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1.
Concentrations of Ag, Au, Cd, Co, Re, Zn and Platinum-group elements (PGE) have been determined in sulfide minerals from zoned sulfide droplets of the Noril’sk 1 Medvezky Creek Mine. The aims of the study were; to establish whether these elements are located in the major sulfide minerals (pentlandite, pyrrhotite, chalcopyrite and cubanite), to establish whether the elements show a preference for a particular sulfide mineral and to investigate the model, which suggests that the zonation in the droplets is caused by the crystal fractionation of monosulfide solid solution (mss). Nickel, Cu, Ag, Re, Os, Ir, Ru, Rh and Pd, were found to be largely located in the major sulfide minerals. In contrast, less than 25% of the Au, Cd, Pt and Zn in the rock was found to be present in these sulfides. Osmium, Ir, Ru, Rh and Re were found to be concentrated in pyrrhotite and pentlandite. Palladium and Co was found to be concentrated in pentlandite. Silver, Cd and Zn concentrations are highest in chalcopyrite and cubanite. Gold and platinum showed no preference for any of the major sulfide minerals. The enrichment of Os, Ir, Ru, Rh and Re in pyrrhotite and pentlandite (exsolution products of mss) and the low levels of these elements in the cubanite and chalcopyrite (exsolution products of intermediate solid solution, iss) support the mss crystal fractionation model, because Os, Ir, Ru, Rh and Re are compatible with mss. The enrichment of Ag, Cd and Zn in chalcopyrite and cubanite also supports the mss fractionation model these minerals are derived from the fractionated liquid and these elements are incompatible with mss and thus should be enriched in the fractionated liquid. Gold and Pt do not partition into either iss or mss and become sufficiently enriched in the final fractionated liquid to crystallize among the iss and mss grains as tellurides, bismithides and alloys. During pentlandite exsolution Pd appears to have diffused from the Cu-rich portion of the droplet into pentlandite.  相似文献   

2.
Concentrations of platinum group elements (PGE), Ag, As, Au, Bi, Cd, Co, Mo, Pb, Re, Sb, Se, Sn, Te, and Zn, have been determined in base metal sulfide (BMS) minerals from the western branch (402 Trough orebodies) of the Creighton Ni–Cu–PGE sulfide deposit, Sudbury, Canada. The sulfide assemblage is dominated by pyrrhotite, with minor pentlandite, chalcopyrite, and pyrite, and they represent monosulfide solid solution (MSS) cumulates. The aim of this study was to establish the distribution of the PGE among the BMS and platinum group minerals (PGM) in order to understand better the petrogenesis of the deposit. Mass balance calculations show that the BMS host all of the Co and Se, a significant proportion (40–90%) of Os, Pd, Ru, Cd, Sn, and Zn, but very little (<35%) of the Ag, Au, Bi, Ir, Mo, Pb, Pt, Rh, Re, Sb, and Te. Osmium and Ru are concentrated in equal proportions in pyrrhotite, pentlandite, and pyrite. Cobalt and Pd (∼1 ppm) are concentrated in pentlandite. Silver, Cd, Sn, Zn, and in rare cases Au and Te, are concentrated in chalcopyrite. Selenium is present in equal proportions in all three BMS. Iridium, Rh, and Pt are present in euhedrally zoned PGE sulfarsenides, which comprise irarsite (IrAsS), hollingworthite (RhAsS), PGE-Ni-rich cobaltite (CoAsS), and subordinate sperrylite (PtAs2), all of which are hosted predominantly in pyrrhotite and pentlandite. Silver, Au, Bi, Mo, Pb, Re, Sb, and Te are found predominantly in discrete accessory minerals such as electrum (Au–Ag alloy), hessite (Ag2Te), michenerite (PdBiTe), and rhenium sulfides. The enrichment of Os, Ru, Ni, and Co in pyrrhotite, pentlandite, and pyrite and Ag, Au, Cd, Sn, Te, and Zn in chalcopyrite can be explained by fractional crystallization of MSS from a sulfide liquid followed by exsolution of the sulfides. The early crystallization of the PGE sulfarsenides from the sulfide melt depleted the MSS in Ir and Rh. The bulk of Pd in pentlandite cannot be explained by sulfide fractionation alone because Pd should have partitioned into the residual Cu-rich liquid and be in chalcopyrite or in PGM around chalcopyrite. The variation of Pd among different pentlandite textures provides evidence that Pd diffuses into pentlandite during its exsolution from MSS. The source of Pd was from the small quantity of Pd that partitioned originally into the MSS and a larger quantity of Pd in the nearby Cu-rich portion (intermediate solid solution and/or Pd-bearing PGM). The source of Pd became depleted during the diffusion process, thus later-forming pentlandite (rims of coarse-granular, veinlets, and exsolution flames) contains less Pd than early-forming pentlandite (cores of coarse-granular).  相似文献   

3.
The Platreef unit of the northern Bushveld Complex comprises a diverse package of pyroxenites, peridotites and mafic lithologies with associated Ni–Cu–platinum-group element (PGE) mineralisation. Base metal sulphides (BMS) are generally more abundant in the Platreef than in other Bushveld PGE deposits, such as the Merensky Reef and the UG2 chromitite, but the Platreef, though thicker, has lower overall PGE grades. Despite a commonly held belief that PGEs are closely associated with sulphide mineralisation, a detailed study by laser ablation ICP-MS (LA-ICP-MS) on a core through the Platreef at Turfspruit suggests that this is not strictly the case. While a significant proportion of the Pd, Os and Ir were found to be hosted by BMS, Pt, irrespective of its whole-rock concentration, was not. Only at the top of the Platreef is Pt directly associated with sulphide minerals where Pt–Pd–(±Sb)–Te–Bi-bearing inclusions were detected in the chalcopyrite portions of large composite sulphides. In contrast, Pd, Os, and Ir occur in solid solution and as discrete inclusions within the BMS throughout the core. For Os and Ir, this is usually in the form of Os–Ir alloys, whereas Pd forms a range of Pd–Te–Bi–(Sb) phases. Scanning electron microscope observations on samples from the top of the core revealed the presence of ≤0.2-mm-long (PtPd)2(Sb,Te,Bi)2 michenerite–maslovite laths within the chalcopyrite portions of large composite sulphides. Additional Pt-bearing minerals, including sperrylite and geversite, and a number of Pd(–Te–Bi–Sb) minerals were observed in, or close to, the alteration rims of these sulphides. This textural association was observed throughout the core. Similar platinum-group minerals (PGMs) were observed within the felsic assemblages composed of quartz, plagioclase, alkali feldspar and clinopyroxene produced by late-stage felsic melts that permeated the Platreef. Many of these PGMs occur a significant distance away from any sulphide minerals. We believe these features can all be linked to the introduction of As, Sb, Te and Bi into the magmatic system through assimilation of sedimentary footwall rocks and xenoliths. Where the degree of contamination was high, all of the Pt and some of the Pd formed As- and Sb-bearing PGM that were expelled to the edges of the sulphide droplets. Many of these were redistributed where they came into contact with late-stage felsic melts. Where no felsic melt interactions occurred, the expelled Pt- and Pd-arsenides and antimonides remained along the margins of the sulphides. At the top of the Platreef, where the effects of contamination were relatively low, some of the Pt remained within the sulphide liquids. On cooling, this formed the micro-inclusions and blade-like laths of Pt–Pd–(Sb)–Bi–Te in the chalcopyrite.  相似文献   

4.
The quasiequilibrium directed crystallization technique was used for experimental simulation of zoning characteristic of Cu-rich pyrrhotite-chalcopyrite and pyrrhotite-cubanite-mooihoekite-haycockite ores at the Oktyabr??sky deposit. Directed crystallization of samples I (Fe 32.55, Cu 10.70, Ni 5.40, S. 51.00, Pt = Pd = Rh = Ir= Au = Ag = 0.05 at %) and II (Fe 33.74, Cu 15.94, Ni 1.48, S. 48.75, Pt = Pd = 0.05 at %) was performed. These samples approximate average composition of the ore. Monosulfide (mms) and intermediate (iss) solid solutions progressively crystallized from the melt. The curves of ore element distribution in samples have been drawn. The partition coefficients (k) of ore elements between solid solutions and sulfide melt have been determined depending on melt composition. The paths of melt, mss, and iss compositions are supplemented by tie lines connecting compositions of equilibrium liquid and solid phases. The phase composition of samples after cooling was studied using an optical microscope, XRD, and microprobe. The zoning of sample I is described by the following sequence of phases: monoclinic pyrrhotite ?? hexagonal pyrrhotite + tetragonal chalcopyrite ?? tetragonal and cubic chalcopyrite + pentlandite + bornite. Crystallized sample II consists of four zones: (1) hexagonal pyrrhotite and isocubanite; (2) hexagonal pyrrhotite, cubanite, and pentlandite; (3) low-S pc-phase close to haycockite and pentlandite; and (4) mooihoekite, pentlandite, and bornite mixtures. This sequence corresponds to the secondary zoning, which reflects both the primary fractionation of components and the solid-phase reactions during cooling of the crystallized sample. The Rh, Ru, and Ir partition coefficients between mss and melt have been measured, and speciation of PGM in samples has been identified. The results obtained are compared with typical natural Cu-rich sulfide ore of the Oktyabr??sky deposit.  相似文献   

5.
Summary The Jinchuan deposit is a platinum group element (PGE)-rich sulfide deposit in China. Drilling and surface sampling show that three categories of platinum group element (PGE) mineralization occur; type I formed at magmatic temperatures, type II occurs in hydrothermally altered zones of the intrusion, and type III in sheared dunite and lherzolite. All ore types were analyzed for Os, Ir, Ru, Rh, Pd, Pt and Au, as well as for Cu, Ni, Co and S. Type I ore has (Pt + Pd)/(Os + Ir + Ru + Rh) ratios of <7 and relatively flat chondrite-normalized noble metal patterns; the platinum group minerals (PGM) are dominated by sperrylite and moncheite associated with chalcopyrite, pyrrhotite and pentlandite. Type II has (Pt + Pd)/(Os + Ir + Ru + Rh) ratios from 40 to 330 and noble metal distribution patterns with a positive slope; the most common PGM are sperrylite and Pd bismuthotelluride phases concentrated mostly at the margins of base metal sulfides. Type III ores have the highest (Pt + Pd)/(Os + Ir + Ru + Rh) ratios from 240 to 710; the most abundant PGM are sperrylite and phases of the Pt–Pd–Te–Bi–As–Cl system. It is concluded that the Jinchuan deposit formed as a result of primary magmatic crystallization followed by hydrothermal remobilization, transport, and deposition of the PGE.  相似文献   

6.
The paper presents concentrations of the platinum-group and chalcophile elements in the base metal sulfides (BMS) from the Jinchuan Ni–Cu sulfide deposit determined by laser ablation-inductively coupled plasma-mass spectrometry. Mass balance calculations reveal that pentlandite hosts a large proportion of Co, Ni and Pd (> 65%), and that pentlandite and pyrrhotite accommodate significant proportions of Re, Os, Ru, Rh, and Ag (~ 35–90%), whereas chalcopyrite contains a small amount of Ag (~ 10%) but negligible platinum-group elements. Iridium and Pt are not concentrated in the BMS and mostly occur in As-rich platinum-group minerals. The enrichments of Co, Ni, Re, Os, Ru, and Rh in pentlandite and pyrrhotite, and Cu in chalcopyrite are consistent with the fractionation of sulfide liquid and exsolution of pentlandite and pyrrhotite from the mono-sulfide solid solution (MSS). The Ir-bearing minerals exsolved from the MSS, depleting pentlandite and pyrrhotite in Ir, whereas sperrylite exsolved from the residual sulfide liquid on cooling. Diffusion of Pd from residual sulfide liquid into pentlandite during its exsolution from the MSS and crystallization of Pt-bearing minerals in the residual sulfide liquid resulted in the enrichment of Pd in pentlandite and decoupling between Pd and Pt in the Jinchuan net-textured and massive ores.  相似文献   

7.
Platinum-group element (PGE) mineralisation within the Platreef at Overysel is controlled by the presence of base metal sulphides (BMS). The floor rocks at Overysel are Archean basement gneisses, and unlike other localities along the strike of the Platreef where the floor is comprised of Transvaal Supergroup sediments, the intimate PGE–BMS relationship holds strong into the footwall rocks. Decoupling of PGE from BMS is rare and the BMS and platinum-group mineral assemblages in the Platreef and the footwall are almost identical. There is minimal overprinting by hydrothermal fluids; therefore, the mineralisation style present at Overysel may represent the most ‘primary’ style of Platreef mineralisation preserved anywhere along the strike. Chondrite-normalised PGE profiles reveal a progressive fractionation of the PGE with depth into the footwall, with Ir, Ru and Rh dramatically depleted with depth compared to Pt, Pd and Au. This feature is not observed at Sandsloot and Zwartfontein, to the south of Overysel, where the footwall rocks are carbonates. There is evidence from rare earth element abundances and the amount of interstitial quartz towards the base of the Platreef pyroxenites that contamination by a felsic melt derived from partial melting of the gneissic footwall has taken place. Textural evidence in the gneisses suggests that a sulphide liquid percolated down into the footwall through a permeable, inter-granular network that was produced by partial melting around grain boundaries in the gneisses that was induced by the intrusion of the Platreef magma. PGE were originally concentrated within a sulphide liquid in the Platreef magma, and the crystallisation of monosulphide solid solution from the sulphide liquid removed the majority of the IPGE and Rh from it whilst still within the mafic Platreef. Transport of PGE into the gneisses, via downward migration of the residual sulphide liquid, fractionated out the remaining IPGE and Rh in the upper parts of the gneisses leaving a ‘slick’ of disseminated sulphides in the gneiss, with the residual liquid becoming progressively more depleted in these elements relative to Pt, Pd and Au. Highly sulphide-rich zones with massive sulphides formed where ponding of the sulphide liquid occurred due to permeability contrasts in the footwall. This study highlights the fact that there is a fundamental floor rock control on the mechanism of distribution of PGE from the Platreef into the footwall rocks. Where the floor rocks are sediments, fluid activity related to metamorphism, assimilation and later serpentinisation has decoupled PGE from BMS in places, and transport of PGE into the footwall is via hydrothermal fluids. In contrast, where the floor is comprised of anhydrous gneiss, such as at Overysel, there is limited fluid activity and PGE behaviour is controlled by the behaviour of sulphide liquids, producing an intimate PGE–BMS association. Xenoliths and irregular bands of chromitite within the Platreef are described in detail for the first time. These are rich in the IPGE and Rh, and evidence from laurite inclusions indicates they must have crystallised from a PGE-saturated magma. The disturbed and xenolithic nature of the chromitites would suggest they are rip-up clasts, either disturbed by later pulses of Platreef magma in a multi-phase emplacement or transported into the Platreef from a pre-existing source in a deeper staging chamber or conduit.  相似文献   

8.
To study the behavior of macrocomponents and admixtures during the fractional crystallization of sulfide melts and the influence of As on noble metals in this process, we performed a quasi-equilibrium directional crystallization of melt of composition (at.%): Fe—35.5, Ni—4.9, Cu—10.4, and S—48.3, with admixtures of Pt, Pd, Rh, Ru, Ir, Au, Ag, As, and Co (each 0.1 at.%), which imitates the average (by Cu contents) compositions of massive ores at the Noril'sk Cu-Ni deposits. The following sequence of phase formation from melt has been established: mss (zone I) / mss + iss (zone II) / iss (zone III) (mss is (FezNi1–z)S1+δ, iss is (FexCuyNi1–x–y)zS1–z); it corresponds to the distribution of main elements along the sample (primary zoning). Distribution curves for macrocomponents in zones I and II of the sample were constructed, as well as the dependencies of their partition coefficients (k) between solid solutions and sulfide melt on the fraction of crystallized melt. The secondary (mineral) zoning resulted from subsolidus phase transformations has been revealed. Five subzones have been recognized: mss + cp (Ia) / mss + cp + pn (Ib) / mss + pc + pn (IIa) / mss + pc + pn + bn (IIb) / pc + bn + pn + unidentified microphases (III). Admixture species in the sample were studied: (1) admixtures dissolved in primary solid solutions and in main minerals resulted from solid-phase transformations and (2) admixtures forming their own mineral phases. The partition coefficients of Co, Rh, and Ru (mss/L), Ru, Ir, and Rh (mss/cp), and Co, Rh, and Pd (mss/pn) were determined. Minerals of noble metals have been recognized: Pt3Fe, PtFe, Au, (Ag,Pd), (Au,Pt), Ag, Ag3Cu, Au3(Cu,Ag,Pd,Pt), etc., and the regularities of their distribution in the sample have been established. It is shown that some noble-metal admixtures are prone to interact with As. Mineral arsenides and sulfoarsenides of noble metals produced during fractional crystallization have been recognized: PtAs2, Pd3As, (RhAsS), (IrAsS), and (Ir,Rh)AsS. The discovered drop-like inclusions of noble-metal arsenides suggest the separation of the initial sulfide-arsenide melt into two immiscible liquids. By indirect features, the micromineral inclusions are divided into primary, crystallized from melt, and secondary, produced in solid-phase reactions. The results of study are compared with literature experimental data obtained by the isothermal-annealing method and with the behavior of noble metals and As during the formation of zonal massive orebodies at the Noril'sk- and Sudbury-type deposits.  相似文献   

9.
Platinum group elements (PGE) enrichment occurs in Zn–Cu and Ni-rich ophiolities in a number of geological settings. Platinum group elements (PGE) mineralization in Pyroxenite from the Faryab ophiolities of Zagros belt in south Iran was studied. The ophiolite rocks represent blocks of Tethyan oceanic crust that were emplaced on the continental margin during the late Cretaceous period. Much of lower ophiolitic section is composed of homogeneous harzburgite, while upper sections harzburgite interlayer with dunite and pyroxenite are included. This study focused on pyroxenite that includes most of sulfide mineralization in Faryab. More than 500 samples were investigated from polished thin sections; that cover all area of Faryab. The sulfide phases include pyrrhotite, pentlandite, millerite, violarite, smythite, and heazlewoodite. The results show that in almost all the samples Os is below the 2 ppb detection limit, Platinum values vary from <5 to 91 ppb and the light PGE (Ru, Rh, and Pd) relative to the heavy PGE (Os, Ir, and Pt) are more concentrated. Calculation showed that in pyroxenites Pd–Pt is occurring with orthopyroxenite and Rh–Os is occurring in clinopyroxenite. Ni/Pd ratios in Faryab vary between 7 and 356 and Pd/Ir ratio is 0.1–27. This indicates that in Faryab area partial melt of mantle occurred. Pd/Rh ratio in Faryab is 0.1–11, and Pd/Pt varies between 0.2 and 1.5. Pd/Ir ratio in Faryab decreases and shows that PGE in Faryab occurred.  相似文献   

10.
Magmatic sulfide deposits consist of pyrrhotite, pentlandite, chalcopyrite (± pyrite), and platinum-group minerals (PGM). Understanding the distribution of the chalcophile and platinum-group element (PGE) concentrations among the base metal sulfide phases and PGM is important both for the petrogenetic models of the ores and for the efficient extraction of the PGE. Typically, pyrrhotite and pentlandite host much of the PGE, except Pt which forms Pt minerals. Chalcopyrite does not host PGE and the role of pyrite has not been closely investigated. The Ni–Cu–PGE ores from the South Range of Sudbury are unusual in that sulfarsenide PGM, rather than pyrrhotite and pentlandite, are the main carrier of PGE, probably as the result of arsenic contribution to the sulfide liquid by the As-bearing metasedimentary footwall rocks. In comparison, the North Range deposits of Sudbury, such as the McCreedy East deposit, have As-poor granites in the footwall, and the ores commonly contain pyrite. Our results show that in the pyrrhotite-rich ores of the McCreedy East deposit Os, Ir, Ru, Rh (IPGE), and Re are concentrated in pyrrhotite, pentlandite, and surprisingly in pyrite. This indicates that sulfarsenides, which are not present in the ores, were not important in concentrating PGE in the North Range of Sudbury. Palladium is present in pentlandite and, together with Pt, form PGM such as (PtPd)(TeBi)2. Platinum is also found in pyrite. Two generations of pyrite are present. One pyrite is primary and locally exsolved from monosulfide solid solution (MSS) in small amounts (<2 wt.%) together with pyrrhotite and pentlandite. This pyrite is unexpectedly enriched in IPGE, As (± Pt) and the concentrations of these elements are oscillatory zoned. The other pyrite is secondary and formed by alteration of the MSS cumulates by late magmatic/hydrothermal fluids. This pyrite is unzoned and has inherited the low concentrations of IPGE and Re from the pyrrhotite and pentlandite that it has replaced.  相似文献   

11.
Noble Metal Enrichment Processes in the Merensky Reef, Bushveld Complex   总被引：21，自引：7，他引：14  
We have analysed sulphides, silicates, and chromites of theMerensky Reef for platinum-group elements (PGEs), Re and Auusing laser ablation-inductively coupled plasma mass spectrometryand synthetic pyrrhotite standards annealed with known quantitiesof noble metals. Os, Ir and Ru reside in solid solution in pyrrhotiteand pentlandite, Rh and part of the Reef’s Pd in pentlandite,whereas Pt, Au, Re and some Pd form discrete phases. Olivineand chromite, often suspected to carry Os, Ir and Ru, are PGEfree. All phases analysed contain noble metals as discrete micro-inclusionswith diameters typically <100 nm. Inclusions in sulphidescommonly have the element combinations Os–Ir–Ptand Pt–Pd–Au. Inclusions in olivine and chromiteare dominated by Pt ± Au–Pd. Few inclusion spectracan be related to discrete noble metal phases, and few inclusionshave formed by sub-solidus exsolution. Rather, some PGE inclusions,notably those in olivine and chromite, are early-magmatic nuggetstrapped when their host phases crystallized. We suggest thatthe silicate melt layer that preceded the Merensky Reef wasPGE oversaturated at early cumulus times. Experiments combinedwith available sulphide–silicate partition coefficientssuggest that a silicate melt in equilibrium with a sulphidemelt containing the PGE spectrum of the Merensky ore would indeedbe oversaturated with respect to the least soluble noble metals.Sulphide melt apparently played little role in enriching thenoble metals in the Merensky Reef; rather, its role was to immobilizea pre-existing in situ stratiform PGE anomaly in the liquid-stratifiedmagma chamber. KEY WORDS: Bushveld Complex; Merensky Reef; laser-ablation ICP-MS; platinum-group mineralization  相似文献   

12.
The Grasvally Norite–Pyroxenite–Anorthosite (GNPA) member within the northern limb of the Bushveld Complex is a mineralized, layered package of mafic cumulates developed to the south of the town of Mokopane, at a similar stratigraphic position to the Platreef. The concentration of platinum-group elements (PGE) in base metal sulfides (BMS) has been determined by laser ablation inductively coupled plasma–mass spectrometry. These data, coupled with whole-rock PGE concentrations and a detailed account of the platinum-group mineralogy (PGM), provide an insight into the distribution of PGE and chalcophile elements within the GNPA member, during both primary magmatic and secondary hydrothermal alteration processes. Within the most unaltered sulfides (containing pyrrhotite, pentlandite, and chalcopyrite only), the majority of IPGE, Rh, and some Pd occur in solid solution within pyrrhotite and pentlandite, with an associated Pt–As and Pd–Bi–Te dominated PGM assemblage. These observations in conjunction with the presence of good correlations between all bulk PGE and base metals throughout the GNPA member indicate the presence and subsequent fractionation of a single PGE-rich sulfide liquid, which has not been significantly altered. In places, the primary sulfides have been replaced to varying degrees by a low-temperature assemblage of pyrite, millerite, and chalcopyrite. These sulfides are associated with a PGM assemblage characterized by the presence of Pd antimonides and Pd arsenides, which are indicative of hydrothermal assemblages. The presence of appreciable quantities of IPGE, Pd and Rh within pyrite, and, to a lesser, extent millerite suggests these phases directly inherited PGE contents from the pyrrhotite and pentlandite that they replaced. The replacement of both the sulfides and PGM occurred in situ, thus preserving the originally strong spatial association between PGM and BMS, but altering the mineralogy. Precious metal geochemistry indicates that fluid redistribution of PGE is minimal with only Pd, Au, and Cu being partially remobilized and decoupled from BMS. This is also indicated by the lower concentrations of Pd evident in both pyrite and millerite compared with the pentlandite being replaced. The observations that the GNPA member was mineralized prior to intrusion of the Main Zone and that there was no local footwall control over the development of sulfide mineralization are inconsistent with genetic models involving the in situ development of a sulfide liquid through either depletion of an overlying magma column or in situ contamination of crustal S. We therefore believe that our observations are more compatible with a multistage emplacement model, where preformed PGE-rich sulfides were emplaced into the GNPA member. Such a model explains the development and distribution of a single sulfide liquid throughout the entire 400–800 m thick succession. It is therefore envisaged that the GNPA member formed in a similar manner to its nearest analogue the Platreef. Notable differences however in PGE tenors indicate that the ore-forming process may have differed slightly within the staging chambers that supplied the Platreef and GNPA member.  相似文献   

13.
It is of great importance to understand the origin of UG2 chromitite reefs and reasons why some chromitite reefs contain relatively high contents of platinum group elements(PGEs: Os, Ir, Ru, Rh,Pt, Pd) or highly siderophile elements(HSEs: Au, Re, PGE). This paper documents sulphide-silicate assemblages enclosed in chromite grains from the UG2 chromitite. These are formed as a result of crystallisation of sulphide and silicate melts that are trapped during chromite crystallisation. The inclusions display negative crystal shapes ranging from several micrometres to 100 μm in size.Interstitial sulphide assemblages lack pyrrhotite and consist of chalcopyrite, pentlandite and some pyrite. The electron microprobe data of these sulphides show that the pentlandite grains present in some of the sulphide inclusions have a significantly higher iron(Fe) and lower nickel(Ni) content than the pentlandite in the rock matrix. Pyrite and chalcopyrite show no difference. The contrast in composition between inter-cumulus plagioclase(An_(68)) and plagioclase enclosed in chromite(An_(13)), as well as the presence of quartz, is consistent with the existence of a felsic melt at the time of chromite saturation.Detailed studies of HSE distribution in the sulphides and chromite were conducted by LA-ICP-MS(laser ablation-inductively coupled plasma-mass spectrometry), which showed the following.(Ⅰ) Chromite contained no detectable HSE in solid solution.(Ⅱ) HSE distribution in sulphide assemblages interstitial to chromite was variable. In general, Pd, Rh, Ru and Ir occurred dominantly in pentlandite, whereas Os,Pt and Au were detected only in matrix sulphide grains and were clearly associated with Bi and Te.(Ⅲ)In the sulphide inclusions,(a) pyrrhotite did not contain any significant amount of HSE,(b) chalcopyrite contained only some Rh compared to the other sulphides,(c) pentlandite was the main host for Pd,(d)pyrite contained most of the Ru, Os, Ir and Re,(e) Pt and Rh were closely associated with Bi forming a continuous rim between pyrite and pentlandite and(f) no Au was detected. These results show that the use of ArF excimer laser to produce high-resolution trace element maps provides information that cannot be obtained by conventional(spot) LA-ICP-MS analysis or trace element maps that use relatively large beam diameters.  相似文献   

14.
Kilauea Iki lava lake formed during the 1959 summit eruption of Kilauea Volcano, then crystallized and differentiated over a period of 35 years. It offers an opportunity to evaluate the fractionation behavior of trace elements in a uniquely well-documented basaltic system. A suite of 14 core samples recovered from 1967 to 1981 has been analyzed for 5 platinum-group elements (PGE: Ir, Os, Ru, Pt, Pd), plus Re. These samples have MgO ranging from 2.4 to 26.9 wt.%, with temperatures prior to quench ranging from 1140 °C to ambient (110 °C). Five eruption samples were also analyzed.Osmium and Ru concentrations vary by nearly four orders of magnitude (0.0006–1.40 ppb for Os and 0.0006–2.01 ppb for Ru) and are positively correlated with MgO content. These elements behaved compatibly during crystallization, mostly likely being concentrated in trace phases (alloy or sulfide) present in olivine phenocrysts or included chromite. Iridium also correlates positively with MgO, although less strongly than Os and Ru. The somewhat poorer correlation for Ir, compared with Os and Ru, may reflect variable loss of Ir as volatile IrF6 in some of the most magnesian samples.Rhenium is negatively correlated with MgO, behaving as an incompatible trace element. Its behavior in the lava lake is complicated by apparent volatile loss of Re, as suggested by a decrease in Re concentration with time of quenching for lake samples vs. eruption samples. Platinum and Pd concentrations are negatively, albeit weakly, correlated with MgO, so these elements were modestly incompatible during crystallization of the major silicate phases. Palladium contents peaked before precipitation of immiscible sulfide liquid, however, and decline sharply in the most differentiated samples. In contrast, Pt appears to have been unaffected by sulfide precipitation. Microprobe data confirm that Pd entered the sulfide liquid before Re, and that Pt is not strongly chalcophile in this system. Occasional high Pt values in both eruption and lava lake samples suggest the presence of unevenly distributed, unidentified Pt-rich trace phases in some Kilauea Iki materials.Estimated mineral (olivine + chromite)/melt D values for Os, Ir, Ru and Pt for equilibrium crystallization for samples from ~ 7 to 27 wt.% MgO are 26, 8.2, 19 and 0.55, respectively. These Os, Ir and Ru estimates are somewhat higher than previous estimates for similar systems. If fractional crystallization is instead assumed, D values are much more similar.Results confirm many prior observations in other mafic systems that olivine (together with included phases) has a major effect on absolute and relative abundances of Re and the PGE. The relatively linear correlations between these elements and MgO potentially permit accurate estimation of the concentrations of these elements in the primary melts of comparable systems, especially in instances where the MgO content of the primary melt is well constrained.  相似文献   

15.
来自蛇绿岩地幔的硫（砷）化物矿物组合   总被引：1，自引：0，他引：1  
近来在西藏雅鲁藏布江蛇绿岩带的罗布莎蛇绿岩块的地幔豆荚状铬铁矿中发现一个包括金刚石、柯石英、自然元素、合金、氧化物以及硫(砷)化物组成的地幔矿物群。该矿物群的硫(砷)化物具有特殊化学成分并呈包裹体分布在贱金属(BM)和铂族元素(PGE)或它们的合金中,大量化学成分分析得知它们主要由下列元素组成:S、As、Te、Fe、Ni、Co、Cu、Pt、Pd、Ru、Rh、Os、Ir、Mn和Ti。根据化学成分可辨别出约30种硫(砷)化物矿物:FeS、NiS、(Ni,Fe)S、Fe3S2、Ni3S2、(Ru,Os,Ir)S2、Rh7As3、Rh5Ni(Cu)As4、Pd4Rh3As3、Pd8As2、Pd3TeAs、Pd7Te3、RuAs、PtAs2、Ni4Rh3As3、Rh(As,S)2、(Rh,Ir)(As,S)2、Ir(As,S)2、MnS、Ti7S3、Ti7N3、Rh3.5Se3.5CuS2、RhS、Ir2S3、(Ir,Cu)2、S3(Co,Ni,Fe)2(As,S)3、(Ir,Pt)(As,S)2、Ru3(As,S)7以及(BM)x(PGE)yS10-(x y)等,其中包括已定名和未定名的矿物。由于矿物粒度小(<25μm),缺乏X射线分析资料,有待进一步研究。  相似文献   

16.
Extremely abundant PGE-minerals(PGM)hosted in chromitites from the Veria ophiolite complex in Macedonia(N.Greece)may be unique among ophiolite complexes.This study focuses on differences between the low-and high-PGE chromitites.New textural,mineralogical and geochemical constraints from those ores are presented,aiming to define factors controlling the PGE enrichment in a supra subduction environment,in the light of postmagmatic processes.The whole ore analyses for mmajor and trace elements indicated an unusually high-IPGE content(up to 25 ppm)and higher Fe,Ca,Mn,Zn and V contents in high-PGE compared to low-PGE in massive chromitites.The wide compositional variation of chromite,even in the same polished section,the occurrence of very fine PGM(less than 20μm)as inclusions within chromite and extremely large(>1000μm),angular or fine-grained PGM aggregates ones within a matrix of highly fragmented chromite-Cr-garnet matrix,may indicate crystallization/recrystallization of chromite from more than one precursor phases.Laurite(RuS2)is very limited,occurring as remnants surrounding by Ru–Os–Ir oxides/hydroxides,of a wide compositional variation.Irarsite occurs as euhedral crystals up to 200μm,surrounding by chromite,as anhedral exsolutions 1–200μm within laurite,or creating segregates with platarsite and relics of(Ru,Pt,Rh,Os)sulfarsenides.Platinum–Ru–Rh–Pd-minerals occur commonly as relatively fine-grained assemblages,up to 50μm,along with irarsite and other relics of(Ru,Pt,Rh,Os)sulfarsenides.Pt-alloys show a variation ranging from tetraferroplatinum to Pt–Ir–Fe–Ni alloys.The presence of laurite relics in large IPGM,awaruite,heazlewoodite,and carbon-bearing material reflecting a super-reducing environment,and the transformation of primary PGM into Os–Ir–Ru-alloys and oxides/hydroxides in association with Fe-chromite and Fe3t-bearing garnet(andradite-uvarovite solidsolution series)may reflect changes of the redox conditions from reducing to oxidizing.The relatively high Na content in hydrous mineral inclusions within high-PGE chromitites suggest a hydrous mantle source and provide the possibility for estimation of the P(average 3.0 kbar)and T(average 874C),indicating formation at a shallow mantle environment.  相似文献   

17.
We have performed six experiments in which we equilibrated monosulfide solid solution (mss) with sulfide melt in evacuated silica capsules containing solid buffers to fix oxygen and sulfur fugacity, at temperatures of 950°C, 1000°C and 1050°C at bulk concentrations of ∼50 ppm for each of the PGE and Au, 5% Ni, and 7% Cu. Concentrations of O, S, Fe, Ni and Cu were determined by electron microprobe, whereas precious metal concentrations were determined by laser-ablation inductively-coupled mass spectrometry. Partition coefficients of all elements studied show minimal dependences on oxygen fugacity from the IW to the QFM buffers when sulfur fugacity is fixed at the Pt-PtS buffer. Cu, Pt, Pd and Au are strongly incompatible and Ru remains moderately to strongly compatible under all conditions studied. At all oxygen fugacities, at the Pt-PtS sulfur buffer, Ir and Rh remain highly compatible in mss. In the single run at both low oxygen and low sulfur fugacity Ir and Rh were found to be strongly incompatible in mss. At QFM and Pt-PtS the partition coefficient for Ni shows weak temperature dependence, ranging from 0.66 at 1050°C to 0.94 at 950°C. At lower oxygen and sulfur fugacity Ni showed much more incompatible behavior. Comparison with the compositions of sulfide ores from the Lindsley deposit of Sudbury suggests that the sulfide magma evolved under conditions close to the QFM and Pt-PtS buffers. The compatible behavior observed for Ni, Ir and Rh at Lindsley and most other magmatic sulfide deposits hosted by mafic rocks requires equilibration of mss and sulfide liquid at moderately high sulfur fugacity and low temperatures near to the solidus of the sulfide magma. We argue that this constraint requires that the sulfide magma must have evolved by equilibrium crystallization, rather than fractional segregation of mss as is commonly supposed.  相似文献   

18.
The Platreef, the putative local analogue of the Merensky Reef, forms the floor to the mafic succession in the northern limb of the Bushveld Complex. We define the Platreef as ‘the lithologically variable unit, dominated by pyroxenite, which is irregularly mineralised with PGE, Cu and Ni, between the Transvaal metasedimentary footwall or Archaean basement and the overlying Main Zone gabbronorite’. We define the mineralisation around calcsilicate xenoliths within the Main Zone in the far north of the limb as a ‘Platreef-style‘ mineralisation. The Platreef (ss) has a strike extent of ∼30 km, whereas Platreef-style mineralisation occurs over a strike length of 110 km. The Platreef varies from 400 m thick in the S to <50 m in the N. The overall strike is NW or N, with dips 40–45°W at surface, shallowing down dip, The overall geometry of the southern Platreef appears to have been controlled by irregular floor topography. The maximum thickness of the southern Platreef occurs in two sub-basins on the farms Macalacaskop and Turfspuit. Lithologically, the southern Platreef is heterogeneous and more variable than sectors further north and, although predominantly pyroxenitic, includes dunites, peridotites and norite cycles with anorthosite in the mid to upper portion. Zones of intense serpentinisation may occur throughout the package. Faults offset the strike of the Platreef: a N–S, steeply dipping set is predominant with secondary ENE and ESE sets dipping 50–70°S. The fault architecture was pre-Bushveld and also locally controlled thickening and thinning of the succession. Country rock xenoliths, <1500 m long, are common. On Macalacaskop, these are typically quartzites and hornfelsed banded ironstones, shales, mudstones and siltstones whereas on Turfspruit dolomitic or calcsilicate xenoliths also occur. Sulphides may reach >30 modal% in some intersections. These are dominated by pyrrhotite, with lesser pentlandite and chalcopyrite, minor pyrite and traces of a wide compositional range of sulphides. In the southern sector, mineralised zones have Cu grades of 0.1–0.25% and Ni 0.15–0.36%. Massive sulphides are localised, commonly, but not exclusively towards the contact with footwall metasedimentary rocks. Magmatic sulphides are disseminated or net-textured ranging from a few microns to 2 cm grains of pyrrhotite and pentlandite with chalcopyrite and minor pyrite. Much of the sulphide is associated with intergranular plagioclase, or quartz-feldspar symplectites, along the margins of rounded cumulus orthopyroxenes. The PGEs in the southern sector occur as tellurides, bismuthides, arsenides, antimonides, bismuthoantimonides and complex bismuthotellurides. PGM are rarely included in the sulphides but occur as micron-sized satellite grains around interstitial sulphides and within alteration assemblages in serpentinised zones. The Pt:Pd ratio ∼1 and PGE grade may be decoupled from S and base metal abundance.  相似文献   

19.
Base-metal sulfides in magmatic Ni-Cu-PGE deposits are important carriers of platinum-group elements (PGE). The distribution and concentrations of PGE in pentlandite, pyrrhotite, chalcopyrite, and pyrite were determined in samples from the mineralized portion of four Merensky Reef intersections from the eastern and western Bushveld Complex. Electron microprobe analysis was used for major elements, and in situ laser ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS) for trace elements (PGE, Ag, and Au). Whole rock trace element analyses were performed on representative samples to obtain mineralogical balances. In Merensky Reef samples from the western Bushveld, both Pt and Pd are mainly concentrated in the upper chromitite stringer and its immediate vicinity. Samples from the eastern Bushveld reveal more complex distribution patterns. In situ LA-ICP-MS analyses of PGE in sulfides reveal that pentlandite carries distinctly elevated PGE contents, whereas pyrrhotite and chalcopyrite only contain very low PGE concentrations. Pentlandite is the principal host of Pd and Rh in the ores. Palladium and Rh concentrations in pentlandite reach up to 700 and 130 ppm, respectively, in the samples from the eastern Bushveld, and up to 1,750 ppm Pd and up to 1,000 ppm Rh in samples from the western Bushveld. Only traces of Pt are present in the base-metal sulfides (BMS). Pyrrhotite contains significant though generally low amounts of Ru, Os, and Ir, but hardly any Pd or Rh. Chalcopyrite contains most of the Ag but carries only extremely low PGE concentrations. Mass balance calculations performed on the Merensky Reef samples reveal that in general, pentlandite in the feldspathic pyroxenite and the pegmatoidal feldspathic pyroxenite hosts up to 100 % of the Pd and Rh and smaller amounts (10–40 %) of the Os, Ir, and Ru. Chalcopyrite and pyrrhotite usually contain less than 10 % of the whole rock PGE. The remaining PGE concentrations, and especially most of the Pt (up to 100 %), are present in the form of discrete platinum-group minerals such as cooperite/braggite, sperrylite, moncheite, and isoferroplatinum. Distribution patterns of whole rock Cu, Ni, and S versus whole rock Pd and Pt show commonly distinct offsets. The general sequence of “offset patterns” of PGE and BMS maxima, in the order from bottom to top, is Pd in pentlandite?→?Pd in whole rock?→?(Cu, Ni, and S). The relationship is not that straightforward in general; some of the reef sequences studied only partially show similar trends or are more complex. In general, however, the highest Pd concentrations in pentlandite appear to be related to the earliest, volumetrically rather small sulfide liquids at the base of the Merensky Reef sequence. A possible explanation for the offset patterns may be Rayleigh fractionation.  相似文献   

20.
Platinum group elements (PGE: Os, Ir, Ru, Rh, Pt, Pd) are important geochemical and cosmochemical tracers. Depending on physical and chemical behaviour the PGEs are divided into two subgroups: IPGE (Ir, Os, Ru) and PPGE (Pd, Pt, Rh). Platinum group elements show strong siderophile and chalcophile affinity. Base metal sulfides control the PGE budget of the Earth’s mantle. Mantle xenoliths contain two types of sulfide populations: (1) enclosed within silicate minerals, and (2) interstitial to the silicate minerals. In terms of PGE characters the included variety shows IPGE enriched patterns — similar to the melt-depleted mantle harzburgite, whereas the interstitial variety shows PPGE enriched patterns — resembling the fractionated PGE patterns of the basalt. These PGE characters of the mantle sulfides have been interpreted to be representative of multi-stages melting process of the mantle that helped to shape the chemical evolution of the Earth.  相似文献   

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