of build-up in levels of Cl attained locally during late or final stages of formation, or during stages of postmagmatic alteration of the complexes. Chlorapatite, which is the most abundant expression of Cl buildup, crystallized from pockets of intercumulus melts [6,21,25] or is a result of phase transformations involving fluorapatite as a precursor phase [46]. In addition, Cl was important in PGE remobilization in the Duluth complex, Minnesota, USA [47]. The amphibole “ferro-chloro-pargasite” likely precipitated from a late phase of hydrous Cl-bearing fluids (e.g., micro-inclusions hosted by PGM), or formed as a result of transformation reactions, which involved a primary plagioclase during deuteric (autometasomatic) events of alteration [6,31,32]. Many of the uncommon compounds rich in Cl likely formed from residual droplets of highly fractionated melts or crystallized from remaining microvolumes of aqueous hydrochloric solutions [41].

The Behavior of Cl during Crystallization of the Monchepluton Complex and the Origin of Calcian Pyromorphite

A recent evaluation of geochemical trends and their link to compositions of rock-forming silicate and oxide minerals at Monchepluton indicates that variations in apatite differ from trends reported for other layered intrusions [6]. Chlorapatite (>6 wt.% Cl) is invariably abundant, and compositional variations in apatite are generally similar in all of the geological divisions of the complex (i.e., the Mounts Nittis, Kumuzhya, Travyanaya, Sopcha, Nyud and Poaz). No relationship exists between the Cl content of apatite and the degree of magnesium enrichment in the coexisting magmatic silicates. Two fields of apatite compositions are recognized: ≤3 wt.% and >6 wt.% Cl, which overlap extensively, consistent with two generations of apatite. The first nucleated early during crystallization of pockets of H2O-bearing intercumulus melts. An inferred stage of degassing of the crystallizing melt likely caused a decoupling of Cl and F. Fluorine at Monchepluton essentially remained in the melt, whereas Cl was partitioned efficiently to an H2O-bearing fluid phase. As a result, at the early stage, the apatite incorporated combinations of the components hydroxylapatite and fluorapatite, with a low content of Cl. At a late stage, chlorapatite precipitated from a Cl-rich fluid. Consequently, “ferro-chloro-pargasite” (4.1 wt.% Cl) formed via reactions of that fluid with plagioclase and pyroxene during an event of autometasomatic alteration occurring in relatively evolved cumulates of gabbronoritic sequences of the Poaz massif (Figure 2) [6].
Features of the geochemical behavior of Cl [6] are useful in recognizing a mode of formation of the phosphohedyphane-like phase occurring in a sulfide vein of the Monchepluton complex. The investigated veins occur close to the nexus (Figure 2); they are representative examples that belong to the entire system of steeply dipping veins of massive sulfide ores (0.1 to 1.4 km long and up to 0.5 m in thickness, locally up to 2–3 m thick). These veins presumably formed by remobilization of early occurrences of magmatic sulfide melts, accumulating and filling the space along the system of early brittle faults developed in the nexus region of the complex: [6] and references therein. In accordance with previous observations at Monchepluton [6], we presume that Cl was locally abundant in a late fluid during the formation of the sulfide Cu–Ni–PGE mineralization of the veins. We propose a secondary origin, related to a low-temperature oxidation of a Pb-bearing precursor, presumably galena, to account for the presence of a pyromorphite–phosphohedyphane solid solution at Monchepluton. This mechanism and mode of formation are consistent with findings on related Cl-rich phosphates of Pb and Ca from other localities [11,17].
We believe that the lead-bearing phosphate likely formed at elevated levels of fO2 via two-stage reactions of precursor grains of galena with components of the residual fluid saturated with respect to an apatite-supergroup mineral and containing Ca (and minor Ba) as incompatible components during crystallization of the sulfide ore:
2PbS + 3O2 → 2PbO + 2SO2
and
4CaO + 16PbO + 2P2O5 + Cl + 9O2 → 4[CaPb4(PO4)3Cl]
Grains of barite, also present in the heavy-mineral concentrate of the veins, could well form according to the following reaction: Ba + SO2 + O2 → BaSO4.
The inferred regime of progressive increase in fO2 is further corroborated by the common occurrence of highly oxidized varieties of ochreous and porous ores, which commonly accompany the primary sulfide ores in the veins at Monchepluton. A progressive rise in intrinsic fO2 is also inferred for some other ultrabasic complexes in the Serpentinite belt of the Kola Peninsula [48,49,50].

5. Conclusions

(1)
We describe the occurrence of a pyromorphite–phosphohedyphane solid solution in zones of massive PGE-bearing Cu–Ni sulfide mineralization in the Monchepluton complex. An elevated level of Cl developed in the cumulates at the hydrothermal stage and migrated along the system of early brittle faults.
(2)
The phosphohedyphane-like phase is a member of the late Pb–S–Te–Bi–As-enriched assemblages, which include Pd–Pt bismuthotellurides and sperrylite, all deposited hydrothermally, from ~750 to below 500 °C, during the formation of the sulfide veins.
(3)
A secondary origin is inferred, involving a low-temperature oxidation of a Pb-bearing precursor, presumably galena, to form grains of the phosphohedyphane-like phase. This mechanism and mode of formation are consistent with findings on related Cl-rich phosphates of Pb and Ca from other localities, which are reviewed.
(4)
There was a progressive increase in fO2, in agreement with the abundance of oxidized varieties of ores in association with primary ores in the veins at Monchepluton and at other ultrabasic complexes of the Kola Peninsula.

Author Contributions

The authors wrote the article together. A.Y.B.: investigations, writing; A.A.N.: writing, discussions; L.P.B.: interpretations, writing; R.F.M.: conclusions, writing. All authors have read and agreed to the published version of the manuscript.

Funding

This study was supported by the Russian Science Foundation (grant #22-27-00419).

Data Availability Statement

The data are available upon a reasonable request (from A.Y.B.).

Acknowledgments

We sincerely thank the Editors and the three anonymous reviewers for their comments on a previous version of our manuscript. We are grateful to the late Sergey S. Kramzaev (ChSU, Cherepovets) for his assistance and efforts during the field investigations. A.Y.B. gratefully acknowledges additional support for this investigation by Cherepovets State University.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Amelin, Y.; Heaman, L.; Semenov, V. U–Pb geochronology of layered mafic intrusions in the eastern Baltic Shield: Implications for the timing and duration of Paleoproterozoic continental rifting. Precambrian Res. 1995, 75, 31–46. [Google Scholar] [CrossRef]
  2. Alapieti, T.T.; Lahtinen, J.J.; Lavrov, M.M.; Smolkin, V.F.; Voitsekhovsky, S.N. Early Proterozoic layered intrusions in the northeastern part of the Fennoscandian Shield. Mineral. Pet. 1990, 42, 1–22. [Google Scholar] [CrossRef]
  3. Balagansky, V.V.; Gorbunov, I.A.; Mudruk, S.V. Palaeoproterozoic Lapland-Kola and Svecofennian orogens (Baltic Shield). Her. (Vestn.) Kola Sci. Cent. RAS 2016, 3, 5–11. (In Russian) [Google Scholar]
  4. Sharkov, E.V.; Chistyakov, A.V. The Early Paleoproterozoic Monchegorsk layered mafite-ultramafite massif in the Kola Peninsula: Geology, petrology, and ore potential. Petrology 2012, 20, 607–639. [Google Scholar] [CrossRef]
  5. Barkov, A.; Martin, R.; Izokh, A.; Nikiforov, A.; Korolyuk, V. Ultramagnesian Olivine in the Monchepluton (Fo96) and Pados-Tundra (Fo93) Layered Intrusions (Kola Peninsula). Russ. Geol. Geophys. 2021, 62, 324–338. [Google Scholar] [CrossRef]
  6. Barkov, A.; Sharkov, E.; Nikiforov, A.; Korolyuk, V.; Silyanov, S.; Lobastov, B. Compositional Variations of Apatite and REE-Bearing Minerals in Relation to Crystallization Trends in the Monchepluton Layered Complex (Kola Peninsula). Russ. Geol. Geophys. 2021, 62, 427–444. [Google Scholar] [CrossRef]
  7. Barkov, A.; Nikiforov, A.; Martin, R. A novel mechanism of spheroidal weathering: A case study from the Monchepluton layered complex, Kola Peninsula, Russia. Bull. Geol. Soc. Finl. 2015, 87, 79–85. [Google Scholar] [CrossRef]
  8. Chashchin, V.V.; Galkin, A.S.; Ozeryanskii, V.V.; Dedyukhin, A.N. Sopcha Lake chromite deposit and its platinum potential, Monchegorsk pluton, Kola Peninsula (Russia). Geol. Ore Deposits 1999, 41, 460–468. [Google Scholar]
  9. Dedeev, A.V.; Khashkovskaya, T.N.; Galkin, A.S. PGE Mineralization of the Monchegorsk layered mafic–ultramafic intrusion of the Kola Peninsula. In The Geology, Geochemistry, Mineralogy and Mineral Beneficiation of Platinum-Group Elements, Canadian Institute of Mining, Metallurgy and Petroleum; Cabri, L.J., Ed.; Canadian Institute of Mining, Metallurgy and Petroleum: Montreal, QC, Canada, 2002; Volume 54, pp. 569–577. [Google Scholar]
  10. Pasero, M.; Kampf, A.R.; Ferraris, C.; Pekov, I.V.; Rakovan, J.; White, T. Nomenclature of the apatite supergroup minerals. Eur. J. Mineral. 2010, 22, 163–179. [Google Scholar] [CrossRef]
  11. Kampf, A.R.; Steele, I.M.; Jenkins, R.A. Phosphohedyphane, Ca2Pb3(PO4)3Cl, the phosphate analog of hedyphane: Description and crystal structure. Am. Mineral. 2006, 91, 1909–1917. [Google Scholar] [CrossRef]
  12. Kampf, A.R.; Housley, R.M. Fluorphosphohedyphane, Ca2Pb3(PO4)3F, the first apatite supergroup mineral with essential Pb and F. Am. Mineral. 2011, 96, 423–429. [Google Scholar] [CrossRef]
  13. Breithaupt, A. Bestimmung neuer Mineral-Specien, 2. Hedyphan. J. Chem. Phys. 1830, 60, 308–316. [Google Scholar]
  14. Hochleitner, R.; Kaliwoda, M.; Rewitzer, C. Natural members of the phosphohedyphane-hedyphane-mimetite series. In Proceedings of the 2nd European Mineralogical Conference Minerals, Rocks and Fluids: Alphabet and Words of Planet Earth, Rimini, Italy, 1–15 September 2016; p. 569. [Google Scholar]
  15. Calos, N.J.; Kennard, C.H.L.; Davis, R.L. Crystal structure of mimetite, Pb5(AsO4)3Cl. Z. Krist. 1990, 191, 125–129. [Google Scholar] [CrossRef]
  16. Dai, Y.; Hughes, J.M.; Moore, P.B. The crystal structures of mimetite and clinomimetite, Pb5(AsO4)3Cl. Can. Mineral. 1991, 29, 369–376. [Google Scholar]
  17. Will, P.; Friedrich, F.; Hochleitner, R.; Gilg, H.A. Fraipontite in the hydrothermally overprinted oxidation zone of the Preguiça mine, Southern Portugal. In Proceedings of the 7th Mid-European Clay Conference, Dresden, Germany, 16–19 September 2014; p. 133. [Google Scholar]
  18. Hoffman, E.L.; MacLean, W.H. Phase relations of michenerite and merenskyite in the Pd-Bi-Te system. Econ. Geol. 1976, 71, 1461–1468. [Google Scholar] [CrossRef]
  19. Barkov, A.Y.; Fleet, M.E. An unusual association of hydrothermal platinum-group minerals from the Imandra layered complex, Kola Peinsula,, northwestern Russia. Can. Mineral. 2004, 42, 455–467. [Google Scholar] [CrossRef]
  20. Boudreau, A.E.; Mathez, E.A.; McAllum, I.S. Halogen Geochemistry of the Stillwater and Bushveld Complexes: Evidence for Transport of the Platinum-Group Elements by Cl-Rich Fluids. J. Pet. 1986, 27, 967–986. [Google Scholar] [CrossRef]
  21. Boudreau, A.E.; McCallum, I.S. Investigations of the Stillwater Complex: Part V. Apatites as indicators of evolving fluid composition. Contrib. Mineral. Pet. 1989, 102, 138–153. [Google Scholar] [CrossRef]
  22. Mutanen, T.; Törnroos, R.; Johanson, B. The Significance of Cumulus Chlorapatite and High-temperature Dashkesanite to the Genesis of PGE Mineralization in the Koitelainen and Keivitsa-Satovaara Complexes, Northern Finland. Geo-Platinum 87 1988, 159–160. [Google Scholar] [CrossRef]
  23. Barkov, A.Y.; Savchenko, E.E.; Menshikov, Y.P. Chlorapatite as indicator of platinum-group elements fluid mobilization in the Lukkulaisvaara intrusion, northern Karelia. Dokl. Akad. Nauk 1993, 328, 84–89. (In Russian) [Google Scholar]
  24. Meurer, W.P.; Hellström, F.A.; Claeson, D.T. The relationship between chlorapatite and PGE-rich cumulates in layered intrusions: The Kläppsjö gabbro, north-central Sweden, as a case study. Can. Mineral. 2004, 42, 279–289. [Google Scholar] [CrossRef]
  25. Barkov, A.Y.; Nikiforov, A.A. Compositional Variations of Apatite, Fractionation Trends, and A PGE-Bearing Zone In the Kivakka Layered Intrusion, Northern Karelia, Russia. Can. Mineral. 2016, 54, 475–490. [Google Scholar] [CrossRef]
  26. Barkov, A.Y.; Nikiforov, A.A. A new criterion for searching zones of PGE mineralization of the “Kivakka Reef” type. Vestn. VGU. Geol. 2015, 4, 75–83. (In Russian) [Google Scholar]
  27. Barkov, A.Y.; Nikulin, I.I.; Nikiforov, A.A.; Lobastov, B.M.; Silyanov, S.A.; Martin, R.F. Atypical Mineralization Involving Pd-Pt, Au-Ag, REE, Y, Zr, Th, U, and Cl-F in the Oktyabrsky Deposit, Norilsk Complex, Russia. Minerals 2021, 11, 1193. [Google Scholar] [CrossRef]
  28. Kislov, E.V.; Konnikov, E.G.; Orsoev, D.A.; Pushkarev, E.V.; Voronina, L.K. The chlorine role in platinum-bearing horizons formation in the Ioko-Dovyren layered massif by the results of fluid-bearing minerals investigations. Dokl. Akad. Nauk 1995, 340, 805–808. (In Russian) [Google Scholar]
  29. Kislov, E.V.; Konnikov, E.G.; Orsoev, D.A.; Pushkarev, E.V.; Voronina, L.K. Chlorine in the genesis of the low-sulfide PGE mineralization in the Ioko-Dovyrenskii layered massif. Geohimiya 1997, 5, 521–528. (In Russian) [Google Scholar]
  30. Spiridonov, E.M. Barium Minerals Barite and Chlorine dominant Ferrokinoshitalite BaFe32+[Cl2/Al2Si2O10] in plagioperidotites of the Yoko-Dovyren intrusion, northern Baikal area: Products of epigenetic low-grade metamorphism. Geochem. Int. 2019, 57, 1221–1229. [Google Scholar] [CrossRef]
  31. Barkov, A.Y.; Martin, R.F.; Tarkian, M.; Poirier, G.; Thibault, Y. Pd-Ag Tellurides from A Cl-Rich Environment in The Lukkulaisvaara Layered Intrusion, Northern Russian Karelia. Can. Mineral. 2001, 39, 639–653. [Google Scholar] [CrossRef]
  32. Barkov, A.Y.; Martin, R.F.; Laajoki, K.V.O.; Alapieti, T.T.; Iljina, M.J. Paragenesis and origin of staurolite from a palladium-rich gabbronorite: An unusual occurrence from the Lukkulaisvaara layered intrusion, Russian Karelia. Neues Jahrb. für Mineral.-Abh. 1999, 175, 191–222. [Google Scholar] [CrossRef]
  33. Duesterhoeft, E.; Raase, P.; Gremler, P. A new occurrence of extremely rare Ferro-Chloro-Pargasite in Tudor, Ontario. Geol. Rundsch. 2017, 106, 2815–2816. [Google Scholar] [CrossRef]
  34. Karpenkov, A.M.; Rudashevsky, N.S.; Shumskaya, N.I. Natural palladium bismuth chloride–phase of Pd4Bi5Cl3 composition. Zap. Vses. Mineral. Obshch. 1981, 110, 86–91. (In Russian) [Google Scholar] [CrossRef]
  35. Li, C.; Naldrett, A.J. Platinum-group minerals from the Deep Copper Zone of the Strathcona deposit, Sudbury, Ontario. Can. Mineral. 1993, 31, 31–44. [Google Scholar] [CrossRef]
  36. Springer, G. Chlorine-bearing and other uncommon minerals in the Strathcona Deep Copper zone, Sudbury district, Ontario. Can. Mineral. 1989, 27, 311–313. [Google Scholar]
  37. Dahlberg, E.H.; Saini-Eidukat, B. A chlorine-bearing phase in drill core of serpentinized troctolitic rocks of the Duluth Complex, Minnesota. Can. Mineral. 1991, 29, 239–244. [Google Scholar]
  38. Saini-Eidukat, B.; Kucha, H.; Keppler, H. Hibbingite, γ-Fe2(OH)3Cl, a new mineral from the Duluth complex, Minnesota, with implications for the oxidation of Fe-bearing compounds and the transport of metals. Am. Mineral. 1994, 79, 555–561. [Google Scholar]
  39. Saini-Eidukat, B.; Rudashevsky, N.S.; Polozov, A.G. Evidence for hibbingite–kempite solid solution. Mineral. Mag. 1998, 62, 251–255. [Google Scholar] [CrossRef]
  40. Barkov, A.Y.; Martin, R.F.; Poirier, G.; Tarkian, M.; Pakhomovskii, Y.A.; Men’shikov, Y.P. Tatyanaite, a new platinum-group mineral, the Pt analogue of taimyrite, from the Noril’sk complex (northern Siberia, Russia). Eur. J. Mineral. 2000, 12, 391–396. [Google Scholar] [CrossRef]
  41. Barkov, A.Y.; Martin, R.F.; Kaukonen, R.J.; Alapieti, T.T. The occurrence of Pb-Cl-(OH) and Pt-Sn-S compounds in the Merensky reef, Bushveld layered complex, South Africa. Can. Mineral. 2001, 39, 1397–1403. [Google Scholar] [CrossRef] [Green Version]
  42. Genkin, A.D.; Troneva, N.V.; Zhuravlev, N.N. The first find in ores of a potassium, iron and copper sulfide–djerfisherite. Geol. Rudn. Mestorozhd. 1969, 5, 57–64. (In Russian) [Google Scholar]
  43. Zaccarini, F.; Thalhammer, O.A.; Princivalle, F.; Lenaz, D.; Stanley, C.; Garuti, G. Djerfisherite in the Guli dunite complex, Polar Siberia: A primary or metasomatic phase? Can. Mineral. 2007, 45, 1201–1211. [Google Scholar] [CrossRef]
  44. Kislov, E.V.; Orsoev, D.A.; Pushkarev, E.V. Halogens in djerfisherite from a magnesian skarn of the platinum-bearing Yoko-Dovyren massif. Geol. Geophys. 1994, 11, 54–57. (In Russian) [Google Scholar]
  45. Rudashevskii, N.S.; Karpenkov, A.M.; Shipova, G.S.; Shishkin, N.N.; Ryabkin, V.A. Thalfenisite, the thallium analogue of djerfisherite. Zap. Vsesoyuzn. Mineral. Obshch. 1979, 108, 696–701. (In Russian) [Google Scholar]
  46. Cawthorn, R.G. Formation of chlor- and fluor-apatite in layered intrusions. Mineral. Mag. 1994, 58, 299–306. [Google Scholar] [CrossRef]
  47. Raič, S.; Mogessie, A.; Krenn, K.; Hauzenberger, C.A.; Tropper, P. Deciphering Magmatic and Metasomatic Processes Recorded by Fluid Inclusions and Apatite within the Cu–Ni ± PGE-Sulfide Mineralized Bathtub Intrusion of the Duluth Complex, NE Minnesota, USA. J. Petrol. 2018, 59, 1167–1192. [Google Scholar] [CrossRef]
  48. Barkov, A.Y.; Korolyuk, V.N.; Barkova, L.P.; Martin, R.F. Double-Front Crystallization in the Chapesvara Ultramafic Subvolcanic Complex, Serpentinite Belt, Kola Peninsula, Russia. Minerals 2019, 10, 14. [Google Scholar] [CrossRef] [Green Version]
  49. Barkov, A.Y.; Nikiforov, A.A.; Korolyuk, V.N.; Barkova, L.P.; Martin, R.F. Anomalous chromite–ilmenite parageneses in the Chapesvara and Lyavaraka ultramafic complexes, Kola Peninsula, Russia. Period Di Mineral. 2020, 89, 299–317. [Google Scholar]
  50. Barkov, A.Y.; Nikiforov, A.A.; Korolyuk, V.N.; Barkova, L.P.; Martin, R.F. The chromian spinels of the Lyavaraka ultrabasic complex, Serpentinite Belt, Kola Peninsula, Russia: Patterns of zoning, hypermagnesian compositions, and early oxidation. Can. Mineral. 2021, 59, 1693–1709. [Google Scholar] [CrossRef]
Figure 1. Location of the Monchepluton layered complex shown in the context of tectonic settings in the northeastern part of the Fennoscandian Shield (after [3] and references therein).
Figure 1. Location of the Monchepluton layered complex shown in the context of tectonic settings in the northeastern part of the Fennoscandian Shield (after [3] and references therein).
Minerals 12 00624 g001
Figure 2. Schematic geological map of the Monchepluton complex ([4], with findings of V.V. Knauf and N.S. Guseva), showing the sampling location in the present investigation.
Figure 2. Schematic geological map of the Monchepluton complex ([4], with findings of V.V. Knauf and N.S. Guseva), showing the sampling location in the present investigation.
Minerals 12 00624 g002
Figure 3. Photographs of fragments of base-metal ores sampled from sulfide veins of the Monchepluton complex. The samples MNP—3 and 4 are shown in (a,b), respectively.
Figure 3. Photographs of fragments of base-metal ores sampled from sulfide veins of the Monchepluton complex. The samples MNP—3 and 4 are shown in (a,b), respectively.
Minerals 12 00624 g003
Figure 4. SEM images showing selected grains of phosphohedyphane-like phase labeled Phs (a), sperrylite, Spy (b,d), and michenerite, Mch (c,d), which are present in heavy-mineral concentrates from sulfide veins of the Monchepluton complex.
Figure 4. SEM images showing selected grains of phosphohedyphane-like phase labeled Phs (a), sperrylite, Spy (b,d), and michenerite, Mch (c,d), which are present in heavy-mineral concentrates from sulfide veins of the Monchepluton complex.
Minerals 12 00624 g004
Figure 5. The energy-dispersive (EDS) spectrum of the phosphohedyphane-type phase from the Monchepluton complex.
Figure 5. The energy-dispersive (EDS) spectrum of the phosphohedyphane-type phase from the Monchepluton complex.
Minerals 12 00624 g005
Figure 6. Correlation of Bi vs. Te in compositions of michenerite from sulfide veins of the Monchepluton complex. Results of a total of forty-four data points (n = 44) are plotted and expressed in values of atoms per formula unit (apfu). The equation of linear regression and calculated value of correlation coefficient (R) are also shown.
Figure 6. Correlation of Bi vs. Te in compositions of michenerite from sulfide veins of the Monchepluton complex. Results of a total of forty-four data points (n = 44) are plotted and expressed in values of atoms per formula unit (apfu). The equation of linear regression and calculated value of correlation coefficient (R) are also shown.
Minerals 12 00624 g006
Figure 7. Correlation of Bi vs. Te in compositions of moncheite (shown by diamonds) and merenskyite (circles) from sulfide veins of the Monchepluton complex. Results of a total of sixteen data points (n = 16) are plotted (in values of atoms per formula unit, apfu). The equation of linear regression and calculated value of correlation coefficient (R) are shown on the plot.
Figure 7. Correlation of Bi vs. Te in compositions of moncheite (shown by diamonds) and merenskyite (circles) from sulfide veins of the Monchepluton complex. Results of a total of sixteen data points (n = 16) are plotted (in values of atoms per formula unit, apfu). The equation of linear regression and calculated value of correlation coefficient (R) are shown on the plot.
Minerals 12 00624 g007
Table 1. Composition of the phosphohedyphane-type phase from the Monchepluton layered complex, Kola Peninsula.
Table 1. Composition of the phosphohedyphane-type phase from the Monchepluton layered complex, Kola Peninsula.
Wt. %apfu
CaO3.54Ca0.76
PbO76.74Pb4.13
P2O515.67Σ4.90
Cl2.81
O≡Cl0.64P2.65
Total98.12Cl0.95
Note: Results of quantitative SEM/EDS analysis are expressed in weight %. Values of atoms per formula unit (apfu) are based on a value of 12 oxygen atoms per formula unit.
Table 2. Compositions of platinum-group minerals in sulfide veins of the Monchepluton layered complex.
Table 2. Compositions of platinum-group minerals in sulfide veins of the Monchepluton layered complex.
PtPdTeBiAsSTotalPtPdPt + PdTeBiTe + BiAsS
Wt.% apfu
1Spy56.38bdlbdlbdl44.22bdl100.60.990.992.010.00
2 55.45bdlbdlbdl43.77bdl99.220.980.982.020.00
3 56.45bdlbdlbdl44.29bdl100.740.990.992.010.00
4 54.93bdlbdlbdl43.650.5399.110.960.961.980.06
5 55.18bdlbdlbdl42.970.3698.510.980.981.980.04
6 54.47bdlbdlbdl43.800.4898.750.950.952.000.05
7 54.93bdlbdlbdl42.540.5398.000.980.981.970.06
8 54.59bdlbdlbdl42.880.6398.100.960.961.970.07
9KtuBdl38.9230.2529.22bdlbdl98.390.980.980.640.381.02
10MchBdl24.5632.8041.78bdlbdl99.140.001.011.011.120.871.99
11 Bdl24.5233.6641.03bdlbdl99.210.001.001.001.150.852.00
12 Bdl24.7233.2241.53bdlbdl99.470.001.011.011.130.861.99
13 3.8222.5828.2944.49bdlbdl99.180.090.961.041.000.961.96
14 4.5421.3128.0445.37bdlbdl99.260.110.911.021.000.991.98
15 3.0922.5628.1645.24bdlbdl99.050.070.961.031.000.981.97
16 3.4122.3528.4246.12bdlbdl100.300.080.941.021.000.991.98
17 1.8623.9932.2940.59bdlbdl98.730.040.991.031.110.851.97
18 bdl24.4133.5341.18bdlbdl99.120.001.001.001.140.862.00
19 bdl24.0528.4845.60bdlbdl98.130.001.021.021.000.981.98
20 bdl23.7128.7645.85bdlbdl98.320.001.001.001.010.992.00
21 bdl24.3431.8242.66bdlbdl98.820.001.011.011.100.901.99
22 5.5920.5027.0945.61bdlbdl98.790.130.891.020.981.001.98
23 2.0623.7129.8743.39bdlbdl99.030.050.991.041.040.921.96
24 5.7620.9126.8346.13bdlbdl99.630.130.901.030.961.011.97
25Mon31.895.5045.1916.49bdlbdl99.070.760.241.001.640.372.00
26 36.291.7640.6519.33bdlbdl98.030.910.080.991.560.452.01
27 35.471.9441.0120.01bdlbdl98.430.880.090.971.560.472.03
28Mrk9.3921.0452.9616.58bdlbdl99.970.200.801.001.680.322.00
29 6.0522.6452.1617.54bdlbdl98.390.130.870.991.670.342.01
30 5.3623.5552.8816.52bdlbdl98.310.110.891.011.680.321.99
Note: Results of quantitative SEM/EDS analyses are listed in weight %. The atomic proportions are based on a total of 3 atoms per formula unit (apfu) for sperrylite (Spy), michenerite (Mch), moncheite (Mon) and merenskyite (Mrk), and on a total of 2 apfu for kotulskite (Ktu). bdl: below detection limit.
Table 3. A review of various minerals and phases enriched in Cl from basic–ultrabasic complexes.
Table 3. A review of various minerals and phases enriched in Cl from basic–ultrabasic complexes.
MineralsComplex, LocalityOccurrenceCommentReferences
ChlorapatiteBushveld, South AfricaLower zone [20,21]
Stillwater, Montana, USA [21]
Koitelainen, Keivitsa-
Satovaara, Finland
Cl-rich Amp[22]
Lukkulaisvaara, northern
Karelia, Russia
Clap in Ol cumulates[23]
Kläppsjö, SwedenGabbroClap–PGM[24]
Kivakka, northern Karelia, RussiaLower zonesClap–PGM[25,26]
Monchepluton, Kola Peninsula, RussiaMounts Nittis, Kumuzh’ya, Travyanaya, Sopcha, Nyud and PoazClap in ultramafic-mafic cumulates[6]
Noril’sk, Siberia, RussiaOktyabr’sky depositPd–Pt, Au–Ag atypical ore[27]
Cl-bearing ApYoko-Dovyren, Baikal region, RussiaPGM-bearing horizon≤2.42 wt.% Cl[28,29]
Cl-bearing mica Yoko-Dovyren, Baikal region, RussiaPGM-bearing horizon≤0.58 wt.% Cl[28,29]
Cl analog of ferrokinoshitaliteYoko-Dovyren, Baikal region, RussiaPl-bearing peridotite [30]
Cl-rich anniteNoril’sk, Siberia, RussiaOktyabr’sky deposit≤7.54 wt.% Cl atypical ore[27]
Cl-rich hastingsite Noril’sk, Siberia, RussiaOktyabr’sky
deposit
≤4.06 wt.% Cl atypical ore[27]
“Ferro-chloro-pargasite”Lukkulaisvaara, northern Karelia, RussiaPegmatitic orthopyroxeniteFcprg–PGM[31,32]
Tudor, Ontario, CanadaGabbro [33]
Monchepluton, Kola Peninsula, RussiaGabbronorite, Mount Poaz [6]
Pd–Bi chlorides Noril’sk, Siberia, RussiaOre-bearing zone [34]
Sudbury, Ontario, CanadaStrathcona Deep Copper zone [35]
HibbingiteSudbury, Ontario, CanadaStrathcona Deep Copper zone [36]
Duluth, Minnesota, USATroctolite [37,38]
Noril’sk, Siberia, RussiaOre zoneSolid solution with kempite[39]
Pyrosmalite-(Fe)Noril’sk, Siberia, RussiaOktyabr’sky, massive sulfidePys-Fe–Tty[40]
Penfieldite-type phaseBushveld, South AfricaMerensky ReefWith PGM in orthocumulate[41]
DjerfisheriteNoril’sk, Siberia, RussiaCu–Ni ores [42]
Guli complex, Polar Siberia, RussiaDunitic rocks [43]
Yoko-Dovyren, Baikal region, RussiaMagnesian skarnIncluded in Spl, Tro[44]
ThalfenisiteNoril’sk, Siberia, RussiaCu–Ni ores [45]
Note: Symbols used: Amp: amphibole, Clap: chlorapatite, Fcprg: ferro-chloro-pargasite, Ol: olivine, Pl: plagioclase, PGM: platinum-group minerals, Spl: spinel, Tty: tatyanaite, Tro: troilite.
Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Share and Cite

MDPI and ACS Style

Barkov, A.Y.; Nikiforov, A.A.; Barkova, L.P.; Martin, R.F. Occurrences of Pd–Pt Bismuthotellurides and a Phosphohedyphane-Like Phase in Sulfide Veins of the Monchepluton Layered Complex, Kola Peninsula, Russia. Minerals 2022, 12, 624. https://0-doi-org.brum.beds.ac.uk/10.3390/min12050624

AMA Style

Barkov AY, Nikiforov AA, Barkova LP, Martin RF. Occurrences of Pd–Pt Bismuthotellurides and a Phosphohedyphane-Like Phase in Sulfide Veins of the Monchepluton Layered Complex, Kola Peninsula, Russia. Minerals. 2022; 12(5):624. https://0-doi-org.brum.beds.ac.uk/10.3390/min12050624

Chicago/Turabian Style

Barkov, Andrei Y., Andrey A. Nikiforov, Larisa P. Barkova, and Robert F. Martin. 2022. "Occurrences of Pd–Pt Bismuthotellurides and a Phosphohedyphane-Like Phase in Sulfide Veins of the Monchepluton Layered Complex, Kola Peninsula, Russia" Minerals 12, no. 5: 624. https://0-doi-org.brum.beds.ac.uk/10.3390/min12050624

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop