Contrasting platinum-group element concentration patterns in cumulates of the Bushveld complex

Chromite-rich lithologies in both the lower and the critical zones of the Bushveld Complex in the Potgietersrus area display flat, chondrite-normalized, platinum-group-element (PGE) concentration patterns, whereas those of associated sulphide-bearing, but chromite-poor rocks are considerably steeper. The low (Pt+Pd)/(Os+Ir+Ru) ratio in the chromite-bearing rocks is maintained irrespective of the amount of sulphide or chromite in the rock. This feature suggests that the partitioning of the individual PGE into PGE-bearing phases during conditions in the magma under which crystallization of chromite in excess of the normal cotectic amounts was favoured differed from conditions under which an immiscible sulphide liquid separated from the same magma in the absence of enhanced chromite crystallization. These changes in the partitioning coefficients of the individual PGE are considered to reflect changes in the solubility of these elements in response to variations in the intensive parameters in the magma necessary to bring about the enhanced crystallization of chromite.     

Petrology of the Basistoppen Sill, East Greenland: A Calculated Magma Differentiation Trend

The 660 m thick Basistoppen sill is an Eocene, tholeiitic, layeredintrusion emplaced in the upper part of the Skaergaard complexshortly after solidification of the Skaergaard magma. Despiteits small size, the Basistoppen sill has one of the most extensivedifferentiation sequences known. The ranges of the solid solutionsin olivine, plagioclase, and pyroxene from the Basistoppen arecomparable to those in the Skaergaard and Bushveld intrusions.The rocks of the sill are orthocumulates composed of approximately35% trapped liquid and 65% cumulus minerals and can be dividedinto zones based on changes in the cumulus mineral assemblage.From the base upward those zones are: a Gabbro Picrite Zonecontaining cumulus olivine, Fe-Cr spinel, and minor biotite;a Bronzite Gabbro Zone containing cumulus orthopyroxene, Ca-richclinopyroxene, plagioclase, and minor Fe-Cr spinel; a PigeoniteGabbro Zone containing cumulus plagioclase, Ca-rich clinopyroxene,pigeonite, magnetite, and minor ilmenite; and a Fayalite DioriteZone containing cumulus plagioclase, Ca-rich clinopyroxene,magnetite, ilmenite, apatite, and olivine. The Basistoppen isoverlain by a zoned granophyre sill that was most likely derivedin part from the Basistoppen magma and in part from melted Precambriangneiss. The excellent exposure, uncomplicated structure, goodchilled margin, and lack of strong modal layering facilitatethe calculation of a differentiation trend for the Basistoppensill. During crystallization the Basistoppen magma became progressivelyricher in Fe, P, Na, K, Zn, Rb, Zr, La, Sm, and Th, became progressivelypoorer in Mg, Ca, Al, Cr, and Ni, and remained relatively unchangedin Si, Sc, and Sr through at least the first 90% of crystallization.     

Controls on disseminated PGE–Cu–Ni sulfide mineralization within the Rietfontein deposit,Eastern Limb,Bushveld Complex,South Africa: Implications for the formation of contact-type magmatic sulfide deposits

The Rietfontein platinum group element (PGE)–Cu–Ni sulfide deposit of the Eastern Limb of the Bushveld Complex hosts disseminated contact-style mineralization that is similar to other economic magmatic sulfide deposits in marginal settings within the complex. The mineralization at Rietfontein consists of disseminated PGE-bearing base metal sulfides that are preferentially located at the contact between a distinct package of marginal norites overlain by a thick heterogeneous unit dominated by gabbronorites with lesser norites and ultramafic rocks. Down-hole composite data and metal scatterplots indicate that the PGE correlate well with Ni, Cu and S and that only minor metal remobilization has taken place within the basal norite sequence. Plots of (Nb/Th)_PM vs. (Th/Yb)_PM indicate that the melts that formed the Rietfontein intrusive sequence were strongly crustally contaminated prior to emplacement at Rietfontein, whereas inverse relationships between PGE tenors and S/Se ratios indicate that these magmas assimilated crustal S, causing S-saturation and the formation of immiscible sulfides under high R-factor conditions that generated high PGE tenor sulfides. Reverse zoning of cumulus minerals at Rietfontein suggests that fresh primitive melts were introduced to a partially fractionated staging chamber. The introduction of new magmas into the chamber caused overpressure and the forced evacuation of the contents of the chamber, leading to the emplacement of the existing magmas within the staging chamber at Rietfontein in two separate pulses. The first pulse of magma contained late-formed cumulus phases, including low Mg# orthopyroxene and plagioclase, was emplaced between footwall unreactive and S-poor Pretoria Group quartzites and a hangingwall sequence of Rooiberg Group felsites, and was rapidly chilled to form the basal norite sequence at Rietfontein. The second pulse of magma contained early formed cumulus phases, including olivine, chromite, and high Mg# orthopyroxene, and was emplaced above the chilled norite sequence as a crystal mush to form gabbronorites and ultramafic rocks. This second pulse of magma also contained PGE-bearing base metal sulfides that accumulated at the contact between this second batch of magma and the already chilled basal norite sequence. The formation of Platreef-type mineralization outside of the Northern Limb of the Bushveld Complex confirms there are a number of areas within the Bushveld Complex that are prospective for this style of mineralization.     

Geochemistry of fractionation of coherent elements (Zr and Hf) during the profound differentiation of peralkaline magmatic systems: A case study of the Lovozero Complex

The paper presents pioneering data on Hf distribution in peralkaline rocks, ores, and rock-forming and accessory minerals of the Lovozero Complex. Variations in the Zr/Hf ratio are determined in all rocks of the Lovozero alkaline massif. This ratio is proved to increase in the course of evolution of alkaline magma because of fractionation of alkaline pyroxene. The Hf distribution coefficient is evaluated for alkali-rich pyroxene, whose crystallization controls Zr and Hf fractionation during the differentiation of alkaline magma. These data and the equation of equilibrium and fractional crystallization are utilized in a model suggested for Zr and Hf fractionation in the course of evolution of the Lovozero intrusion.     

The nature and genesis of marginal Cu–PGE–Au sulphide mineralisation in Paleogene Macrodykes of the Kangerlussuaq region, East Greenland

The Kangerlussuaq region of East Greenland hosts a variety of early Tertiary extrusive and intrusive igneous rocks related to continental break up and the passage of the ancestral Iceland plume. These intrusive bodies include a number of gabbroic macrodykes, two of which—the Miki Fjord Macrodyke, and the newly discovered Togeda Macrodyke—contain Cu–PGE–Au sulphide mineralisation along their margins. Sulphides occur as disseminated interstitial blebs and rounded globules of chalcopyrite and pyrrhotite with some Fe–Ti oxides and platinum-group minerals, comprising largely Pd bismuthides and tellurides. The globules are interpreted to have formed from fractionation of trapped droplets of an immiscible Cu- and Pd-rich sulphide melt and show geopetal indicators. Sulphur isotopes imply a local crustal source of S in these from pyritic sediments of the Kangerlussuaq Basin. Thus, generation of these sulphide occurrences was controlled by local country rock type. Low Ni/Cu and Pt/Pd ratios, also present in the Platinova reefs in the Skaergaard Intrusion, indicate that early fractionation of olivine may have depleted the magma of Ni and suggest the likely presence of a large magma chamber at depth. Xenoliths of Ni-rich olivine cumulates in the Miki Fjord Macrodyke may have been sourced from such a body. The location of thus far unidentified conduit or feeder zones to the macrodykes beneath the present day surface may represent potential targets for more massive sulphide orebodies.     

Petrogenesis of gabbro and orthopyroxene gabbro from the Phenai Mata Igneous Complex,Deccan volcanic province: Products of concurrent assimilation and fractional crystallization

We report the occurrence of orthopyroxene gabbro from the Phenai Mata Igneous Complex (containing thoeliitic and alkaline rocks) that occur within Deccan Traps. The P-T calculations based on two pyroxene thermometry vary from 8.5±1.0 kbar and 963±39 °C. These gabbroic rocks exhibit high Mg# (0.67 to 0.71). But their primary magma signature can be negated due to their high SiO₂ (> 50 wt %), low Ni (32–35 ppm) and Cr (105–182 ppm) contents. Further, simple fractional crystallization was not responsible for the modification of the magma. Modeling carried out using trace element concentrations revealed that concurrent assimilation and fractional crystallization (AFC) was responsible for the genesis of these rocks. Small pods of magma could have accumulated in the crustal portions and concurrent assimilation and fractional crystallization have taken place in the generation of gabbro and orthopyroxene gabbro in the present study area.     

Contrasting sulphide contents of the Bushveld and Sudbury Igneous Complexes

The Sudbury Igneous Complex (SIC) contains abundant sulphides, especially near the base, and hosts one of the worlds largest nickel and copper deposits. The Bushveld Complex (BC) contains relatively little sulphide, but hosts the worlds largest platinum-group element deposits. The most recent calculations of the sulphur solubility in magmas that produced the BC are based on the sulphur solubility of mid-ocean ridge basalts that have less SiO₂ than Bushveld magmas. Such a difference may lead to an overestimation of sulphur solubility by as much as 25%. The revised sulphur solubility curve presented here for Bushveld magmas may also have relevance to the SIC in view of its siliceous nature. Sulphur solubility curves can be used to determine the proportion of sulphide expected in cumulate rocks once sulphur saturation is attained. These models are tested using observed sulphide contents in both intrusions. The observed decreasing sulphur contents (>0.3–0.05% S) from the base of the SIC upward are broadly consistent with these sulphur solubility curves, and are consistent with sulphide saturation through the entire mafic portion. In contrast, the lower half of the BC contains extremely little sulphur (generally <0.02% S), except for two thin layers, which is not consistent with sustained sulphide saturation at any level. Previous interpretations of the sulphur content of Bushveld rocks have suggested that the Lower and Critical Zones were sulphide saturated, but that they had then lost some of the sulphide due to various processes. The present sulphide content of the cumulates of the BC is so low that, if they had once been saturated, over 90% of all the sulphide must have been removed. Mass balance calculations indicate that these large amounts of displaced sulphur remain unaccounted for in such models. Instead, the observed sulphur contents are in reasonable agreement with that expected in a cumulate sequence forming from a sulphur-undersaturated magma. Whereas the Merensky Reef and Bastard pyroxenite contain minor sulphides, the compositions of the immediate hanging wall rocks indicate sulphide undersaturation. Such an abrupt return to sulphide undersaturation is not consistent with models involving sulphide formation from large volumes of magma. One possible explanation for these two observations is that intermittent sulphur degassing occurred through a fractured roof of the BC, so that the magma was never continuously sulphur-saturated with respect to an immiscible sulphide liquid.     

Sulfide saturation history of the Stillwater Complex, Montana: chemostratigraphic variation in platinum group elements

A platinum group element (PGE) investigation of a 5.3?km-thick stratigraphic section of the Stillwater Complex, Montana was undertaken to refine and test a geochemical technique to explore for platiniferous horizons in layered mafic/ultramafic complexes. PGE, Au, major, and trace elements were determined in 92 samples from outcrops along traverses in the Chrome Mountain and Contact Mountain areas in the western part of the Stillwater Complex where the J-M reef occurs ～1,460?m above the floor of the intrusion. A further 29 samples from a drill hole cored in the immediate vicinity of the J-M reef were analyzed to detail compositional variations directly above and below the J-M reef. Below the J-M reef, background concentrations of Pt (10?ppb) and Pd (7?ppb) are features of peridotites with intermediate S concentrations (mostly 100–200?ppm) and rocks from the Bronzitite, Norite I, and Gabbronorite I zones (mostly <100?ppm S). A sustained increase in S abundance commences at the J-M reef and continues to increase and peaks in the center of the 600?m-thick middle banded series. Over this same interval, Pt, Pd, and Au are initially elevated and then decrease in the order Pd?>?Pt?>?Au. Within the middle and upper banded series, S abundances fluctuate considerably, but exhibit an overall upward increase. The behavior of these elements records periodic sulfide saturation during deposition of the Peridotite zone, followed by crystallization under sulfide-undersaturated conditions until saturation is achieved at the base of the J-M reef. Following formation of the reef, sulfide-saturated conditions persisted throughout the deposition of most of the remaining Lower Layered Series. This resulted in a pronounced impoverishment in PGE abundance in the remaining magma, a condition that continued throughout deposition of the remainder of a succession, which is characterized by very low Pt (1.5?ppb) and Pd (0.7?ppb) abundances. Because only unmineralized rock was selected for study in the 5.3?km-thick section, the results provide an unbiased picture of the variation in background PGE levels during crystallization of the Stillwater Complex. In contrast, the variations in the drill core samples through the reef provide a detailed record of ore formation. Plots of Pt, Pd, Pd/S, and Pt?+?Pd as a function of stratigraphic height in the intrusion show that the location of the J-M reef is defined by an abrupt change in these concentrations and ratios. Although this is the most abrupt change, three other anomalies in PGE abundance and ratios are apparent in the profiles and coincide with known laterally extensive sub-economic sulfide concentrations above the J-M reef. The uppermost of these is the PGE-bearing Picket Pin sulfide horizon. The relative ease with which mineralized horizons can be pinpointed in these diagrams indicates that a similar approach could be used in exploration programs in other ultramafic/mafic intrusions. Our observations exclude the possibilities of either magma mixing within the Stillwater chamber or the fluxing of a volatile-rich fluid as the mechanisms responsible for the genesis of the J-M reef. Rather, our data indicate that the J-M reef formed from a parental magma that was strongly enriched in PGE; this magma likely formed at depth below the Stillwater magma chamber by the interaction of the parental magma with S-rich meta-sedimentary rocks, followed by the re-dissolution of these sulfides in the Stillwater magma.     

Petrology of the Marginal Border Series of the Skaergaard Intrusion

The Marginal Border Series (MBS) of the Skaergaard intrusionconsists of rocks formed by in situ crystallization againstthe walls of the intrusion. Most of these rocks are productsof fractional crystallization, though samples believed to representchilled liquid occur locally at the intrusive contact. The MBScomprises only 5% of the exposed volume of the intrusion, butwithin its thickness, the order of crystallization and the compositionsof fractionated rocks and minerals vary systematically withdistance inward from the intrusive contact in largely the samemanner as rocks and minerals upward through the Layered Series(LS). Earliest differentiates are cumulates of olivine and plagioclase.The most basic compositions of cumulus plagioclase (An₇₂) andolivine (Fo₈₄) in these rocks indicate that the amount of fractionationpreceding formation of the exposed LS was substantially lessthat previously believed. Field and compositional data indicatethat picritic blocks are xenoliths rather than cumulates ofthe Skaergaard magma. Xenoliths of gneiss in all stages of reactionare locally abundant; however, there is no evidence that uppercrustal material contaminated the magma from which the MBS cumulatesformed. Compositions of cumulus minerals in the MBS differ fromthose in comparable LS rocks. Cumulates in the lower marginscontain more calcic plagioclase, more magnesian augite in allbut the late differentiates, and more iron-rich olivine. Thecompositions of cumulus olivine and to a lesser degree thoseof other mafic silicates, were modified to more iron-rich compositionsby re-equilibration with relatively large amounts of interstitialliquid. The lower MBS and LS crystallized from the same magma, but fractionationoccurred at different rates on the walls and floor of the intrusion.The upper margin may have crystallized from a magma of modifiedcomposition and fractionated at rates different from that inthe lower margin and Upper Border Series (UBS). Crystals onthe floor and roof of the intrusion accumulated faster or moreefficiently than on the walls. At any given stage of fractionation,crystals also accumulated against all sides of the magma chamberat about the same rate. Either the rates of cooling, crystallization,and crystal retention affected accumulation rates locally asfunctions of rock type and geometry of the walls, or these rateswere largely independent of wall rock owing to buffering ofconductive heat loss possibly to an envelope of hydrothermalfluid circulating around the crystallizing magma. The appearanceor disappearance of cumulus minerals in the lower MBS occursat higher structural levels than in the LS and at lower structurallevels than in the UBS. These relationships together with cumulusmineral compositions indicate that magma at the margins wasalways somewhat less fractionated than that at the floor androof of the chamber. It is proposed that these relationshipsreflect the combined effects of liquid and crystal fractionationof the magma within largely independent convection systems inthe lower and upper parts of the chamber.     

Trace elements in the Merensky Reef and adjacent norites Bushveld Complex South Africa

Trace elements were analysed in rocks and minerals from three sections across the Merensky Reef in the Rustenburg Platinum Mine in the Bushveld Complex of South Africa. Whole rocks and separated minerals were analysed by inductively coupled plasma-mass-spectrometer (ICP-MS) and in situ analyses were carried out by ion microprobe and by laser-source ICP-MS. Merensky Reef pyroxenites contain extremely high concentrations of a wide range of trace elements. These include elements incompatible with normal silicate minerals as well as siderophile and chalcophile elements. For major elements and compatible trace elements, the measured concentrations in cumulus phases and the bulk rock compositions are similar. For highly incompatible elements, however, concentrations in bulk rocks are far higher than those measured in the cumulus phases. In situ analyses of plagioclase have far lower concentrations of Th, Zr and rare earth elements than ICP-MS analyses of bulk separates of plagioclase, a difference that is attributed to the presence of trace-element-rich accessory phases in the bulk mineral separates. We used these data to calculate the trace-element composition of the magmas parental to the Merensky Unit and adjacent norites. We argue that there is no reason to assume that the amount of trapped liquid in the Merensky orthopyroxenite was far greater than in the norites and we found that the pyroxenite formed from a liquid with higher concentrations of incompatible trace elements than the liquid that formed the norites. We propose that the Bushveld Complex was fed by magma from a deeper magma chamber that had been progressively assimilating its crustal wall rocks. The magma that gave rise to the Merensky Unit was the more contaminated and unusually rich in incompatible trace elements, and when it entered the main Bushveld chamber it precipitated the unusual phases that characterize the Merensky Reef. The hybrid magma segregated sulphides or platinum-group-element-rich phases during the course of the contamination in the lower chamber. These phases accumulated following irruption into the main Bushveld chamber to form the Merensky ore deposits.     

Petrology of the Proterozoic Potato River Layered Intrusion, Northern Wisconsin, USA

The Potato River intrusion is a Keweenawan (1100 Ma) mafic plutonemplaced in Keweenawan volcanics and earlier Proterozoic metasedimentaryrocks along the southeastern flank of the Lake Superior syncline.It comprises the following lithostratigraphic zones: a thinto absent Border zone of altered olivine gabbro; a Lower zoneof olivine gabbro; a Picritic zone of picrite and troctolite;a Middle zone of olivine gabbro and leucogabbro; an Upper zoneof quartz leucogabbro and ferrogabbro; and a Roof zone of granophyricand granitic rocks. Fractional crystallization is evident fromcompositional changes in the rocks and cumulus minerals withstratigraphic height. Elements concentrated in the cumulus mineralsolivine and plagioclase (Mg, Fe²⁺, Al, Ca, Ni, Co, Cr, Sr) decreasewith height; elements concentrated in the trapped liquid (Na,K, La, Y, Zr, Nb, Rb, Ba) increase with height; and other elements(Ti, Fe³⁺, P, Ga, V, Sc, Cu, Zn) show complicated behavior relatedto the appearance of additional cumulus phases such as clinopyroxene,Fe-Ti oxides, and apatite. Lower zone rocks contain some sulfide,probably from sulfur derived from the country rock, and theUpper zone has sulfides probably precipitated from an immisciblesulfide liquid. The sulfide-bearing rocks have similaritiesto those of other intrusions, such as Bushveld, Stillwater,and Skaergaard. The picritic and troctolitic rocks of the Picritic zone indicatethat the intrusion was open to additional injections of maficmagma. Roof zone granophyric rocks are residual liquids intrudedalong the upper margin of the intrusion during regional tilting,but Roof zone granitic rocks are probably melted country rock.An attempt is made to estimate by reverse stratigraphic summationthe compositional path of the magma that solidified above thePicritic zone. The first compositions are highly aluminous,which suggests that the upper part of the intrusion has beenenriched in plagioclase by convection-aided crystal sorting.A complementary unit of mafic rocks is not exposed, but it couldbe present down dip. Some of the later compositions are similarto typical Keweenawan high-Al tholeiites. The magma did notundergo extreme iron enrichment, probably because of oxygenfugacity buffering.     

Geochemistry of an Alaskan-type mafic-ultramafic complex in Eastern Desert,Egypt:New insights and constraints on the Neoproterozoic island arc magmatism

Mikbi intrusion(MI) is a part of the Neoproterozoic Nubian Shield located along the NE-SW trending major fracture zones prevailing southern Eastern Desert of Egypt. In this study, we present for the first time detailed mineralogical and bulk-rock geochemical data to infer some constraints on the parental magma genesis and to understand the tectonic processes contributed to MI formation. Lithologically, it is composed of fresh peridotite, clinopyroxenite, hornblendite, anorthosite, gabbronorite, pyroxene amphibole gabbro, amphibole gabbro and diorite. All rocks have low Th/La ratios(mostly <0.2) and lack positive Zr and Th anomalies excluding significant crustal contamination. They show very low concentrations of Nb, Ta, Zr and Hf together with sub-chondritic ratios of Nb/Ta(2-15) and Zr/Hf(19-35),suggesting that their mantle source was depleted by earlier melting extraction event. The oxygen fugacity(logfO_2) estimated from diorite biotite is around the nickel-nickel oxide buffer(NNO) indicating crystallization from a relatively oxidized magma. Amphiboles in the studied mafic-ultramafic rocks indicate relative oxygen fugacity(i.e. ΔNNO; nickel-nickel oxide) of 0.28-3 and were in equilibrium mostly with 3.77-8.24 wt.% H_2 O_melt(i.e. water content in the melt), consistent with the typical values of subduction-related magmas. Moreover, pressure estimates(0.53-6.79 kbar) indicate polybaric crystallization and suggest that the magma chamber(s) was located at relatively shallow crustal levels. The enrichment in LILE(e.g., Cs, Ba, K and Sr) and the depletion in HFSE(e.g., Th and Nb) relative to primitive mantle are consistent with island arc signature. The olivine, pyroxene and amphibole compositions also reflect arc affinity. These inferences suggest that their primary magma was derived from partial melting of a mantle source that formerly metasomatized in a subduction zone setting. Clinopyroxene and bulkrock data are consistent with orogenic tholeiitic affinity. Consequently, the mineral and bulk-rock chemistry strongly indicate crystallization from hydrous tholeiitic magma. Moreover, their trace element patterns are subparallel indicating that the various rock types possibly result from differentiation of the same primary magma. These petrological, mineralogical and geochemical characteristics show that the MI is a typical Alaskan-type complex.     

Changes in Silicic Melt Structure Between the Two Bandelier Caldera-Forming Eruptions, New Mexico, USA: Evidence from Zirconium and Light Rare Earth Elements

The Cerro Toledo Rhyolite is a group of high-silica rhyolitedomes and tephras which were erupted during the period betweenthe Lower Bandelier Tuff (LBT) at 1?45 Ma and the Upper BandelierTuff (UBT) at 1?12 Ma. The tephra sequence reflects the changingcomposition of the most fractionated liquids at the top of themagma chamber or chambers owing to crystallization during this0?33-Ma interval, over which it is possible to trace magma evolutionin detail. Incompatible elements such as Cs and Lu generallyincrease in concentration upsection through the tephra sequence.By contrast, Zr initially decreases upsection from 153 ppm to134 ppm in the middle, then increases upward to 320 ppm in themost evolved rhyolites. The Zr/Cs and Hf/Cs ratios initiallydecline, then become constant. The dramatic rise in Zr at nearlyconstant Zr/Cs suggests suppression of zircon crystallizationand a change from a high degree of zircon oversaturation toone of marginal oversaturation in the most evolved magmas. Theobserved Zr trends in the Cerro Toledo Rhyolite are oppositeto those (1) predicted by experimental studics of Zr solubilityin silicic magmas and (2) observed in the Bishop Tuff. LREEshow broadly similar relations to Zr and Hf. We have examined two parameters—iron content and volatilecontent of the magma—which may have controlled the crystallizationbehavior of zircon and the LREE-rich phase(s). The dramaticincrease in Zr and LREE in the most evolved Cerro Toledo Rhyolitesand basal UBT plinian tephras is accompanied by similar increasesin iron and halogen contents. If changa in the halogen contentsof matrix glasses are indicative of changes in overall volatilelevels at the top of the magma chamber(s), the increase in volatilesand iron may have modified the structural state of the magmaand increased the solubilities of zircon and the LREE-rich phase(s),thereby raising the saturation levels of Zr and LREE and stabilizingthese elements in the melt. Disruption of the melt structuremay have resulted from (1) Fe as a network modifier or quasi-molecularcomplex, (2) breaking of bridging oxygens by anions such asOH^– and F^–, and/or (3) complexing of Al and alkalisby OH, F, and/or Cl.     

Present condition of Mt. Elbrus volcano

The Freetown layered complex, located on the western coast of Sierra Leone, is a rift-related tholeiitic intrusion associated with the Jurassic (～193 Ma) opening of the Atlantic Ocean at midlatitude. The complex is ～ 60 km long, 14 km wide, and 7 km thick along a major E-W traverse extending from Waterloo to York. Gravity data and dips of laminations in the layered rocks suggest that the intrusive complex is lopolithic in shape, with some parts presently being submarine.

The exposed rocks consist of a rhythmically layered sequence of troctolite, olivine gabbro, gabbronorite, gabbro, and anorthosite. The complex has been divided into four zones delineated by (1) topographic expression, whereby the base of each zone forms a scarp, and the top forms dip slopes and strike valleys; and (2) cyclical repetition of rock types (Wells, 1962). A new detailed stratigraphic section along the Waterloo-York traverse is presented, in which Zone 3 is subdivided into an upper 2000-m-thick anorthosite-gabbro interval and a lower 1700-m-thick rhythmically layered subzone.

Inverted pigeonite first became a cumulus phase at the bottom of Zone 2, before disappearing near the middle of Zone 3 at the anorthosite-gabbro interval, only to reappear at the top of Zone 4 with cumulus titanomagnetite. Mineral compositions in the complex range from An₇₂ to An₇₂ plagioclase, Fo₅₆ to Fo₇₅ olivine, En_38.5 to En_44.8 augite, and En_54.9 to En_74.6 orthopyroxene. The compositions of plagioclase and olivine in Zone 2 vary irregularly, although the overall trend is toward reverse differentiation. By contrast, Zone 4 is characterized by a rapid decrease in Fo and An from the base of the zone upward, followed by an increase. Cryptic variation also is shown by the Ni content of olivine and Cr content of clinopyroxene.

The overall pattern of cryptic variation in the complex suggests continual leakage of fresh magma into the chamber, followed by oscillatory spikes in the rhythmically layered subzone of Zone 3, where major influxes of new magma occurred. The changes in mineral compositions and modal abundances as a function of stratigraphic height are the result of magma recharge, followed by mixing of new and evolved resident magmas in the Freetown magma chamber. This probably resulted in the expansion of the chamber and crystallization in situ without any discharge. The inferred crystallization sequence for each zone is different, reflecting different magma compositions and changes that occur in the magmas during crystallization. The alternative hypotheses that the Freetown Complex formed from a single parental magma, or that mineral layering was the result of the crystallization sequence Fe-Ti oxides→olivine→pyroxene→plagioclase, are not supported by the evidence.     

Selective concentration of cesium in analcime during hydrothermal alteration,Yellowstone National Park,Wyoming

Chemical and mineralogical studies of fresh and hydrothermally altered rhyolitic material in Upper and Lower Geyser Basins, Yellowstone National Park, show that all the altered rocks are enriched in Cs and that Cs is selectively concentrated in analcime. The Cs content of unaltered rhyolite lava flows, including those from which the altered sediments are derived, ranges from 2.5 to 7.6 ppm. The Cs content of analcime-bearing altered sedimentary rocks is as high as 3000 ppm, and in clinoptilolite-bearing altered sedimentary rocks Cs content is as high as 180 ppm. Altered rhyolite lava flows which were initially vitrophyres, now contain up to 250 ppm Cs, and those which were crystallized prior to hydrothermal alteration contain up to 14 ppm. Mineral concentrates of analcime contain as much as 4700 ppm Cs. The Cs must have been incorporated into the analcime structure during crystallization, rather than by later cation substitution, because analcime does not readily exchange Cs. The $\text{Cs}\text{Cl}$ of the fluids circulating through the hydrothermal system varies, suggesting that Cs is not always a conservative ion and that Cs is lost from upflowing thermal waters due to water-rock interaction resulting in crystallization of Cs-bearing analcime.The source of Cs for Cs enrichment of the altered rocks is from leaching of rhyolitic rocks underlying the geyser basins, and from the top of the silicic magma chamber that underlies the area.Analcime is an important natural Cs sink, and the high Cs concentrations reported here may prove to be an important indicator of the environment of analcime crystallization.     

Platinum-group Elements and Microstructures of Normal Merensky Reef from Impala Platinum Mines, Bushveld Complex

The Merensky Reef of the Bushveld Complex contains one of theworld’s largest concentrations of platinum-group elements(PGE). We have investigated ‘normal’ reef, its footwalland its hanging wall at Impala Platinum Mines. The Reef is 46cm thick and consists from bottom to top of leuconorite, anorthosite,chromitite and a very coarse-grained melanorite. The footwallis leuconorite and the hanging wall is melanorite. The onlyhydrous mineral present is biotite, which amounts to 1%, orless, of the rock. All of the rocks contain 0·1–5%interstitial sulphides (pyrrhotite, pentlandite and chalcopyrite),with the Reef rocks containing the most sulphides (1–5%).Lithophile inter-element ratios suggest that the magma fromwhich the rocks formed was a mixture of the two parental magmasof the Bushveld Complex (a high-Mg basaltic andesite and a tholeiiticbasalt). The Reef rocks have low incompatible element contentsindicating that they contain 10% or less melt fraction. Nickel,Cu, Se, Ag, Au and the PGE show good correlations with S inthe silicate rocks, suggesting control of the abundance of thesemetals by sulphides. The concentration of the chalcophile elementsand PGE in the silicate rocks may be modelled by assuming thatthe rocks contain sulphide liquid formed in equilibrium withthe evolving silicate magma. It is, however, difficult to modelthe Os, Ir, Ru, Rh and Pt concentrations in the chromititesby sulphide liquid collection alone, as the rocks contain 3–4times more Os, Ir, Ru, Rh and Pt than the sulphide-collectionmodel would predict. Two possible solutions to this are: (1)platinum-group minerals (PGM) crystallize from the sulphideliquid in the chromitites; (2) PGM crystallize directly fromthe silicate magma. To model the concentrations of Os, Ir, Ru,Rh and Pt in the chromitites it is necessary to postulate thatin addition to the 1% sulphides in the chromitites there isa small quantity (0·005%) of cumulus PGM (laurite, cooperiteand malanite) present. Sulphide liquids do crystallize PGM atlow f_S2. Possibly the sulphide liquid that was trapped betweenthe chromite grains lost some Fe and S by reaction with thechromite and this provoked the crystallization of PGM from thesulphide liquid. Alternatively, the PGM could have crystallizeddirectly from the silicate magma when it became saturated inchromite. A weakness of this model is that at present the exactmechanism of how and why the magma becomes saturated in PGMand chromite synchronously is not understood. A third modelfor the concentration of PGE in the Reef is that the PGE arecollected from the underlying cumulus pile by Cl-rich hydrousfluids and concentrated in the Reef at a reaction front. Althoughthere is ample evidence of compaction and intercumulus meltmigration in the Impala rocks, we do not think that the PGEwere introduced into the Reef from below, because the rocksunderlying the Reef are not depleted in PGE, whereas those overlyingthe Reef are depleted. This distribution pattern is inconsistentwith a model that requires introduction of PGE by intercumulusfluid percolation from below. KEY WORDS: Merensky Reef; platinum-group elements; chalcophile elements; microstructures     

Pan-African adakitic rocks of the north Arabian–Nubian Shield: petrological and geochemical constraints on the evolution of the Dokhan volcanics in the north Eastern Desert of Egypt

The Precambrian basement of Egypt is part of the Red Sea Mountains and represents the north-western part of the Arabian–Nubian Shield (ANS). Five volcanic sections are exposed in the Egyptian basement complex, namely El Kharaza, Monqul, Abu Had, Mellaha and Abu Marwa. They are located in the north Eastern Desert (ED) of Egypt and were selected for petrological and geochemical studies as they represent the Dokhan volcanics. The volcanics divide into two main pulses, and each pulse was frequently accompanied by deposition of immature molasse type sediments, which represent a thick sequence of the Hammamat group in the north ED. Compositionally, the rocks form a continuum from basaltic andesite, andesite, dacite (lower succession) to rhyodacite and rhyolite (upper succession), with no apparent compositional gaps. These high-K calc-alkaline rocks have strong affinities to subduction-related rocks with enriched LILEs (Rb, Ba, K, Th, Ce) relative to high field strength elements (Nb, Zr, P, Ti) and negative Nb anomalies relative to NMORB. The lower succession displays geochemical characteristics of adakitic rocks with SiO₂ >53 wt%, Al₂O₃ >15 wt%, MgO >2.5 wt%, Mg# >49, Sr >650 ppm, Y <17 ppm, Yb <2 ppm, Ni >25 ppm, Cr >50 ppm and Sr/Y >42.4. They also have low Nb, Rb and Zr compared to the coexisting calc-alkaline rhyodacites and rhyolites. The highly fractionated rhyolitic rocks have strong negative Eu anomalies and possess the geochemical characteristics of A-type suites. Trace element geochemical signatures indicate a magma source consistent with post-collisional suites that retain destructive plate signatures associated with subduction zones. The adakitic rocks in the northern ANS are generated through partial melting of delaminated mafic lower crust interacting with overlying mantle-derived magma. The Dokhan volcanics were likely generated by a combination of processes, including partial melting, crystal fractionation and assimilation.     

Fluid and magmatic processes in the formation of the Ary-Bulak ongonite massif (eastern Transbaikalia)

The paper discusses the formation conditions of the Ary-Bulak ongonite massif (eastern Transbaikalia). Studies of melt and fluid inclusions have shown that, along with crystalline phases and a silicate melt, ongonitic magma contained aqueous–saline fluids of different types, fluoride melts compositionally similar to fluorite, sellaite, cryolite, chiolite, and more complex aluminum fluorides as well as silicate melts with abnormal Cs and As contents. An ongonite melt crystallized with the participation of P–Q fluids as vapor solutions, presumably NaF-containing and slightly admixed with chlorides. We studied the properties and composition of brine inclusions from Ca- and F-rich rocks on the margin of the massif. Depending on the thermophysical properties of the host rocks and ongonite melt, the duration of its crystallization has been estimated for a magma chamber of the size and shape of the Ary-Bulak massif. Magma chamber cooling has been modeled, and the density, viscosity, and Rayleigh number of the ongonite melt have been estimated from the composition of silicate glasses in melt inclusions. These data strongly suggest intense convection in the residual magma chamber lasting for centuries. We have calculated possible fluid overpressure during the crystallization and degassing of the ongonite melt in a closed magma chamber.Calcium- and fluorine-rich aphyric and porphyritic rocks on the southwestern margin of the massif might have formed by the following mechanism. Local decompression in the magma chamber quenched an oxygen-containing calcium fluoride melt accumulated at the crystallization front, and then these rocks altered during the interaction with fluids. When penetrating the marginal zone, a P–Q magmatic fluid which coexisted with the melt in the residual chamber cooled and changed its composition and properties. This caused the fluid to boil and segregate into immiscible phases: a vapor solution and a brine extremely rich in Cl, F, K, Cs, Mn, Fe, and Al. The fluoride and silicate liquids were immiscible; the silicate melts had abnormal Cs and As contents; changes in the composition and properties of the magmatic fluids caused them to boil and produce brines. All this is evidence for complex fluid–magma interaction and heterogeneous ongonitic magma during the crystallization of the Ary-Bulak rocks. These processes were favored by the low viscosity and high mobility of the F- and water-rich ongonite melt, intense melt convection in the residual chamber, and rising fluid pressure during its degassing.     

Geochronology and geochemistry of the Nantianwan mafic–ultramafic complex,Emeishan large igneous province: metallogenesis of magmatic Ni–Cu sulphide deposits and geodynamic setting

The Nantianwan mafic–ultramafic complex is situated in the northwest part of the Panxi district, southwest China. It consists predominantly of gabbros, gabbronorites, and lherzolites. LA–ICP–MS U–Pb zircon dating of the gabbronorites yields an age of 259.7 ± 0.6 million years, consistent with the ages of other mafic–ultramafic intrusions in the Emeishan large igneous province (ELIP). Gabbronorites and lherzolites host Cu–Ni sulphide ores. Cumulus texture is pronounced in these rocks, containing magnesium-rich olivine (up to 81.4% forsterite). SiO₂ contents of the lherzolites range from 42.93 to 44.18 wt.%, whereas those of the gabbronorites vary between 44.89 and 52.76 wt.%. Analysed samples have low rare earth element (REE) contents (23.22–30.16 ppm for lherzolites and 25.21–61.05 ppm for gabbronorites). Both lherzolites and gabbronorites have similar chondrite-normalized REE patterns, suggesting that they are comagmatic. All samples are slightly enriched in large ion lithophile elements (LILEs, e.g. Rb, Ba, and Sr) relative to high field strength elements (HFSEs, e.g. Nb, Ta, and Ti), very similar to those of ocean island basalts (OIBs). The presence of cumulus textures and geochemical signatures indicates that fractional crystallization played an important role in the petrogenesis of these rocks. Initial (⁸⁷Sr/⁸⁶Sr) _t (t?=?260 Ma) ratios and ?_Nd(t) values of the mafic–ultramafic suite vary from 0.70542 to 0.70763, and??0.4 to 1.7, respectively. Compared to the Cu–Ni-bearing Baimazhai and Limahe intrusions in the ELIP, which were considerably contaminated by variable crustal materials, the Nantianwan complex exhibits much lower (⁸⁷Sr/⁸⁶Sr) _t . Their ?_Nd(t) versus (Th/Nb)_PM ratios also indicate that the ore-bearing magmas did not undergo significant crustal contamination. In combination with (Tb/Yb)_PM versus (Yb/Sm)_PM modelling, we infer that the magmas originated from an incompatible elements-enriched spinel-facies lherzolite that itself formed by interaction between the Emeishan plume and the lithospheric mantle. Most plots of NiO versus Fo contents of olivine suggest that sulphides are separated from the parental magma by liquid immiscibility, which is also supported by bulk-rock Cu/Zr ratios of the lherzolites (7.04–102.67) and gabbronorites (0.88–5.56). We suggest that the gabbronorites and lherzolites experienced undersaturation to oversaturation of sulphur; the latter may be due to fractional crystallization in a high-level magma chamber, accounting for the sulphide segregation.     

The mineralogy and chemical composition of the Woodlawn massive sulphide orebody

The main Woodlawn ore lens is a polymetallic, massive sulphide deposit’ with pyrite the major constituent, variable sphalerite, galena and chalcopyrite, and minor arsenopyrite, tetrahedrite‐tennantite, pyrrhotite and electrum. The silicate gangue minerals are chlorite, quartz, talc and sericitic mica. Other mineralization in the vicinity consists of footwall copper ore in chlorite schist and several smaller massive sulphide lenses. The predominant country rocks are felsic volcanics and shales, with abundant quartz, chlorite and mica, and talc in mineralized zones.

An important textural feature of the massive ore is the fine compositional banding. Bands, which vary in thickness from a few tens of micrometres to several millimetres, are produced by variations in the sulphide content. Post‐depositional metomorphism and minor fracturing have only slightly modified this banding.

Apart from the major element constituents—Pb, Zn, Fe, Cu and S—the ore is characterized by significant (100–1000 ppm) values for Ag, As, Cd, Mn, Sb and Sn, and lower (1–100 ppm) values of Au, Bi, Co, Ga, Hg, Mo, Ni, Tl. In and Ge. Variations in the base‐metal sulphide content, the gangue mineralogy, and trace elements, are used to separate the orebody into hanging‐wall and footwall zones. The hanging‐wall zone shows a more variable trace element content, with higher Tl, Sn, Ni, Mn, Ge and Sb, but lower Ag, Cd, and Mo, than the footwall zone.

In general style of mineralization, mineralogy, and chemistry, the Woodlawn deposit resembles other volcanogenic massive sulphide deposits in eastern Australia, in New Brunswick in Canada, and the Kuroko deposits of Japan.