亲铜元素的地球化学行为研究进展及其在岩浆硫化物矿床中的应用

亲铜元素在岩浆演化和硫化物熔离过程中的行为是解释岩浆硫化物矿床形成过程的一个窗口,通过实验研究来探讨亲铜元素的地球化学行为,并用于岩浆硫化物矿床的定量化研究是此类矿床今后的一个发展方向。本文总结了硫和亲铜元素在岩浆演化过程中的行为规律,并阐明了在岩浆硫化物矿床中的应用,在如下五个方面分别做了讨论：① 通过实验对玄武质岩浆中S溶解度的研究,总结出引起硫化物饱和的4个控制因素: 岩浆混合、温度迅速降低、壳源混染、快速的结晶分异作用;② 通过Ni在橄榄石和硅酸盐熔浆中的分配,定量模拟了岩浆演化过程中,橄榄石中的Ni含量随着橄榄石成分（Fo）变化的规律;③ 总结了Ni—Cu—PGE—Au在液态硫化物和硅酸盐岩浆中的分配系数,总结了控制分配系数的因素,并探讨了“R因素”对亲铜元素富集的控制机理;④ 橄榄石被硫化物包围时,与硫化物发生交换反应,通过交换反应系数（KD）可以定量估算硫化物熔浆中Ni的含量;⑤ 通过实验得出的亲铜元素在单硫化物固溶体（MSS）和液态硫化物之间的分配,总结了岩浆铜镍硫化物矿床中的分带现象。最后探讨了岩浆硫化物矿床存在的问题和发展方向。     

Composition of rock-forming minerals in the Kivakka layered massif,northern Karelia,and systematic variations in the chemistries of minerals in the rhythmic layering subzone

Data obtained on the compositions of rock-forming minerals from the Kivakka layered intrusion indicate that the #Fe of olivine increases up the vertical section of the intrusion, and the #Mg of the pyroxenes and the anorthite contents of the plagioclase simultaneously decrease, which reflects the fractionation of the parental melt. Emphasis is placed onto the compositional variability of minerals in the layered unit. A method is developed for the reliable calculation of the composition of pyroxenes before their exoslution (separately for ortho-and clinopyroxene). The composition of minerals in the zone of intercalating melano-, meso-, and leucocratic norites remains practically unchanged, which is generally consistent with the results of mathematical simulations: compositional variations of the bronzite (#Mg) and plagioclase (An content) during the crystallization of the bronzite-plagioclase cotectic were no greater than 5 mol %. The variations in the concentrations of trace elements in the cumulus and intercumulus clinopyroxene occurred to be the most informative. It was determined that the Cr concentration in the cumulus augite is statistically significantly lower than that in the intercumulus augite, which is at variance with fractionation laws and led us to suggest that the rocks with cumulus pyroxenes were formed by a melt with a higher degree of fractionation than those of the intercumulus melts of the adjacent layers.     

含硫化物镁铁质-超镁铁质侵入体中橄榄石Mg、Ni含量的制约:原理、模式及Voisey's Bay侵入体样品研究

镁铁质-超镁铁质岩浆结晶分离早期形成镁铁矿物,镁铁矿物中的Ni和Mg是相容元素。随着结晶分离作用的进行,Ni、Mg在硅酸盐岩浆及后形成的硅酸盐物质中的丰度下降。橄榄石中Ni含量及硅酸盐物质MgO/FeO比值都与母岩浆的相关值相关,据此可推断母岩浆的信息,它们之间可由实验测得的系数相联系。当岩浆饱和硫化物时,在结晶分离过程中硫化物珠滴会与镁铁硅酸盐物质一道析出,同时,与硫化物非饱和岩浆相比,过多的Ni会随之析出。这也反映在Ni、Mg含量比无硫化物分离时有更迅速的降低上。Ni、Mg含量变化值可以在VoiseysBay侵入体的模式曲线上反映出,加拿大Labrador的这一侵入体赋存了一个世界级的Ni-Cu-Co硫化物矿床。过去的作法是将侵入体中橄榄石的Ni、Mg含量与Simkin和Smith得出的各种火成岩中橄榄石的Ni、Mg含量相比较以确定Ni亏损,进而假定橄榄石来自硫化物饱和、有经济价值的岩浆。现在的研究显示这种简单的对比会导致错误。将样品数据与模式曲线对比并反映出侵入体矿物结晶堆积特征是重要的方法。使用这一方法,样品数据能很好地被模式曲线拟合。以在VoiseysBay的研究为例,当硫化物液相与硅酸盐矿物被去除后,硫化物非饱和的分离作用期就会显现出来,随后是硅酸盐结晶作用期。     

Geochemical structure of the Yoko-Dovyren layered dunite-troctolite-gabbro-norite massif,northern Baikal area

The application of the principle and algorithm of the cluster analysis of rock compositions in magmatic complexes, which were described elsewhere, made it possible to reveal the spaceless and spatial geochemical structure of the Yoko-Dovyren layered mafic-ultramafic massif. The diversity of rocks composing this intrusion was demonstrated to comprise eleven discrete geochemical types (clusters): dunites, harzburgites, melanotroctolites, troctolites, two types of olivine gabbro, two types of olivine gabbronorites, quartz gabbronorites, and granophyres. These geochemical types of rocks and the corresponding fractionation parameters (the iron atomic fraction f of mafic minerals and the anorthite concentration An of plagioclase) define a succession corresponding to the tendencies in the crystallization of a magma of respective composition. This geochemical succession is in complete agreement with the succession in which rocks were formed in the intrusion (from dunite in its bottom part to quartz gabbronorites and granophyres near its roof) and is complicated by cyclical repetitions. The main tendency revealed in the cyclic layering is as follows: cyclical intercalations consist of rocks corresponding to the neighboring members of the rock succession (plagiodunites and melanotroctolites, melanotroctolites and troctolites, troctolites and olivine gabbro, olivine gabbro and olivine gabbronorites). These tendencies are closely similar to those identified in the Kivakka intrusion, a fact suggesting that these tendencies can be common for all layered complexes of mafic and ultramafic rocks. Original Russian Text ? A.A. Yaroshevskii, S.V. Bolikhovskaya, E.V. Koptev-Dvornikov, 2006, published in Geokhimiya, 2006, No. 10, pp. 1027–1039.     

Chalcophile element geochemistry of the Boggy Plain zoned pluton, southeastern Australia: a S-saturated barren compositionally diverse magmatic system

The behavior of the platinum group elements (PGE) and Re in felsic magmas is poorly understood due to scarcity of data. We report the concentrations of Ni, Cu, Re, and PGE in the compositionally diverse Boggy Plain zoned pluton (BPZP), which shows a variation of rock type from gabbro through granodiorite and granite to aplite with a SiO₂ range from 52 to 74 wt %. In addition, major silicate and oxide minerals were analyzed for Ni, Cu, and Re, and a systematic sulfide study was carried out to investigate the role of silicate, oxide, and sulfide minerals on chalcophile element geochemistry of the BPZP. Mass balance calculation shows that the whole rock Cu budget hosted by silicate and oxide minerals is <13 wt % and that Cu is dominantly located in sulfide phases, whereas most of the whole rock Ni budget (>70 wt %) is held in major silicate and oxide minerals. Rhenium is dominantly hosted by magnetite and ilmenite. Ovoid-shaped sulfide blebs occur at the boundary between pyroxene phenocrysts and neighboring interstitial phases or within interstitial minerals in the gabbro and the granodiorite. The blebs are composed of pyrrhotite, pyrite, chalcopyrite, and S-bearing Fe-oxide, which contain total trace metals (Co, Ni, Cu, Ag, Pb) up to ~16 wt %. The mineral assemblage, occurrence, shape, and composition of the sulfide blebs are a typical of magmatic sulfide. PGE concentrations in the BPZP vary by more than two orders of magnitude from gabbro (2.7–7.8 ppb Pd, 0.025–0.116 ppb Ir) to aplite (0.05 ppb Pd, 0.001 ppb Ir). Nickel, Cu, Re, and PGE concentrations are positively correlated with MgO in all the rock types although there is a clear discontinuity between the granodiorite and the granite in the trends for Ni, Rh, and Ir when plotted against MgO. Cu/Pd values gradually increase from 6,100 to 52,600 as the MgO content decreases. The sulfide petrology and chalcophile element geochemistry of the BPZP show that sulfide saturation occurred in the late gabbroic stage of magma differentiation. Segregation and distribution of these sulfide blebs controlled Cu and PGE variations within the BPZP rocks although the magma of each rock type may have experienced a different magma evolution history in terms of crustal assimilation and crystal fractionation. The sulfide melt locked in the cumulate rocks must have sequestered a significant portion of the chalcophile elements, which restricted the availability of these metals to magmatic-hydrothermal ore fluids. Therefore, we suggest that the roof rocks that overlay the BPZP were not prospective for magmatic-hydrothermal Cu, Au, or Cu–Au deposits.     

Petrogenesis of the Greenhills Complex,Southland, New Zealand: magmatic differentiation and cumulate formation at the roots of a Permian island-arc volcano

A Permian (~265 Ma) intrusive complex which formed as a magmatic feeder reservoir to an immature island-arc volcano is fortuitously exposed in southern New Zealand. Known as the Greenhills Complex, this intrusion was emplaced at shallow crustal levels and consists of two layered bodies which were later intruded by a variety of dykes. Cumulates, which include dunite, olivine clinopyroxenite, olivine gabbro, and hornblende gabbro-norite, are related products of parent-magma fractionation. Both primary (magmatic) and secondary platinum-group minerals occur within dunite at one locality. Using the composition of cumulus minerals, mafic dykes and melt inclusions, we have determined that the parent magmas of the complex were hydrous, low-K island-arc tholeiites of ankaramitic affinities. Progressive magmatic differentiation of this parent magma generated fractionated melt of high-alumina basalt composition which is now preserved only as dykes which cut the Complex. Field evidence and cumulus mineral profiles reveal that the magma chambers experienced turbulent magmatic conditions during cumulate-rock formation. Recharge of the chambers by primitive magma is likely to have coincided with eruption of residual melt at the surface. Similar processes are inferred to account for volcanic-rock compositions in other parts of this arc terrane and in modern island-arc systems.     

Nb-Ta-Ti-W-Sn-oxide minerals as indicators of a peraluminous P- and F-rich granitic system evolution: Podlesí, Czech Republic

Summary The strongly peraluminous, P- and F-rich granitic system at Podlesí in the Krušné Hory Mountains, Czech Republic, resembles the zonation of rare element pegmatites in its magmatic evolution (biotite → protolithionite → zinnwaldite granites). All granite types contain disseminated Nb-Ta-Ti-W-Sn minerals that crystallized in the following succession: rutile + cassiterite (in biotite granite), rutile + cassiterite → ferrocolumbite (in protolithionite granite) and ferrocolumbite → ixiolite → ferberite (in zinnwaldite granite). Textural features of Nb-Ta-Ti-W minerals indicate a pre-dominantly magmatic origin with only minor post-magmatic replacement phenomena. HFSE remained in the residual melt during the fractionation of the biotite granite. An effective separation of Nb + Ta into the melt and Sn into fluid took place during subsequent fractionation of the protolithionite granite, and the tin-bearing fluid escaped into the exocontact. To the contrast, W contents are similar in both protolithionite and zinnwaldite granites. Although the system was F-rich, only limited Mn-Fe and Ta-Nb fractionation appeared. Enrichment of Mn and Ta was suppressed due to foregoing crystallization of Mn-rich apatite and relatively low Li content, respectively. The content of W in columbite increases during fractionation and enrichment in P and F in the melt. Ixiolite (up to 1 apfu W) instead of columbite crystallized from the most fluxes-enriched portions of the melt (unidirectional solidification textures, late breccia).     

A laser ablation inductively coupled plasma mass spectrometry study of the distribution of chalcophile elements among sulfide phases in sedimentary and magmatic rocks of the Duluth Complex,Minnesota, USA

Nickel-copper sulfide deposits occur in the basal unit of the Partridge River Intrusion, Duluth Complex (Minnesota, USA). Many lines of evidence suggest that these sulfides are formed after assimilation of the proterozoic S-rich black shales, known as the Bedded Pyrrhotite Unit. In addition to S, black shales are enriched in Te, As, Bi, Sb and Sn (TABS) and the basaltic magma of the intrusion is contaminated by the partial melt of the black shales. The TABS are chalcophile and together with the platinum-group elements, Ni and Cu partitioned into the magmatic sulfide liquid that segregated from the Duluth magma. The TABS are important for the formation of platinum-group minerals (PGM) thus their role during crystallization of the base metal sulfide minerals could affect the distribution of the PGE. However, the concentrations of TABS in magmatic Ni-Cu-PGE deposits and their distribution among base metal sulfide minerals are poorly documented. In order to investigate whether the base metal sulfide minerals host TABS in magmatic Ni-Cu-PGE deposits, a petrographic and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) study has been carried out on base metal sulfide and silicate phases of the Partridge River Intrusion, Duluth Complex.Petrographic observations showed that the proportions of the base metal sulfide minerals vary with rock type. The sulfide assemblage of the least metamorphosed Bedded Pyrrhotite Unit from outside the contact metamorphic aureole consists of pyrite with minor pyrrhotite plus chalcopyrite (<5%), whereas within the contact aureole the sulfide assemblage of the Bedded Pyrrhotite Unit rocks consists dominantly of pyrrhotite (>95%) with small amount of chalcopyrite (<2%). The sulfide mineral assemblage in the xenoliths of the Bedded Pyrrhotite Unit and in the mafic rocks of the basal unit contains two additional sulfides, pentlandite and cubanite.Our LA-ICP-MS study shows that sulfides of the Bedded Pyrrhotite Unit are rich in TABS; consistent with these S-rich black shales being the source of TABS that contaminated the mafic magma. Most of the TABS are associated with sulfides and platinum-group minerals in the rocks of the Bedded Pyrrhotite Unit from the contact aureole, the Bedded Pyrrhotite Unit xenoliths and the mafic rocks of the Duluth Complex. In addition to these phases the laser maps show that silicate phases, i.e., orthopyroxene and plagioclase contain Sn and Pb respectively. In contrast, in the least metamorphosed samples of the Bedded Pyrrhotite Unit from outside the contact aureole although the pyrite contains some TABS mass balance calculations indicates that most the TABS are contained in other phases. In these rocks, galena hosts significant amounts of Te, Bi, Sb, Sn and Ag and few very small grains of Sb-rich phases were also observed. The host phases for As were not established but possibly organic compounds may have contributed.     

Fractionation of platinum, palladium, nickel, and copper in sulfide–arsenide systems at magmatic temperature

Experimentally derived phase relations of arsenide in sulfide melt are presented to quantify the fractionation paths of As-bearing sulfide melts. When a natural sulfide melt reaches arsenide saturation, a separate Ni–PGE-rich arsenide melt exsolves. The arsenic saturation concentration in an Fe–Ni–Cu sulfide melt is between 0.5 and 1.5 wt%. The affinities of the chalcophile metals for an immiscible arsenide melt follow the order Pt > Pd > Ni ? Fe ≈ Cu. In natural systems, arsenide exsolution will be triggered by the activity of the nickel arsenide components dissolved in sulfide melt, Ni being the most common base metal with strong affinity to the As^n? anionic species. Arsenic may have a major effect on the fractionation paths of sulfide melts even if no separate arsenide phase forms. Arsenic, and probably many other chalcogens and metalloids in magmatic melts, may undergo associations with Pt and Pd well before discrete PGE minerals become stable phases.     

The Permian Huangshanxi Cu–Ni deposit in western China: intrusive–extrusive association,ore genesis,and exploration implications

The Permian Huangshanxi Cu–Ni deposit is the second largest magmatic sulfide deposit discovered to date in a major Ni–Cu province related to protracted basaltic magmatism in eastern Xinjiang, China. It is hosted by a small mafic–ultramafic intrusion comprised predominantly of lherzolites, olivine websterites, gabbronorites, and gabbros. The Huangshanxi intrusion is coeval with Permian basalts of tholeiitic and alkaline affinities in the Tuha and Tarim basins, respectively. To evaluate a possible genetic relationship between the Huangshanxi intrusion and a specific type of coeval basalt in the region, as well as ore genesis in the intrusion, we have carried out an integrated mineralogical, petrological, and geochemical study. Our data reveal that the Huangshanxi intrusive rocks are characterized by relatively flat chondrite-normalized REE patterns, depletion in Nb and Ta, and elevated εNd values varying between 6 and 10. These features are similar to those of coeval tholeiitic basalts in the nearby Tuha basin, but are significantly different from those of coeval alkaline basalts in the relatively remote Tarim basin. The geochemical similarities and differences suggest that the Huangshanxi intrusion is genetically related to the tholeiitic basalts in the Tuha basin, not to the alkaline basalts in the Tarim basin, as suggested previously by some researchers. This implies that regional exploration for the Huangshanxi-type Cu–Ni deposits should be centered in the Tuha basin instead of the Tarim basin. More specifically, the uplifted areas around the Tuha basin where similar intrusions may have been brought close to the surface should be carefully examined for mineralization potential. Intrusive relations and mass balance constraints from incompatible trace elements and sulfide abundances suggest that the Huangshanxi intrusion represents a dynamic magma conduit through which multiple pulses of magma ascended to higher levels or to the surface. Numerical simulation of magma evolution and mixing calculations using Sr–Nd isotopes indicate that selective assimilation of S-bearing crustal materials is important for sulfide saturation during the early stages of magma evolution when lherzolites formed. Fractional crystallization may have also played a role in the attainment of sulfide saturation during the later stages of magma evolution when olivine websterites and gabbronorites formed. In both cases, immiscible sulfide droplets were retained in the conduit to form disseminated sulfide lenses while the fractionated silicate liquids and buoyant phases such as plagioclase continued to ascend. Extremely low PGE tenors in the sulfide ores of the Huangshanxi deposit suggest that the parental magma was highly depleted in chalcophile elements possibly due to previous sulfide segregation at depth.     

The petrology of the layered gabbro intrusion, eastern gabbro, Coldwell alkaline complex, Northwestern Ontario, Canada: evidence for multiple phases of intrusion in a ring dyke

The Coldwell alkaline complex is a large (> 350 km²) gabbro and syenite intrusion on the north shore of Lake Superior. It was emplaced at 1108 Ma during early magmatic activity associated with the formation of the Mid-Continent Rift of North America. The eastern gabbro forms a partial ring dyke on the outer margin of the complex and consists of at least three discrete intrusions. The largest of these is the layered gabbro that comprises a 300 m thick fine- to medium-grained basal unit overlain by up to 1100 m of variably massive to layered gabbroic cumulates which vary from olivine gabbro to anorthosite. Several xenoliths of Archaean metamorphic rocks that range in size from 10's to 100's of meters are present in the central part of the intrusion. Within discrete horizons in the layered gabbro are many centimeter- to meter-scale, gabbroic xenoliths. The main cumulus minerals, in order of crystallization, are plagioclase, olivine and clinopyroxene ± Fe-Ti oxides. Biotite and Fe-Ti-oxide are the dominant intercumulus phases. Orthopyroxene occurs not as a cumulus phase but as peritectic overgrowths on cumulus olivine. A detailed petrographic and mineral chemical study of samples from two stratigraphically controlled traverses through the layered gabbro indicates that the stratigraphy cannot be correlated along the 33 km strike of the ring dyke. Mineral compositions show both normal and reversed fractionation trends. These patterns are interpreted to record at least three separate intrusions of magma into restricted dilatant zones within the ring dyke possibly associated with ongoing caldera collapse. Calculations of parental melt composition using mineral — melt equilibria show that even the most primitive gabbros crystallized from an evolved magma with mg# of 0.42-0.49. The presence of orthopyroxene overgrowths on cumulus olivine suggests rising silica activity in the melt during crystallization and implies a subalkaline parentage for the layered gabbro.     

Volkovsky deposit of titanomagnetite and copper-titanomagnetite ores with accompanying noble-metal mineralization, the Central Urals, Russia

The geology of the Volkovsky deposit, the composition of its rocks, titanomagnetite and copper-titanomagnetite ores with accompanying noble-metal mineralization, and their formation conditions are considered. Special attention is paid to the recently revealed noble-metal mineralization and its attendant character in respect to titanomagnetite ore is shown. Ore minerals and their relationships are characterized. Initially immiscible sulfide segregations are described and their evolution is traced up to interrelations with oxide and silicate cumulates. The distribution of noble metals (NM) in titanomagnetite and copper-titanomagnetite ores is discussed. Throughout ore formation, NM gradually accumulated in silicates, oxides, and sulfides. The highest NM concentrations are related to the sulfide schlieren and veinlike segregations in gabbroic rocks. It is suggested that the deposit was formed as a product of fractionation of basaltic magma. The copper-iron ore was deposited from the residual melt enriched in Cu, Fe, Ti, V and volatile P and S in a wide temperature range of 800 to 570°C. Noble metals concentrated in parallel with their own minerals (largely tellurides and native gold) at the final stage of crystallization of gabbroic intrusion.     

Platinum group element (PGE) geochemistry to understand the chemical evolution of the Earth’s mantle

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.     

http://www.sciencedirect.com/science/article/pii/S1674987111000429

The three most crucial factors for the formation of large and super-large magmatic sulfide deposits are: (1) a large volume of mantle-derived mafic-ultramafic magmas that participated in the formation of the deposits; (2) fractional crystallization and crustal contamination, particularly the input of sulfur from crustal rocks, resulting in sulfide immiscibility and segregation; and (3) the timing of sulfide concentration in the intrusion. The super-large magmatic Ni-Cu sulfide deposits around the world have been found in small mafic-ultramafic intrusions, except for the Sudbury deposit. Studies in the past decade indicated that the intrusions hosting large and super-large magmatic sulfide deposits occur in magma conduits, such as those in China, including Jinchuan (Gansu), Yangliuping (Sichuan), Kalatongke (Xinjiang), and Hongqiling (Jilin). Magma conduits as open magma systems provide a perfect environment for extensive concentration of immiscible sulfide melts, which have been found to occur along deep regional faults. The origin of many mantle-derived magmas is closely associated with mantle plumes, intracontinental rifts, or post-collisional extension. Although it has been confirmed that sulfide immiscibility results from crustal contamination, grades of sulfide ores are also related to the nature of the parental magmas, the ratio between silicate magma and immiscible sulfide melt, the reaction between the sulfide melts and newly injected silicate magmas, and fractionation of the sulfide melt. The field relationships of the ore-bearing intrusion and the sulfide ore body are controlled by the geological features of the wall rocks. In this paper, we attempt to demonstrate the general characteristics, formation mechanism,tectonic settings, and indicators of magmatic sulfide deposits occurring in magmatic conduits which would provide guidelines for further exploration.     

The Significance of the Mesostasis of Basic Layered Igneous Rocks

Many layered igneous rocks consist of two main parts: the cumulus(plus adcumulus and heteradcumulus) material and the pore material,or mesostasis, produced by the crystallization of the trappedliquid. Knowledge of the chemistry of the mesostasis will beuseful in deducing magma fractionation trends and in the determinationof solid/liquid trace element partition coefficients, whichin turn will be significant in helping to elucidate the petrogeneticrelationship between certain basalts and layered gabbros. Anew geochemical method for the determination of both the compositionand amount of mesostasis in layered rocks is proposed. Thismethod uses elements of contrasting behaviour and is best appliedto rhythmically layered rocks rich in mafic or felsic minerals.Data on strontium, cobalt, and uranium are used to apply themethod to two rocks from the Skaergaard intrusion. The resultsobtained are in agreement with published data.     

New data on distribution of REEs in sulfide minerals and Sm-Nd dating of ore genesis of layered basic intrusions

This paper presents data on the distribution of REEs in sulfide minerals from ore-bearing gabbronorites in the Penikat layered intrusion and the results of their isotopic-geochronological Sm-Nd study. A new procedure for determination of REEs in the samples without preliminary separating and concentrating was tested on standard samples to be further used for analysis of sulfide minerals. Analysis of the spectra of the REE distribution in sulfides represents a distribution trend that is similar to the already studied bulk rock and allows deducing that the character of the REE distribution in sulfide minerals from gabbronorites in the Penikat layered intrusion was inherited from the parent magma melt; while the formation of sulfides took place at the stage of rock crystallization. The performed complex studies allow considering that sulfides can be successfully used together with the rock-forming minerals in Sm-Nd dating of ore-bearing mafite-ultramafite intrusions.     

Fractionation of the noble metals by physical processes

During partial melting in the earth’s mantle, the noble metals become fractionated. Os, Ir, Ru, and Rh tend to remain in the mantle residue whereas Pt, Pd, and Re behave mildly incompatible and are sequestered to the silicate melt. There is consensus that sulfide plays a role in the fractionation process; the major noble metal repository in the mantle is sulfide, and most primitive mantle melts are sulfide-saturated when they leave their mantle sources. However, with sulfide–silicate partitioning, the fractionation cannot be modeled properly. All sulfide–silicate partition coefficients are so extremely high that a silicate melt segregating from a mantle source with residual sulfide should be largely platinum-group elements free. We offer a physical alternative to sulfide–silicate chemical partitioning and provide a mechanism of generating a noble metal-rich melt from a sulfide-saturated source: Because sulfide is at least partially molten at asthenospheric temperature, it will behave physically incompatible during melt segregation, and a silicate melt segregating from a mantle residue will entrain molten residual sulfide in suspension and incorporate it in the basaltic pool melt. The noble metal abundances of a basalt then become independent of sulfide–silicate chemical partitioning. They reflect the noble metal abundances in the drained sulfide fraction as well as the total amount of sulfide entrained. Contrary to convention, we suggest that a fertile, sulfide-rich mantle source has more potential to generate a noble metal-enriched basaltic melt than a refractory mantle source depleted by previous partial melting events.     

Chalcophile element partitioning between sulfide phases and hydrous mantle melt: Applications to mantle melting and the formation of ore deposits

Understanding the geochemical behavior of chalcophile elements in magmatic processes is hindered by the limited partition coefficients between sulfide phases and silicate melt, in particular at conditions relevant to partial melting of the hydrated, metasomatized upper mantle. In this study, the partitioning of elements Co, Ni, Cu, Zn, As, Mo, Ag, and Pb between sulfide liquid, monosulfide solid solution (MSS), and hydrous mantle melt has been investigated at 1200 °C/1.5 GPa and oxygen fugacity ranging from FMQ−2 to FMQ+1 in a piston-cylinder apparatus. The determined partition coefficients between sulfide liquid and hydrous mantle melt are: 750–1500 for Cu; 600–1200 for Ni; 35–42 for Co; 35–53 for Pb; and 1–2 for Zn, As, and Mo. The partition coefficients between MSS and hydrous mantle melt are: 380–500 for Cu; 520–750 for Ni; ∼50 for Co; <0.5 for Zn; 0.3–6 for Pb; 0.1–2 for As; 1–2 for Mo; and >34 for Ag. The variation of the data is primarily due to differences in oxygen fugacity. These partitioning data in conjunction with previous data are applied to partial melting of the upper mantle and the formation of magmatic-hydrothermal Cu–Au deposits and magmatic sulfide deposits.I show that the metasomatized arc mantle may no longer contain sulfide after >10–14% melt extraction but is still capable of producing the Cu concentrations in the primitive arc basalts, and that the comparable Cu concentrations in primitive arc basalts and in MORB do not necessarily imply similar oxidation states in their source regions.Previous models proposed for producing Cu- and/or Au-rich magmas have been reassessed, with the conclusions summarized as follows. (1) Partial melting of the oxidized (fO₂ > FMQ), metasomatized arc mantle with sulfide exhaustion at degrees >10–14% may not generate Cu-rich, primitive arc basalts. (2) Partial melting of sulfide-bearing cumulates in the root of thickened lower continental crust or lithospheric mantle does not typically generate Cu- and/or Au-rich magmas, but they do have equivalent potential as normal arc magmas in forming magmatic-hydrothermal Cu–Au deposits in terms of their Cu–Au contents. (3) It is not clear whether partial melting of subducting metabasalts generates Cu-rich adakitic magmas, however adakitic magmas may extract Cu and Au via interaction with mantle peridotite. Furthermore, partial melting of sulfide-bearing cumulates in the deep oceanic crust may be able to generate Cu- and Au-rich magmas. (4) The stabilization of MSS during partial melting may explain the genetic link between Au-Cu mineralization and the metasomatized lithospheric mantle.The chalcophile element tonnage, ratio, and distribution in magmatic sulfide deposits depend on a series of factors. This study reveals that oxygen fugacity also plays an important role in controlling Cu and Ni tonnage and Cu/Ni ratio in magmatic sulfide deposits. Cobalt, Zn, As, Sn, Sb, Mo, Ag, Pb, and Bi concentrations and their ratios in sulfide, due to their different partitioning behavior between sulfide liquid and MSS, can be useful indices for the distribution of platinum-group elements and Au in magmatic sulfide deposits.     

Distribution and mineralogy of platinum-group elements in altered chromitites of the Campo Formoso layered intrusion (Bahia State, Brazil): control by magmatic and hydrothermal processes

Summary Polyphase, penetrative hydrothermal metasomatism in chromitites of the Campo Formoso layered intrusion produced spectacular chromite – ferrian chromite zoning and transformed the primary intercumulus silicates into a chlorite – serpentine – carbonate – talc assemblage. Alteration did not substantially modify the composition of chromite cores and the distribution of platinum-group elements (PGE) through the sequence of chromitite layers, which still are consistent with magmatic fractionation processes. Texture and composition of laurite and Os–Ir–Ru alloys included in chromite cores indicate that these PGM were not altered, and are probably magmaticin origin. In contrast, the PGM located in the intergranular chlorite matrix (laurite, Ir–Ru–Rh sulfarsenides and Pt–Pd compounds with Sb, Bi and Te) display evidence of hydrothermal reworking. These PGM are intimately intergrown with low-temperature Ni-sulfides. The paragenesis suggests that the Ni-sulfides-PGM assemblage formed at the expenses of unknown PGM precursors, which must have been originally present in the intercumulus silicate matrix. Mechanism of formation involves a sequence of dissolution-precipitation events controlled by variation of redox conditions during chromite alteration. The presence of a secondary ore mineral assemblage consisting of galena, bismuthinite, native antimony, and various Pb–Sb compounds suggests a possible contribution of fluids derived from the adjacent granite.     

Platinum-group element systematics in Mid-Oceanic Ridge basaltic glasses from the Pacific, Atlantic, and Indian Oceans

The concentrations of Ir, Ru, Pt and Pd have been determined in 29 Mid-Oceanic Ridge basaltic (MORB) glasses from the Pacific (N = 7), the Atlantic (N = 10) and the Indian (N = 11) oceanic ridges and the Red Sea (N = 1) spreading centers. The effect of sulfide segregation during magmatic differentiation has been discussed with sample suites deriving from parental melts produced by high (16%) and low (6%) degrees of partial melting, respectively. Both sample suites define positive and distinct covariation trends in platinum-group elements (PGE) vs. Ni binary plots. The high-degree melting suite displays, for a given Ni content, systematically higher PGE contents relative to the low-degree melting suite. The mass fraction of sulfide segregated during crystallization (X_sulf), the achievement of equilibrium between sulfide melt and silicate melts (R_eff), and the respective proportions between fractional and batch crystallization processes (S_b) are key parameters for modeling the PGE partitioning behavior during S-saturated MORB differentiation. Regardless of the model chosen, similar sulfide melt/silicate melt partition coefficients for Ir, Ru, Pt and Pd are needed to model the sulfide segregation process, in agreement with experimental data. When corrected for the effect of magmatic differentiation, the PGE data display coherent variations with partial melting degrees. Iridium, Ru and Pt are found to be compatible in nonsulfide minerals whereas the Pd behaves as a purely chalcophile element. The calculated partition coefficients between mantle sulfides and silicate melts (assuming a PGE concentration in the oceanic mantle at ∼0.007 × CI-chondritic abundances) increase from Pd (∼10³) to Ir (∼10⁵). This contrasting behavior of PGE during S-saturated magmatic differentiation and mantle melting processes can be accounted for by assuming that Monosufide Solid Solution (Mss) controls the PGE budget in MORB melting residues whereas MORB differentiation processes involve Cu-Ni-rich sulfide melt segregation.