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Extreme enrichment of selenium in the Apliki Cyprus-type VMS deposit, Troodos, Cyprus

  • Andrew J. Martin (a1), Iain McDonald (a1), Christopher J. MacLeod (a1), Hazel M. Prichard (a1) and Katie McFall (a1)...
Abstract

The Troodos ophiolite Cyprus hosts the type locality for Cyprus-type, mafic volcanogenic massive sulfide (VMS) deposits. Regional soil geochemical data for Troodos are highly variable with the Solea graben, one of three regional graben structures on Cyprus, showing enrichment in Te and Se. Of the three VMS sampled within the Solea graben, Apliki exhibits the most significant enrichment in Se. Samples from the South Apliki Breccia Zone; a zone of hematite-rich breccia containing euhedral pyrite and chalcopyrite, contain up to 4953 and 3956 ppm Se in pyrite and chalcopyrite, respectively. Four paragenetic stages are identified at Apliki and different generations of pyrite are distinguishable using trace-element chemistry analysed via laser ablation inductively coupled plasma mass spectrometry. Results indicate stage I pyrite formed under reduced conditions at high temperatures >280°C and contains 182 ppm (n = 22 σ = 253) Se. Late stage III pyrite which is euhedral and overprints chalcopyrite and hematite is enriched in Se (averaging 1862 ppm; n = 23 σ = 1394). Sulfide dissolution and hematite formation displaced large amounts of Se as hematite cannot accommodate high concentrations of Se in its crystal structure. The mechanisms proposed to explain the pronounced change in redox are twofold. Fault movement leading to localized seawater ingress coupled with a decreasing magmatic flux that generated locally oxidizing conditions and promoted sulfide dissolution. A Se/S ratio of 9280 indicates a probable magmatic component for late stage III pyrite, which is suggested as a mechanism explaining the transition from oxidizing back to reduced conditions. This study highlights the significance of changes in redox which promote sulfide dissolution, mobilization and enrichment of Se.

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This paper is published as part of a thematic set in memory of Professor Hazel M. Prichard

Associate Editor: John Bowles

Deceased Jan 2017

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References
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Adamides, N. (2010) Mafic-dominated volcanogeneic sulfide deposits in the Troodos ophiolite, Cyprus Part 2 – A review of genetic models and guides for exploration. Applied Earth Science, 119, 193204.
Adamides, N. (2011) Mafic-dominated volcanogenic sulfide deposits in the Troodos ophiolite, Cyprus Part 1 – The deposits of the Solea graben. Applied Earth Science, 119, 6577.
Auclair, G., Fouquet, Y. and Bohn, M. (1987) Distribution of selenium in high temperature hydrothermal sulfide deposits at 13 degrees north, East Pacific Rise. Canadian Mineralogist, 25, 577587.
Barrie, M.D.H. (1999) Classification of volcanic-associated massive sulfide deposits based on host-rock composition. Reviews in Economic Geology, 8, 111.
Bendnarz, U. and Schmincke, H.-U. (1990) Chemical patterns of seawater and hydrothermal alteration in the northeastern Troodos extrusive series and the sheeted dyke complex (Cyprus). Pp 639654 in: OPHIOLITES Oceanic Crustal Analogues (Malpas, J., Moores, E.M., Panayiotou, A. and Xenophontos, C., editors). Troodos 87, Ophiolites and Oceanic Lithosphere. Geological Survey Department of Cyprus, Nicosia, Cyprus.
Bickle, M.J. and Teagle, D.A.H. (1992) Strontium alteration in the Troodos ophiolite: implications for fluid fluxes and geochemical transport in mid-ocean ridge hydrothermal systems. Earth and Planetary Science Letters, 113, 219237.
Bustamante, M.L. and Gaustad, G. (2014) The evolving copper-tellurium byproduct system: a review of changing production techniques & their implications. Pp 1116 in: Rare Metal Technology 2014 (Neelameggham, N.R., Alam, S., Oosterhof, H., Jha, A. and Wang, S., editors). The Minerals, Metals & Materials Society, 143rd Annual Meeting. John Wiley & Sons, UK.
Butler, I.B. and Nesbitt, R.W. (1999) Trace element distributions in the chalcopyrite wall of a black smoker chimney: insights from laser ablation inductively coupled plasma mass spectrometry (LA–ICP–MS). Earth and Planetary Science Letters, 167, 335345.
Chen, M., Campbell, I.H., Xue, Y., Tian, W., Ireland, T.R., Holden, P., Cas, R.A.F., Hayman, P.C. and Das, R. (2015) Multiple sulfur isotope analyses support a magmatic model for the volcanogenic massive sulfide deposits of the Teutonic Bore Volcanic Complex, Yilgarn Craton, Western Australia. Economic Geology, 110, 14111423.
Choi, J. and Lowell, R.P. (2015) The response of two-phase hydrothermal systems to changing magmatic heat input at mid-ocean ridges. Deep Sea Research, 121, 1730 [Part II Topical Studies in Oceanography, Exploring New Frontiers in Deep-Sea Research: In Honor and Memory of Peter A. Rona].
Cohen, D.R., Rutherford, N.F., Morisseau, E. and Zissimos, A.M. (2012) Geochemical patterns in the soils of Cyprus. Science of the Total Environment, 420, 250262.
Cox, D. and Singer, D.A. (1986) Mineral Deposit Models. US Geological Survey Bulletin 1693, 1st ed. U.S Geological Survey, Reston, Virginia, USA.
de Ronde, C.E.J., Massoth, G.J., Butterfield, D.A., Christenson, B.W., Ishibashi, J., Ditchburn, R.G., Hannington, M.D., Brathwaite, R.L., Lupton, J.E., Kamenetsky, V.S., Graham, I.J., Zellmer, G.F., Dziak, R.P., Embley, R.W., Dekov, V.M., Munnik, F., Lahr, J., Evans, J.E. and Takai, K. (2011) Submarine hydrothermal activity and gold rich mineralization at Brothers Volcano, Kermadec Arc, New Zealand. Mineralium Deposita, 46, 541584.
Doyle, M.G. and Allen, R.L. (2003) Subsea-floor replacement in volcanic-hosted massive sulfide deposits. Ore Geology Reviews, 23, 183222.
Economou-Eliopoulos, M., Eliopoulos, D.G. and Chryssoulis, S. (2008) A comparison of high-Au massive sulfide ores hosted in ophiolite complexes of the Balkan Peninsula with modern analogues: Genetic significance. Ore Geology Reviews, 33, 81100.
Eddy, C.A., Dilek, Y., Hurst, S. and Moores, E.M. (1998) Seamount formation and associated caldera complex and hydrothermal mineralization in ancient oceanic crust, Troodos ophiolite (Cyprus). Tectonophysics, 292, 189210.
Escartín, J. and Canales, J.-P. (2011) Detachments in oceanic lithosphere: deformation, magmatism, fluid flow and ecosystems. EOS, Transactions AGU (92), 4, 25 January 2011.
Franklin, J.M., Gibson, H.L., Jonasson, I.R. and Galley, A.G. (2005) Volcanogenic Massive Sulfide Deposits. Pp 523560 in: Economic Geology 100th Anniversary Volume (Hedenquist, J.W., Thompson, J.F.H., Goldfarb, R.J. and Richards, J.P., editors.) Society of Economic Geologists.
Galley, A., Hannington, M. and Jonasson, I., 2007. Volcanogenic Massive Sulfide Deposits. Pp. 141161 in: Mineral Deposits of Canada: A Synthesis of Major Deposit-Types, District Metallogeny, the Evolution of Geological Provinces, and Exploration Methods. (Goodfellow, W.D., editor). Geological Association of Canada, Special Publication, No. 5.
Gass, I.G. (1968) Is the Troodos Massif of Cyprus a fragment of Mesozoic ocean floor? Nature, 220(5162), 3942.
Gass, I.G. (1980) The Troodos massif: Its role in the unravelling of the ophiolite problem and its significance in the understanding of constructive plate margin processes. Pp. 2335 in: Ophiolites, Proceedings: International Ophiolite Symposium, Cyprus 1979 (Panayiotou, A., editor). The Geological Survey Department, Nicosia, Cyprus.
Gass, I.G., MacLeod, C.J., Murton, B.J., Panayiotou, A., Simonian, K.O. and Xenophontos, C. (1994) The Geological Evolution of the Southern Troodos Transform Fault Zone. Cyprus Geological Survey Memoir 9, Geological Survey Department, Nicosia, Cyprus
Genna, D. and Gaboury, D. (2015) Deciphering the hydrothermal evolution of a VMS system by LA-ICP-MS using trace elements in pyrite: an example from the Bracemac-McLeod Deposits, Abitibi, Canada, and implications for exploration. Economic Geology, 110, 20872108.
Gill, S.B., Piercey, S.J. and Layton-Matthews, D. (2016) Mineralogy and metal zoning of the Cambrian Zn-Pb-Cu-Ag-Au Lemarchant Volcanogenic Massive Sulfide (VMS) deposit, Newfoundland. Canadian Mineralogist, 54, 13071344.
Gillis, K.M. and Roberts, M.D. (1999) Cracking at the magma–hydrothermal transition: evidence from the Troodos Ophiolite, Cyprus. Earth and Planetary Science Letters, 169, 227244.
Gillis, K.M. and Robinson, P.T. (1980) Multistage alteration in the extruisve sequence of the Troodos ophiolite, Cyprus. Pp. 655664 in: OPHIOLITES Oceanic Crustal Analogues (Malpas, J., Moores, E.M., Panayiotou, A. and Xenophontos, C., editors). Troodos 87, Ophiolites and Oceanic Lithosphere. Geological Survey Department of Cyprus, Nicosia, Cyprus.
Gillis, K.M. and Robinson, P.T. (1990) Patterns and processes of alteration in the lavas and dykes of the Troodos Ophiolite, Cyprus. Journal of Geophysical Research, 95, 2152321548.
Graham, S.D., Holwell, D.A., McDonald, I., Jenkin, G.R.T., Hill, N.J., Boyce, A.J., Smith, J. and Sangster, C. (2017) Magmatic Cu-Ni-PGE-Au sulfide mineralisation in alkaline igneous systems: An example from the Sron Garbh intrusion, Tyndrum, Scotland. Ore Geology Reviews, 80, 961984.
Grundler, P.V., Brugger, J., Etschmann, B.E., Helm, L., Liu, W., Spry, P.G., Tian, Y., Testemale, D. and Pring, A. (2013) Speciation of aqueous tellurium(IV) in hydrothermal solutions and vapors, and the role of oxidized tellurium species in Te transport and gold deposition. Geochimica et Cosmochimica Acta, 120, 298325.
Hannington, M.D. and Barrie, C.T. (1999) The giant Kidd Creek volcanogenic massive sulfide deposit: Western Abitibi Subprovince, Canada. Economic Geology, 10, 111.
Hannington, M.D., Galley, A., Herzig, P. and Petersen, S. (1998) Comparison of the TAG mound and stockwork complex with Cyprus-type massive sulfide deposits. Pp. 389415 in: Ocean Drilling Program Scientific Results (Herzig, O.M., Humphris, S.E., Miller, D.J. and Zierenberg, R.A., editors). Texas A&M University, College Station, Texas, USA.
Herzig, P.M., Hannington, M.D. and Arribas, A. Jr. (1998) Sulfur isotopic composition of hydrothermal precipitates from the Lau back-arc: implications for magmatic contributions to seafloor hydrothermal systems. Mineralium Deposita, 33, 226237.
Holwell, D.A., Keays, R.R., McDonald, I. and Williams, M.R. (2015) Extreme enrichment of Se, Te, PGE and Au in Cu sulfide microdroplets: evidence from LA-ICP-MS analysis of sulfides in the Skaergaard Intrusion, east Greenland. Contributions to Mineralogy and Petrology, 170, 126.
Humphris, S.E. and Cann, J.R. (2000) Constraints on the energy and chemical balances of the modern TAG and ancient Cyprus seafloor sulfide deposits. Journal of Geophysical Research, 105, 2847728488.
Huston, D.L. and Large, R.R. (1989) A chemical model for the concentration of gold in volcanogenic massive sulfide deposits. Ore Geology Reviews, 4, 171200.
Huston, D.L., Sie, S.H. and Suter, G.F. (1995) Selenium and its importance to the study of ore genesis: the theoretical basis and its application to volcanic-hosted massive sulfide deposits using pixeprobe analysis. Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, 104, 476480.
Jowitt, S.M., Osborn, R.G.M., Thomas, R.D.H., Naden, J., Gunn, A.G., Herrington, R.J. and Nicolaides, S. (2005) ′T′-type mineralisation – a pseudo-epithermal style of VHMS associated gold mineralisation, Cyprus. Mineral Deposit Research: Meeting the Global Challenge, 635637.
Jowitt, S.M., Jenkin, G.R.T., Coogan, L.A. and Naden, J. (2012) Quantifying the release of base metals from source rocks for volcanogenic massive sulfide deposits: Effects of protolith composition and alteration mineralogy. Journal of Geochemical Exploration, 118, 4759.
Keith, M., Haase, K.M., Klemd, R., Krumm, S. and Strauss, H. (2016) Systematic variations of trace element and sulfur isotope compositions in pyrite with stratigraphic depth in the Skouriotissa volcanic-hosted massive sulfide deposit, Troodos ophiolite, Cyprus. Chemical Geology, 423, 718
Layton-Matthews, D., Peter, J.M., Scott, S.D. and Leybourne, M.I. (2008) Distribution, mineralogy, and geochemistry of selenium in felsic volcanic-hosted massive sulfide deposits of the Finlayson Lake District, Yukon Territory, Canada. Economic Geology, 103, 6188.
Layton-Matthews, D., Leybourne, M.I., Peter, J.M., Scott, S.D., Cousens, B. and Eglington, B.M. (2013) Multiple sources of selenium in ancient seafloor hydrothermal systems: Compositional and Se, S, and Pb isotopic evidence from volcanic-hosted and volcanic-sediment-hosted massive sulfide deposits of the Finlayson Lake District, Yukon, Canada. Geochimica et Cosmochimica Acta, 117, 313331.
Lu, D., Chang, Y., Yang, H. and Xie, F. (2015) Sequential removal of selenium and tellurium from copper anode slime with high nickel content. Transactions of Nonferrous Metal Society of China, 25, 13071314.
Maslennikov, V.V., Maslennikova, S.P., Large, R.R. and Danyushevsky, L.V. (2009) Study of trace element zonation in vent chimneys from the Silurian Yaman-Kasy volcanic-hosted massive sulfide deposit (Southern Urals, Russia) using laser ablation-inductively coupled plasma mass spectrometry (LA-ICPMS). Economic Geology, 104, 11111141.
Melekestseva, I.Y., Maslennikov, V.V., Tret'yakov, G.A., Nimis, P., Beltenev, V.E., Rozhdestvenskaya, I.I., Maslennikova, S.P., Belogub, E.V., Danyushevsky, L., Large, R., Yuminov, A.M. and Sadykov, S.A. (2017) Gold- and Silver-Rich Massive Sulfides from the Semenov-2 Hydrothermal Field, 13°31.13'N, Mid-Atlantic Ridge: A Case of Magmatic Contribution? Economic Geology, 112, 741773.
Miyashiro, A. (1973) The Troodos Ophiolitic Complex was probably formed in an island arc. Earth and Planetary Science Letters, 19, 218224.
Moores, E.M., Varga, R.J., Verosub, K.L. and Ramsden, T.W. (1990) Regional structure of the Troodos dyke complex. Pp. 2735 in: Ophiolites: Oceanic Crustal Analogues (Malpas, J., Moores, E.M., Panayiotou, A. and Xenophontos, C., editors). Proceedings of the Symposium on Ophiolites and Oceanic Lithosphere, Troodos 87. Geological Survey Deptarment, Nicosia, Cyprus.
Moss, R.L., Tzimas, E., Kara, H., Willis, P. and Kooroshy, J. (2013) The potential risks from metals bottlenecks to the deployment of strategic energy technologies. Energy Policy, Special section: Long Run Transitions to Sustainable Economic Structures in the European Union and Beyond, 55, 556564.
Nuriel, P., Katzir, Y., Abelson, M., Valley, J.W., Matthews, A., Spicuzza, M.J. and Ayalon, A. (2009) Fault-related oceanic serpentinization in the Troodos ophiolite, Cyprus: implications for a fossil oceanic core complex. Earth and Planetary Science Letters, 282, 3446.
Patten, C.G.C., Pitcairn, I.K., Teagle, D.A.H. and Harris, M. (2016) Mobility of Au and related elements during the hydrothermal alteration of the oceanic crust: implications for the sources of metals in VMS deposits. Mineralium Deposita, 51, 179200.
Patten, C.G.C., Pitcairn, I.K. and Teagle, D.A.H. (2017) Hydrothermal mobilisation of Au and other metals in supra-subduction oceanic crust: Insights from the Troodos ophiolite. Ore Geology Reviews, 86, 487508.
Pearce, J.A., Lippard, S.J. and Roberts, S. (1984) Characteristics and tectonic significance of supra-subduction zone ophiolites. Pp. 7796 in: Ophiolites and Oceanic Lithosphere (Gass, I.G., Lippard, S.J. and Shelton, A.W., editors). Geological Society of London, No. 13.
Pearce, J.A. and Robinson, P.T. (2010) The Troodos ophiolitic complex probably formed in a subduction initiation, slab edge setting. Gondwana Research, A Tribute to Miyashiro, 18, 6081.
Perkins, W.T. (2011) Extreme selenium and tellurium contamination in soils – An eighty year-old industrial legacy surrounding a Ni refinery in the Swansea Valley. Science of the Total Environment, 412–413, 162169.
Prichard, H.M., Knight, R.D., Fisher, P.C., McDonald, I., Zhou, M.-F. and Wang, C.Y. (2013) Distribution of platinum-group elements in magmatic and altered ores in the Jinchuan intrusion, China: an example of selenium remobilization by postmagmatic fluids. Mineralium Deposita, 48, 767786.
Rahm, M., Hoffmann, R. and Ashcroft, N.W. (2016) Atomic and ionic radii of elements 1–96. Chemistry – A European Journal, 22, 1462514632.
Rautenschlein, M., Jenner, G.A., Hertogen, J., Hofmann, A.W., Kerrich, R., Schmincke, H.-U. and White, W.M. (1985) Isotopic and trace element composition of volcanic glasses from the Akaki Canyon, Cyprus: implications for the origin of the Troodos ophiolite. Earth and Planetary Science Letters, 75, 369383.
Revan, M.K., Genç, Y., Maslennikov, V.V., Maslennikova, S.P., Large, R.R. and Danyushevsky, L.V. (2014) Mineralogy and trace-element geochemistry of sulfide minerals in hydrothermal chimneys from the Upper-Cretaceous VMS deposits of the eastern Pontide orogenic belt (NE Turkey). Ore Geology Reviews, 63, 129149.
Richardson, C.J., Cann, J.R., Richards, H.G. and Cowan, J.G. (1987) Metal-depleted root zones of the Troodos ore-forming hydrothermal systems, Cyprus. Earth and Planetary Science Letters, 84, 243253.
Robertson, A. and Xenophontos, C. (1993) Development of concepts concerning the Troodos ophiolite and adjacent units in Cyprus. Geological Society of London Special Publication, 76, 85119.
Robertson, A.H.F. (2002) Overview of the genesis and emplacement of Mesozoic ophiolites in the Eastern Mediterranean Tethyan region. Lithos, 65, 167.
Robinson, P. and Malpas, J. (1987) The Troodos ophiolite of Cyprus: New perspectives on its origin and emplacement. Pp. 13-26 in: OPHIOLITES Oceanic Crustal Analogues (Malpas, J., Moores, E.M., Panayiotou, A. and Xenophontos, C., editors). Troodos 87, Ophiolites and Oceanic Lithosphere. Geological Survey Department of Cyprus, Nicosia, Cyprus.
Robinson, P.T., Melson, W.G., O'Hearn, T. and Schmincke, H.-U. (1983) Volcanic glass compositions of the Troodos ophiolite, Cyprus. Geology, 11, 400404.
Safina, N.P., Melekestseva, I.Y., Nimis, P., Ankusheva, N.N., Yuminov, A.M., Kotlyarov, V.A. and Sadykov, S.A. (2016) Barite from the Saf'yanovka VMS deposit (Central Urals) and Semenov-1 and Semenov-3 hydrothermal sulfide fields (Mid-Atlantic Ridge): a comparative analysis of formation conditions. Mineralium Deposita, 51, 491507.
Schiffman, P., Bettison, L.A. and Smith, B. (1990) Epidosites of the Solea graben. Pp 673684 in: OPHIOLITES Oceanic Crustal Analogues (Malpas, J., Moores, E.M., Panayiotou, A. and Xenophontos, C., editors). Troodos 87, Ophiolites and Oceanic Lithosphere. Geological Survey Department of Cyprus, Nicosia, Cyprus.
Seyfried, W. and Bischoff, J.L. (1977) Hydrothermal transport of heavy metals by seawater: The role of seawater/basalt ratio. Earth and Planetary Science Letters, 34, 7177.
Seyfried, W.E. Jr. and Mottl, M.J. (1982) Hydrothermal alteration of basalt by seawater under seawater-dominated conditions. Geochimica at Cosmochimica Acta, 46, 9851002.
Sillitoe, R.H., Hannington, M.D. and Thompson, J.F.H. (1996) High sulfidation deposits in the volcanogenic massive sulfide environment. Economic Geology, 91, 204212.
Smith, J.W., Holwell, D.A., McDonald, I. and Boyce, A.J. (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 Geology Reviews, 73, Part 1, 148174.
Tornos, F. (2006) Environment of formation and styles of volcanogenic massive sulfides: The Iberian Pyrite Belt. Ore Geology Reviews, 28, 259307.
Tornos, F., Peter, J.M., Allen, R. and Conde, C. (2015) Controls on the siting and style of volcanogenic massive sulfide deposits. Ore Geology Reviews, 68, 142163.
Varga, R.J. (1991) Modes of extension at oceanic spreading centres: evidence from the Solea graben, Troodos ophiolite, Cyprus. Journal of Structural Geology, 13, 517537.
Varga, R.J. and Moores, E.M. (1985) Spreading structure of the Troodos ophiolite, Cyprus. Geology, 13, 846850.
Varga, R.J. and Moores, E.M. (1990) Intermittent magmatic spreading and tectonic extension in the Troodos Ophiolite: implications for exploration for black smoker-type ore deposits. Pp. 5364 in: OPHIOLITES Oceanic Crustal Analogues (Malpas, J., Moores, E.M., Panayiotou, A. and Xenophontos, C., editors). Troodos 87, Ophiolites and Oceanic Lithosphere. Geological Survey Department of Cyprus, Nicosia, Cyprus.
Vibetti, N.J. (1993) Chemical alteration trends, fluid inclusion patterns and stable isotope compositions in the plutonic sequence of the Troodos ophiolite, Cyprus. Journal of African Earth Sciences. Middle East, 17, 193202.
Yamaoka, K., Matsukura, S., Ishikawa, T. and Kawahata, H. (2015) Boron isotope systematics of a fossil hydrothermal system from the Troodos ophiolite, Cyprus: Water–rock interactions in the oceanic crust and subseafloor ore deposits. Chemical Geology, 396, 6173.
Yildirim, N., Dönmez, C., Kang, J., Lee, I., Pirajno, F., Yıldırım, E., Günay, K., Seo, J.H., Farquhar, J. and Chang, S.W. (2016) A magnetite-rich Cyprus-type VMS deposit in Ortaklar: A unique VMS style in the Tethyan metallogenic belt, Gaziantep, Turkey. Ore Geology Reviews, 79, 425442.
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