Partitioning of nickel, copper, iridium, rhenium, platinum, and palladium between monosulfide solid solution and sulfide liquid: Effects of composition and temperature

1996 ◽  
Vol 60 (7) ◽  
pp. 1231-1238 ◽  
Author(s):  
C. Li ◽  
S.-J. Barnes ◽  
E. Makovicky ◽  
J. Rose-Hansen ◽  
M. Makovicky
Keyword(s):  
Solid Solution ◽  
Sulfide Liquid ◽  
Monosulfide Solid Solution ◽  
Nickel Copper

Partition coefficients for Ni, Cu, Pd, Pt, Rh, and Ir between monosulfide solid solution and sulfide liquid and the formation of compositionally zoned Ni – Cu sulfide bodies by fractional crystallization of sulfide liquid

1997 ◽  
Vol 34 (4) ◽  
pp. 366-374 ◽  
Author(s):  
Sarah-Jane Barnes ◽  
E. Makovicky ◽  
M. Makovicky ◽  
J. Rose-Hansen ◽  
S. Karup-Moller
Keyword(s):  
Solid Solution ◽  
Sulfur Content ◽  
Fractional Crystallization ◽  
Copper Sulfide ◽  
Partition Coefficients ◽  
Crystal Fractionation ◽  
Sulfide Liquid ◽  
Monosulfide Solid Solution ◽  
Experimental Systems ◽  
Nickel Copper

Many nickel–copper sulfide orebodies contain Cu- and Fe-rich portions. The Fe-rich ore is generally richer in Os, Ir, Ru, and Rh and poorer in Pt, Pd, and Au than the Cu-rich ore. In komatiite-hosted ores Ni tends to be concentrated in the Cu-rich ore, whereas in tholeiitic ores it tends to be concentrated in the Fe-rich ore. The origin of this zonation could be due to crystal fractionation of Fe-rich monosulfide solid solution from a sulfide liquid. The crystal fractionation would produce an Fe-rich cumulate enriched in Os, Ir, Ru, and Rh and a fractionated liquid enriched in Cu, Pt, Pd, and Au. This model can be tested for zoned orebodies by applying experimentally determined partition coefficients for the metals into monosulfide solid solution. We have compared our experimental results with those of other workers to show that the partition coefficients are strongly influenced by the sulfur content of the system. There is a positive correlation between the partition coefficients and sulfur content of the monosulfide solid solution and between the partition coefficients and the sulfur content of the liquid. In sulfur-saturated and sulfur-over-saturated experimental systems, the metals behave in a manner consistent with the model, that is, Os, Ir, Ru, and Rh are compatible with monosulfide solid solution, Cu, Pd, and Pt are incompatible, and Ni has a partition coefficient close to 1. The use of the experimental partition coefficients is demonstrated in the numerical modelling of a zoned komatiite-related ore (Alexo, Abitibi Greenstone Belt) and a zoned tholeiite-related ore (Oktyabr'sky, Noril'sk region, Siberia). In both cases, the experimental partition coefficients numerically model the composition zones of the actual ores. This supports the model of fractional crystallization of a monosulfide solid solution from a sulfide liquid to form zoned orebodies. Furthermore, it indicates that the experimentally determined partition coefficients are geologically reasonable.

Magnetite Chemistry by LA-ICP-MS Records Sulfide Fractional Crystallization in Massive Nickel-Copper-Platinum Group Element Ores from the Norilsk-Talnakh Mining District (Siberia, Russia): Implications for Trace Element Partitioning into Magnetite

2020 ◽  
Vol 115 (6) ◽  
pp. 1245-1266 ◽  
Author(s):  
Charley J. Duran ◽  
Sarah-Jane Barnes ◽  
Eduardo T. Mansur ◽  
Sarah A.S. Dare ◽  
L. Paul Bédard ◽  
...  
Keyword(s):  
Solid Solution ◽  
Fractional Crystallization ◽  
Platinum Group Element ◽  
Group Element ◽  
Sulfide Liquid ◽  
Mining District ◽  
Monosulfide Solid Solution ◽  
Sulfide Deposits ◽  
Chalcophile Elements ◽  
Platinum Group

Abstract Mineralogical and chemical zonations observed in massive sulfide ores from Ni-Cu-platinum group element (PGE) deposits are commonly ascribed to the fractional crystallization of monosulfide solid solution (MSS) and intermediate solid solution (ISS) from sulfide liquid. Recent studies of classic examples of zoned orebodies at Sudbury and Voisey’s Bay (Canada) demonstrated that the chemistry of magnetite crystallized from sulfide liquid was varying in response to sulfide fractional crystallization. Other classic examples of zoned Ni-Cu-PGE sulfide deposits occur in the Norilsk-Talnakh mining district (Russia), yet magnetite in these orebodies has received little attention. In this contribution, we document the chemistry of magnetite in samples from Norilsk-Talnakh, spanning the classic range of sulfide composition, from Cu poor (MSS) to Cu rich (ISS). Based on textural features and mineral associations, four types of magnetite with distinct chemical composition are identified: (1) MSS magnetite, (2) ISS magnetite, (3) reactional magnetite (at the sulfide-silicate interface), and (4) hydrothermal magnetite (resulting from sulfide-fluid interaction). Compositional variability in lithophile and chalcophile elements records sulfide fractional crystallization across MSS and ISS magnetites and sulfide interaction with silicate minerals (reactional magnetite) and fluids (hydrothermal magnetite). Estimated partition coefficients for magnetite in sulfide systems are unlike those in silicate systems. In sulfide systems, all lithophile elements are compatible and chalcophile elements tend to be incompatible with magnetite, but in silicate systems some lithophile elements are incompatible and chalcophile elements are compatible with magnetite. Finally, comparison with magnetite data from other Ni-Cu-PGE sulfide deposits pinpoints that the nature of parental silicate magma, degree of sulfide evolution, cocrystallizing phases, and alteration conditions influence magnetite composition.

scholarly journals Composition of iron oxides in Archean and Paleoproterozoic mafic-ultramafic hosted Ni-Cu-PGE deposits in northern Fennoscandia: application to mineral exploration

2020 ◽  
Vol 55 (8) ◽  
pp. 1515-1534
Author(s):  
M. Moilanen ◽  
E. Hanski ◽  
J. Konnunaho ◽  
T. Törmänen ◽  
S.-H. Yang ◽  
...  
Keyword(s):  
Trace Element ◽  
Iron Oxides ◽  
Oxide Phase ◽  
Massive Sulfide ◽  
Sulfide Liquid ◽  
Monosulfide Solid Solution ◽  
Sulfide Deposits ◽  
Northern Fennoscandia ◽  
Pge Mineralization ◽  
Wide Range

Abstract Using electron probe microanalyzer (EPMA) and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS), we analyzed major and trace element compositions of iron oxides from Ni-Cu-PGE sulfide deposits hosted by mafic-ultramafic rocks in northern Fennoscandia, mostly focusing on Finland. The main research targets were the Archean Ruossakero Ni-(Cu) deposit; Tulppio dunite and related Ni-PGE mineralization; Hietaharju, Vaara, and Tainiovaara Ni-(Cu-PGE) deposits; and Paleoproterozoic Lomalampi PGE-(Ni-Cu) deposit. In addition, some reference samples from the Pechenga (Russia), Jinchuan (China), and Kevitsa (Finland) Ni-Cu-PGE sulfide deposits, and a barren komatiite sequence in the Kovero area (Finland) were studied. Magnetite and Cr-magnetite show a wide range of trace element compositions as a result of the variation of silicate and sulfide melt compositions and their post-magmatic modification history. Most importantly, the Ni content in oxide shows a positive correlation with the Ni tenor of the sulfide phase in equilibrium with magnetite, regardless of whether the sulfide assemblage is magmatic or post-magmatic in origin. The massive sulfide samples contain an oxide phase varying in composition from Cr-magnetite to magnetite, indicating that Cr-magnetite can crystallize directly from sulfide liquid. The Mg concentration of magnetites in massive sulfide samples is lowest among the samples analyzed, and this can be regarded as a diagnostic feature of an oxide phase crystallized together with primitive Fe-rich MSS (monosulfide solid solution). Our results show that magnetite geochemistry, plotted in appropriate discrimination diagrams, together with petrographical observations could be used as an indicator of potential Ni-(Cu-PGE) mineralization.

scholarly journals Magmatic sulfides in high-potassium calc-alkaline to shoshonitic and alkaline rocks

Solid Earth ◽  
2020 ◽  
Vol 11 (1) ◽  
pp. 1-21 ◽  
Author(s):  
Ariadni A. Georgatou ◽  
Massimo Chiaradia
Keyword(s):  
Solid Solution ◽  
Early Stage ◽  
Volcanic Field ◽  
Geodynamic Setting ◽  
Calc Alkaline ◽  
High Potassium ◽  
Western Turkey ◽  
Monosulfide Solid Solution ◽  
Magmatic Sulfides ◽  
Saturation Stage

Abstract. We investigate the occurrence and chemistry of magmatic sulfides and their chalcophile metal cargo behaviour during the evolution of compositionally different magmas from diverse geodynamic settings both in mineralised and barren systems. The investigated areas are the following: (a) the Miocene Konya magmatic province (hosting the Doğanbey Cu–Mo porphyry and Inlice Au epithermal deposits, representing post-subduction) and (b) the Miocene Usak basin (Elmadag, Itecektepe, and Beydagi volcanoes, the latter associated with the Kişladağ Au porphyry in western Turkey, representing post-subduction). For comparison we also investigate (c) the barren intraplate Plio-Quaternary Kula volcanic field west of Usak. Finally, we discuss and compare all the above areas with the already studied (d) Quaternary Ecuadorian volcanic arc (host to the Miocene Llurimagua Cu–Mo and Cascabel Cu–Au porphyry deposits, representing subduction). The volcanism of the newly studied areas ranges from basalts to andesites–dacites and from high-K calc-alkaline to shoshonitic series. Multiphase magmatic sulfides occur in different amounts in rocks of all investigated areas, and, based on textural and compositional differences, they can be classified into different types according to their crystallisation at different stages of magma evolution (early versus late saturation). Our results suggest that independently of the magma composition, geodynamic setting, and association with an ore deposit, sulfide saturation occurred in all investigated magmatic systems. Those systems present similar initial metal contents of the magmas. However, not all studied areas present all sulfide types, and the sulfide composition depends on the nature of the host mineral. A decrease in the sulfide Ni∕Cu (a proxy for the monosulfide solid solution (mss) to intermediate solid solution (iss) ratio) is noted with magmatic evolution. At an early stage, Ni-richer, Cu-poorer sulfides are hosted by early crystallising minerals, e.g. olivine–pyroxene, whereas, at a later stage, Cu-rich sulfides are hosted by magnetite. The most common sulfide type in the early saturation stage is composed of a Cu-poor, Ni-rich (pyrrhotite mss) phase and one to two Cu-rich (cubanite, chalcopyrite iss) phases, making up ∼84 and ∼16 area % of the sulfide, respectively. Sulfides resulting from the late stage, consisting of Cu-rich phases (chalcopyrite, bornite, digenite iss), are hosted exclusively by magnetite and are found only in evolved rocks (andesites and dacites) of magmatic provinces associated with porphyry Cu (Konya and Ecuador) and porphyry Au (Beydagi) deposits.

The Occurrence and Origin of Pentlandite-Chalcopyrite-Pyrrhotite Loop Textures in Magmatic Ni-Cu Sulfide Ores

2020 ◽  
Vol 115 (8) ◽  
pp. 1777-1798 ◽  
Author(s):  
Stephen J. Barnes ◽  
Valentina Taranovic ◽  
Louise E. Schoneveld ◽  
Eduardo T. Mansur ◽  
Margaux Le Vaillant ◽  
...  
Keyword(s):  
Grain Boundary ◽  
Peritectic Reaction ◽  
Inductively Coupled Plasma ◽  
Mass Spectrometry Analysis ◽  
Sulfide Liquid ◽  
Monosulfide Solid Solution ◽  
Spectrometry Analysis ◽  
Inductively Coupled ◽  
Regional Deformation ◽  
Wide Range

Abstract Pentlandite is the dominant Ni-hosting ore mineral in most magmatic sulfide deposits and has conventionally been interpreted as being entirely generated by solid-state exsolution from the high-temperature monosulfide solid solution (MSS) (Fe,Ni)1–xS. This process gives rise to the development of loops of pentlandite surrounding pyrrhotite grains. Recently it has been recognized that not all pentlandite forms by exsolution. Some may form as the result of peritectic reaction between early formed MSS and residual Ni-Cu–rich sulfide liquid during differentiation of the sulfide melt, such that at least some loop textures may be genuinely magmatic in origin. Testing this hypothesis involved microbeam X-ray fluorescence mapping to image pentlandite-pyrrhotite-chalcopyrite intergrowths from a range of different deposits. These deposits exemplify slowly cooled magmatic environments (Nova, Western Australia; Sudbury, Canada), globular ores from shallow-level intrusions (Norilsk, Siberia), extrusive komatiite-hosted ores from low and high metamorphic-grade terranes, and a number of other deposits. Our approach was complemented by laser ablation-inductively coupled plasma-mass spectrometry analysis of palladium in varying textural types of pentlandite within these deposits. Pentlandite forming coarse granular aggregates, together with loop-textured pentlandite where chalcopyrite also forms part of the loop framework, consistently has the highest Pd content compared with pentlandite clearly exsolved as lamellae from MSS or pyrrhotite. This is consistent with much of granular and loop pentlandite being formed by peritectic reaction between Pd-rich residual sulfide liquid and early crystallized MSS, rather than forming entirely by subsolidus grain boundary exsolution from MSS, as has hitherto been assumed. The wide range of Pd contents in pentlandite in individual samples reflects a continuum of processes between peritectic reaction and grain boundary exsolution. Textures in metamorphically recrystallized ores are distinctly different from loop-textured ores, implying that loop textures cannot be regenerated (except in special circumstances) by metamorphic recrystallization of original magmatic-textured ores. The presence of loop textures can therefore be taken as evidence of a lack of penetrative deformation and remobilization at submagmatic temperatures, a conclusion of particular significance to the interpretation of the Nova deposit as having formed synchronously with the peak of regional deformation at temperatures within the sulfide melting range.

Platinum Group Element Enrichment of Natural Quenched Sulfide Solid Solutions, the Norilsk 1 Deposit, Russia

2020 ◽  
Vol 115 (6) ◽  
pp. 1343-1361
Author(s):  
Valeriya D. Brovchenko ◽  
Sergey F. Sluzhenikin ◽  
Elena V. Kovalchuk ◽  
Sofia V. Kovrigina ◽  
Vera D. Abramova ◽  
...  
Keyword(s):  
Solid Solution ◽  
High Temperature ◽  
Solid Solutions ◽  
Platinum Group Element ◽  
Group Element ◽  
Temperature Fields ◽  
Chemical Compositions ◽  
Monosulfide Solid Solution ◽  
Icp Ms ◽  
Platinum Group

Abstract The deepest terminations of the Mount Rudnaya subvertical massive sulfide offshoots of the Norilsk 1 orebody are composed of exceptionally fine grained sulfides that are believed to be natural quenched sulfide solid solutions. Copper-rich intermediate solid solution (ISS) and Fe-rich monosulfide solid solution (MSS) form an equigranular and lamellar matrix hosting MSS- and ISS-dominant globules. The nonstoichiometric chemical compositions of the solid solutions plot within their high-temperature fields known from experiments. MSS contains 19 to 35 wt % Ni, 0.09 to 0.45 wt % Co, and up to 0.6 wt % Cu and is heterogeneously enriched in Rh (up to 32 ppm), Ir (up to 0.6 ppm), Pt (up to 65 ppm), and Pd (up to 168 ppm). ISS occurs as the lamellar intergrowths of the chalcopyrite (Ccpss) and cubanite (Cubss) solid solutions, which bear up to 4.74 wt % Ni and 0.2 wt % Co and are heterogeneously enriched in Zn, Ag, and In. The assemblage of platinum group minerals (PGMs) is hosted mostly in the ISS and is dominated by Pt-Fe alloys and minerals of the rustenburgite-atokite series, like the set of PGMs at the Norilsk 1 deposit. Similar Pt-Pd-Sn compounds in the laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) spectra of profiles through MSS and ISS are interpreted to be trapped microinclusions. The pentlandite contains up to 0.13 wt % Pt, up to 4.62 wt % Pd, <0.53 wt % Co, and <0.4 wt % Cu according to electron microprobe analysis. LA-ICP-MS data and mapping show that Pd content in the pentlandite increases toward contacts with ISS and decreases toward contacts with MSS, supporting a reaction origin of pentlandite. The wide variations of the concentrations of major and trace elements in the solid solutions, as well as the coexistence of Pd-poor (a few ppm Pd) and Pd-rich (over 4.62 wt % Pd) pentlandite within a single sample, seem to characterize the different generations of the MSS to MSS-ISS globules, antecrysts, and phenocrysts with the distinct histories of enrichment due to exchange with fractionated Cu-platinum group element-rich residue. The directional distribution of Pd of high-temperature primary magmatic origin is preserved due to rapid quenching of the sulfides from ~650°C.

Genesis of the Jinbaoshan PGE-(Cu)-(Ni) deposit: Distribution of chalcophile elements and platinum-group minerals

2021 ◽  
Vol 59 (6) ◽  
pp. 1511-1542
Author(s):  
Yiguan Lu ◽  
C. Michael Lesher ◽  
Liqiang Yang ◽  
Matthew I. Leybourne ◽  
Wenyan He ◽  
...  
Keyword(s):  
Solid Solution ◽  
Platinum Group Element ◽  
Platinum Group Elements ◽  
Group Element ◽  
Monosulfide Solid Solution ◽  
Platinum Group Minerals ◽  
Pd Alloy ◽  
Platinum Group ◽  
Lower Temperature ◽  
Subduction System

ABSTRACT The Jinbaoshan platinum group element-(Cu)-(Ni) deposit in southwest China is a sulfide-poor magmatic platinum-group element deposit that experienced multiple phases of post-magmatic modification. The sulfide assemblages of most magmatic Ni-Cu-platinum-group element deposits in China and elsewhere in the world are dominated by pentlandite-pyrrhotite-chalcopyrite with lesser magnetite and minor platinum-group minerals. However, Jinbaoshan is characterized by (1) hypogene violarite-pyrite 1-millerite-chalcopyrite and (2) supergene violarite-(polydymite)-pyrite 2-chalcopyrite assemblages. The platinum-group minerals are small (0.5–10 μm diameter) and include moncheite Pt(Te,Bi)2, mertieite-I Pd11(Sb,As)4, the atokite Pd3Sn – rustenburgite Pt3Sn solid solution, irarsite IrAsS, and sperrylite PtAs2 hosted mainly by violarite, silicates (primarily serpentine), and millerite. The platinum-group minerals occur in two sulfide assemblages: (1) mertieite-I-dominant (with irarsite, palladium, and Pd-alloy) in the hypogene assemblage and (2) moncheite-dominant (with irarsite, sperrylite, and atokite) in the supergene assemblage. Palladium and intermediate platinum-group elements (Os, Ir, Ru) are concentrated mainly in violarite, polydymite, and pyrite 2. Platinum is seldom hosted by base metal sulfides and occurs mainly as discrete platinum-group minerals, such as moncheite, sperrylite, and merenskyite. Violarite and polydymite in the Jinbaoshan deposit contain more Pb-Ag than pentlandite and pyrrhotite in the Great Dyke and Lac des Iles deposit. The formation of the sulfide assemblages in Jinbaoshan can be interpreted to have occurred in three stages: (1) a magmatic Fe-Ni-Cu sulfide melt crystallized Fe-Ni monosulfide and Cu-rich intermediate solid solutions, which inverted to a primary pyrrhotite-pentlandite-chalcopyrite-magnetite assemblage; (2) an early-secondary hypogene voilarite-millterite-pyrite 1-chalcopyrite assemblage formed by interaction with a lower-temperature magmatic-hydrothermal deuteric fluid; and (3) a late-secondary supergene violarite-polydymite-pyrite 2-chalcopyrite assemblage formed during weathering. Late-magmatic-hydrothermal fluids enriched the mineralization in Pb-Ag-Cd-Zn, which are incompatible in monosulfide solid solution, added Co-Pt into violarite, and expelled Pd to the margins of hypogene violarite and millerite, which caused Pd depletion in the hypogene violarite and the formation of mertieite-I. Supergene violarite inherited Pd and intermediate platinum-group elements from primary pentlandite. Thus, the unusual sulfide assemblages in the Jinbaoshan platinum-group element-(Cu)-(Ni) deposit results from multiple overprinted post-magmatic processes, but they did not significantly change the chalcophile element contents of the mineralization, which is interpreted to have formed at high magma:sulfide ratios (R factors) through interaction of crustally derived sulfide and a hybrid picritic-ferropicritic magma derived from subduction-metasomatized pyroxenitic mantle during impingement of the Emeishan plume on the Paleo-Tethyan oceanic subduction system.

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