Geochemistry and mineralogy of the Platreef and “Critical Zone” of the northern lobe of the Bushveld Complex, South Africa: implications for Bushveld stratigraphy and the development of PGE mineralisation

The northern lobe of the Bushveld Complex is currently a highly active area for platinum-group element (PGE) exploration. This lobe hosts the Platreef, a 10–300-m thick package of PGE-rich pyroxenites and gabbros, that crops out along the base of the lobe to the north of Mokopane (formerly Potgietersrus) and is amenable to large-scale open pit mining along some portions of its strike. An early account of the geology of the deposit was produced by Percy Wagner where he suggested that the Platreef was an equivalent PGE-rich layer to the Merensky Reef that had already been traced throughout the eastern and western lobes of the Bushveld Complex. Wagner’s opinion remains widely held and is central to current orthodoxy on the stratigraphy of the northern lobe. This correlates the Platreef and an associated cumulate sequence that includes a chromitite layer—known as the Grasvally norite-pyroxenite-anorthosite (GNPA) member—directly with the sequence between the UG2 chromitite and the Merensky Reef as it is developed in the Upper Critical Zone of the eastern and western Bushveld. Implicit in this view of the magmatic stratigraphy is that similar Critical Zone magma was present in all three lobes prior to the development of the Merensky Reef and the Platreef. However, when this assumed correlation is examined in detail, it is obvious that there are significant differences in lithologies, mineral textures and chemistries (Mg# of orthopyroxene and olivine) and the geochemistry of both rare earth elements (REE) and PGE between the two sequences. This suggests that the prevailing interpretation of the stratigraphy of the northern lobe is not correct. The “Critical Zone” of the northern lobe cannot be correlated with the Critical Zone in the rest of the complex and the simplest explanation is that the GNPA-Platreef sequence formed from a separate magma, or mixture of magmas. Chilled margins of the GNPA member match the estimated initial composition of tholeiitic (Main Zone-type) magma rather than a Critical Zone magma composition. Where the GNPA member is developed over the ultramafic Lower Zone, hybrid rocks preserve evidence for mixing between new tholeiitic magma and existing ultramafic liquid. This style of interaction and the resulting rock sequences are unique to the northern lobe. The GNPA member contains at least seven sulphide-rich horizons with elevated PGE concentrations. Some of these are hosted by pyroxenites with similar mineralogy, crystallisation sequences and Pd-rich PGE signatures to the Platreef. Chill zones are preserved in the lowest Main Zone rocks above the GNPA member and the Platreef and this suggests that both units were terminated by a new influx of Main Zone magma. This opens the possibility that the Platreef and GNPA member merge laterally into one another and that both formed in a series of mixing/quenching events involving tholeiitic and ultramafic magmas, prior to the main influx of tholeiitic magma that formed the Main Zone.     

Petrology, geochemistry and the mechanisms determining the distribution of platinum-group element and base metal sulphide mineralisation in the Platreef at Overysel, northern Bushveld Complex, South Africa

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.     

铂族元素在地壳中的富集:以布什维尔德杂岩为例

地幔是地壳铂族元素富集的主要源库。铂族元素迁移主要有两个途径:(1)地幔部分熔融物质侵入地壳;(2)地幔板片就位于俯冲/碰撞带。前一途径比后一途径重要得多。地幔物质进入地壳造成铂族元素富集并成为可供开采的主矿产而非副产品,这一过程可包含许多成矿作用机制:(i)基性侵入体中Ni-Cu硫化物矿浆的发育,岩浆冷却与分离结晶作用导致富含Cu,Pt,Pd的硫化物矿浆的形成;(ii)层状侵入体一定层位形成高品位的铂族元素硫化物层,伴生或不伴生铬铁岩;(iii)富铂族元素及硫化物的岩浆沿着层状侵入体的边缘就位;(iv)直至层状侵入体结晶分异作用晚期的硫化物不混溶滞后分离;(v)不发育硫化物不混溶作用的铬铁矿结晶作用;(vi)低程度硫化物浸染带中的热液作用与铂族元素富集;(vii)乌拉尔-阿拉斯加型侵入体重结晶过程中的铂族元素与铬铁矿的次生富集作用,岩体在风化过程中形成砂矿床;(viii)黑色页岩形成过程中Pt的富集。南非布什维尔德火成杂岩蕴藏世界Pt资源的75%,Pd资源的54%,Rh资源的82%,并具有(ii)、(iii)、(iv)、(v)、(vi)成矿作用的实例。在这些作用中,作用(ii)形成的现有经济储量和资源量占90%,作用(iii)占9%。Merensky矿层(占总资源量30%)是一个铂族元素富集层位,它含1~3铬铁矿薄层,在可采宽度内硫化物平均含量为1%~3%(质量分数)。硫化物一般被认为是铂族元素的主要聚集体。该矿层由两个或两个以上含硫化物的基性热岩浆上升汇聚而成。这些岩浆的汇聚造成超镁铁质堆晶岩的厚度(主要是斜方辉石岩,某些地区包括橄榄岩)变化于50cm至数米之间。开采通常集中在厚度不到1m的地带。矿层的成因至今仍存在争议,一些观点认为铂族元素来自下部上升的热液流体,另一些观点认为铂族元素来自上部岩浆的硫化物沉降作用,并形成了Merensky辉石岩。已经知道矿层上覆的辉石岩、苏长岩和斜长岩中矿物来自两种岩浆类型:一种富含MgO(12%,质量分数)和Cr,而贫Al2O3(12%);另一种含典型的粒玄岩成分。UG-2铬铁岩含有全部经济资源量的58%,由一0.6~1m厚的铬铁岩层(有时见辉石岩夹层)和上覆的1~3层由铬铁矿所构成的薄层。虽然硫化物被认为至少是某些情况下对铂族元素的富集起作用,但UG-2的硫化物含量(0.5%~1.5%)显著低于Merensky矿层。UG-2层之下共有13个铬铁岩层位,所有的都含铂族元素,虽然铂族元素总含量和(Pt+Pd)/(Ru+Ir+Os)比值远低于UG-2。UG-2内所含的辉石岩"夹层"具高的87Sr/86Sr比值,说明与顶部熔融岩石的混合促进了铬铁岩和硫化物的形成。作用(iii)的主要实例是Platreef。目前它占总资源量的9%。不过,沿该带正积极开展找矿勘探工作,这一比例将来还会提高。这一矿层的厚度比Merensky和UG-2都要大,目前开采厚度达50多米。Platreef呈带状,上部为斜方辉石岩的堆晶岩;下部为辉石岩、长石辉石岩和苏长岩,它们与页岩、铁矿层和白云岩强烈相互作用,直接形成了底盘岩石。笔者认为Platreef是不同期次岩浆作用的结果,这些作用形成了不同的单元产物,包括布什维尔德主岩浆房的UG-2和Merensky矿层。新的岩浆进入主岩浆房会造成先存岩浆移位、岩浆错动并会冲破岩浆房的壁。圆筒状、带状岩管中的超镁铁岩含极高的Pt品位,在布什维尔德杂岩的下部切穿堆晶层,被认为是热液再活化的产物。它们现在未被开采,只是构成存封的铂族元素资源,对整个杂岩体资源没有重要的贡献。     

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.     

Precious and base metal geochemistry and mineralogy of the Grasvally Norite–Pyroxenite–Anorthosite (GNPA) member,northern Bushveld Complex,South Africa: implications for a multistage emplacement

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.     

Trace Element and Platinum Group Element Distributions and the Genesis of the Merensky Reef, Western Bushveld Complex, South Africa

The Merensky Reef of the Bushveld Complex is one of the world'slargest resources of platinum group elements (PGE); however,mechanisms for its formation remain poorly understood, and manycontradictory theories have been proposed. We present precisecompositional data [major elements, trace elements, and platinumgroup elements (PGE)] for 370 samples from four borehole coresections of the Merensky Reef in one area of the western BushveldComplex. Trace element patterns (incompatible elements and rareearth elements) exhibit systematic variations, including small-scalecyclic changes indicative of the presence of cumulus crystalsand intercumulus liquid derived from different magmas. Ratiosof highly incompatible elements for the different sections areintermediate to those of the proposed parental magmas (CriticalZone and Main Zone types) that gave rise to the Bushveld Complex.Mingling, but not complete mixing of different magmas is suggestedto have occurred during the formation of the Merensky Reef.The trace element patterns are indicative of transient associationsbetween distinct magma layers. The porosity of the cumulatesis shown to affect significantly the distribution of sulphidesand PGE. A genetic link is made between the thickness of theMerensky pyroxenite, the total PGE and sulphide content, petrologicaland textural features, and the trace element signatures in thesections studied. The rare earth elements reveal the importantrole of plagioclase in the formation of the Merensky pyroxenite,and the distribution of sulphide. KEY WORDS: Merensky Reef; platinum group elements; trace elements     

Pressure fluctuations and the formation of the PGE-rich Merensky and chromitite reefs, Bushveld Complex

The Merensky Reef and the underlying Upper Group 2 chromitite layer, in the Critical Zone of the Bushveld Complex, host much of the world’s platinum-group element (PGE) mineralization. The genesis is still debated. A number of features of the Merensky Reef are not consistent with the hypotheses involving mixing of magmas. Uniform mixing between two magmas over an area of 150 by 300 km and a thickness of 3–30 km seems implausible. The Merensky Reef occurs at the interval where Main Zone magma is added, but the relative proportions of the PGE in the Merensky Reef are comparable to those of the Critical Zone magma. Mineral and isotopic evidence in certain profiles through the Merensky Unit suggest either mixing of minerals, not magmas, and in one case, the lack of any chemical evidence for the presence of the second magma. The absence of cumulus sulphides immediately above the Merensky Reef is not predicted by this model. An alternative model is proposed here that depends upon pressure changes, not chemical processes, to produce the mineralization in chromite-rich and sulphide-rich reefs. Magma was added at these levels, but did not mix. This addition caused a temporary increase in the pressure in the extant Critical Zone magma. Immiscible sulphide liquid and/or chromite formed. Sinking sulphide liquid and/or chromite scavenged PGE (as clusters, nanoparticles or platinum-group minerals) from the magma and accumulated at the floor. Rupturing of the roof resulted in a pressure decrease and a return to sulphur-undersaturation of the magma.     

Crustal Contamination and Fluid-Rock Interaction during the Formation of the Platreef, Northern Limb of the Bushveld Complex, South Africa

The Platreef is the main platinum group element (PGE)-bearingfacies of the northern limb of the Bushveld complex, but unlikethe Merensky Reef of the eastern and western limbs, it is indirect contact with the country rock. Mineral separate     

The Merensky Cyclic Unit and its impact on footwall cumulates below Normal and Regional Pothole reef types in the Western Bushveld Complex

The Merensky Reef of the Bushveld Complex occurs in its highest stratigraphic position as a heterogeneous, pegmatitic, feldspathic melanorite bounded by two narrow chromitite stringers at the base of the Merensky Cyclic Unit (MCU). In the Swartklip Facies of the Rustenburg Layered Suite, the occurrence of widespread thermal and mechanical erosion termed “potholing” has led to the subdivision of the Merensky Reef into Normal Reef and Regional Pothole Reef sub-facies. The transition between the two sub-facies occurs where the MCU transgresses the lower chromitite stringer of the Normal Merensky Reef and cuts down into the underlying cumulate lithologies. In the Regional Pothole Reef at the Northam Platinum Mine, several economic reef types are identified, where the Merensky Reef becomes conformable to cumulate layering, in particular, to the footwall marker (NP2 reef type) and the upper pseudoReef (P2 reef type). The Normal Merensky Reef, as well as the P2 and NP2 Reefs, contains economic platinum group element (PGE) grades and includes the lower portion of the MCU melanorite and the Merensky Chromitite. Whole rock geochemistry indicates that this package is compositionally identical in Normal, P2, and NP2 Reefs, suggesting that the base of the MCU is a relatively homogeneous drape over both Normal and Regional Pothole Reef regions. However, the lower sections of the three Reefs are variables depending on the depth of transgression of the MCU. In the Normal and P2 reef types, transgression by the MCU was arrested within harzburgites, melanorites, and norites, resulting in coarse, pegmatitic textures in the immediate footwall units. For the NP2 Reef, transgression by the MCU was arrested within leucocratic rocks and resulted in the formation of troctolites below the Merensky Chromitite. These troctolites are characterised by a coupled relationship between olivine and sulphides and by changes in major element chemistry and PGE contents relative to equivalent units in the footwall of the Normal Reef. Along with micro-textural relationships, these features suggest that troctolization of leucocratic cumulates in the NP2 Reef beneath the Merensky chromitite was a result of a reactive infiltration of a chromite-saturated melt and an immiscible sulphide liquid from the overlying MCU, rather than a significant fluid flux from below. In all reef types, the concentration of S defines symmetrical peaks centred on the Merensky Chromitite (and chromitites from pre-existing cyclic units in Normal and P2 Reefs), whereas PGE concentrations define asymmetrical peaks with higher PGE contents in reconstituted footwall rocks relative to the MCU melanorite. This signature is attributable to a magmatic model of PGE collection followed by deposition towards the base of the MCU and within reconstituted footwall rocks. The continuity of the asymmetrical magmatic PGE signature between the Normal Reef and Regional Pothole Reef sub-facies indicates that PGE mineralization inherent to the Merensky magma occurred as a drape over a variably eroded and subsequent texturally and geochemically reworked or reconstituted footwall.     

The petrogenesis of Merensky Reef potholes at the Western Platinum Mine, Bushveld Complex: Sr-isotopic evidence for synmagmatic deformation

Potholes represent areas where the normally planar PGE-rich Merensky Reef of the upper Critical Zone of the Bushveld Complex transgresses its footwall, such geometric relationships being unusual in layered intrusions. The recognition of vertical dykes of Merensky pyroxenite in the footwall suggests downward collapse of crystal mush into pull-apart sites resulting from tensional deformation due to the loading effects of major new magma additions. In contrast, crosscutting anorthosite veins display physical and isotopic evidence of upward emplacement. The Merensky Reef and its footwall have distinct initial Sr-isotope ratios (R ₀ > 0.7066 and <0.7066, respectively), which may be used to constrain these processes related to pothole formation. Merensky Reef in potholes (R ₀ = 0.7069−0.7078) shows no isotopic evidence of assimilation of, or reaction with, footwall material. Discrete, discordant replacement bodies of anorthosite extend from the footwall lithologies to cross-cut the Merensky Reef and its hanging wall. The initial Sr-isotope ratio in these replaced rocks is totally reset to footwall values (R ₀ = 0.7066), and immediately adjacent stratiform lithologies are slightly modified towards footwall values. In contrast, Neptunian pyroxenitic (Merensky) dykes cross-cutting the footwall lithologies, with a large surface area to volume ratio, and low Sr content, do not display footwall-like Sr-isotope initial-ratios (R ₀ = 0.7077), and thus show no evidence for assimilation of or reaction with footwall material. Furthermore, pegmatoidal replacement pyroxenite (“replacement pegmatoid”), at the base of the Merensky Reef within potholes, has a high initial-ratio (R ₀ > 0.7071), and so models of pervasive metasomatism by footwall material are not applicable. This isotopic evidence indicates that there was no active interaction of footwall material with the overlying magma during, or after, the formation of Merensky Reef potholes, a basic tenet of existing pothole formation hypotheses involving footwall mass-transfer. In contrast, the isotopic data are entirely consistent with an extensional model for pothole formation, with the more radiogenic Merensky magma migrating laterally to fill extensional zones in the footwall layers. Received: 11 October 1997 / Accepted: 21 December 1998     

Platinum-group element (PGE) deposits and occurrences: Mineralization styles,genetic concepts,and exploration criteria

PGE mineralization has been identified in various rock types and at various stratigraphic levels in layered intrusions of any age, size and magmatic lineage, but the most important deposits occur as relatively narrow stratiform reefs in the lower to central ultramafic–mafic portions of large tholeiitic intrusions of late Archean to early Proterozoic age. One of the main challenges in exploration is that the reefs tend to be sulfide-poor. In many chromitites, magnetitites and silicate-hosted ores, the rocks contain no visible sulfides, possibly due to (late) magmatic sulfide resorption. As a result, some deposits may have been overlooked, particularly those in the upper portions of the intrusions that were in the past considered to be relatively unprospective. Amongst lithogeochemical tools, Cu/Pd ratios have proven to be particularly useful to evaluate the PGE potential of intrusions and to delineate the position of the reefs within the intrusions.The origin of the PGE mineralization remains controversial. A possible explanation for the low sulfide contents of many PGE-rich intrusions is that most of their parental magmas were strongly undersaturated in sulfur and at least partially derived from the S-poor and PGE-enriched sub-continental lithospheric mantle. Sulfide saturation upon emplacement in the crust may have been reached during differentiation. Empirical evidence supports theoretical considerations that chromite and magnetite precipitation may be particularly conducive to trigger sulfide melt saturation, due to a pronounced decrease in FeO content of the magma. The importance of magma mixing in triggering sulfide supersaturation remains unclear. The same applies to contamination; some intrusions show a distinct crustal component, but many others do not, and there is little if any correlation between sulfide content and crustal component. Together with the general paucity of sulfides in the intrusions this could suggest that contamination is not critical in reef formation and may indeed be a negative factor.Other processes may also be relevant to reef formation. Data from the well-studied Bushveld Complex suggest that the magmas had reached sulfide saturation prior to emplacement, and that sulfides were entrained in the magma during ascent and emplacement. Sulfide entrainment has previously been recognised as one of the key factors in the formation of massive Ni–Cu sulfide deposits, and it is suggested here that it is also relevant to the formation of PGE deposits.     

Enrichment of Platinum-group Elements (PGE) and Re-Os Isotopic Tracing for Porphyry Copper (Gold) Deposits

Platinum-group elements （PGE） in PGE-rich porphyry copper （gold） deposits are mainly Pt and Pd, whereas the concentrations of other PGE （Ru, Rh, Os, Ir） are significantly low. Moreover, Pt and Pd mainly exist in sulfides in the forms of crystal lattice or tiny platinum-group mineral （PGM） inclusions. The present data show that there is a positive relationship between Pt and Pd concentrations and Cu （Au） in porphyry copper （gold） deposits. The comparison of chondrite-normalized PGE distribution patterns between the ore-bearing porphyry intrusions and ore-barren porphyry intrusions in arc setting, 187^Os/188^Os, 87^Sr/86^Sr and S isotopes for porphyry copper （gold） deposits shows that PGEs were mainly derived from the mantle, and fluids from subduction zones devoted trivial PGE to the magma. The porphyry copper （gold） deposits associated with subducted events are most probably enriched in PGE, whereas those related to crustal thickening, lithospheric delamination or underplating rarely concentrate PGE. The osmium isotopic compositions in porphyry copper （gold） deposits reveal that （187^Os/188^Os）i values are highly variable and not lower than those of primitive upper mantle （PUM） and mantle peridotite, however, osmium concentrations are commonly lower than mantle peridotite, suggesting that parental magmas of some porphyry intrusions had experienced crustal contamination during magma evolution. Experimental investigations have proved that PGE exist in the forms of Cl^- and HS^- complexes during transportation and migration of the oreforming fluids. This paper summarizes previous studies including crucial controlling factors and mechanisms for PGE enrichment, and points out that the mantle-derived magmas parental to porphyry intrusions are the prerequisite for PGE enrichment in porphyry copper （gold） deposits. Favorable physical and chemical conditions （including salinity, temperature, pressure, pH, and oxygen fugacity） in hydrothermal fluids crucially control the     

Noble Metal Enrichment Processes in the Merensky Reef, Bushveld Complex

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     

Precious metal enrichment in the Platreef,Bushveld Complex,South Africa: evidence from homogenized magmatic sulfide melt inclusions

Magmatic sulfide deposits are the most significant source of platinum-group elements (PGE) in the world. Key to understanding their genesis is determining the processes and timing of sulfide saturation, metal enrichment and crustal contamination. In this study, we have identified droplets of magmatic sulfide from the Platreef, South Africa, where droplets of sulfide have been trapped in the earliest crystallising phase, chromite. Due to their early entrapment at high temperatures, metal concentrations and ratios that they display are indicative of a very early-stage sulfide liquid in the system, as they will have cooled and fractionated within an essentially closed system, unlike interstitial blebs that crystallise in an open system as the magma cools. Analysis of these droplets in an opaque mineral like chromite by LA-ICP-MS is problematic as some of the fractionated inclusion is necessarily lost during cutting and polishing to initially identify the inclusion. This particularly affects the ability to representatively sample the most fractionated phases such as gold and platinum minerals. Here, using a novel technique whereby the inclusions are homogenized and quickly quenched, so that any cutting, polishing and subsequent LA-ICP-MS analysis samples a truly representative portion of the droplet. This has been used to show that early sulfide liquids in the Platreef were highly PGE-rich and had Pt/Pd ratios of close to unity that supports genetic models invoking sulfide saturation and metal enrichment prior to intrusion, with pre-enriched sulfides entrained within the Platreef magma.     

The geology and structure of the Rustenburg Layered Suite in the Potgietersrus/Mokopane area of the Bushveld Complex,South Africa

A new geological map of the Rustenburg Layered Suite south of the Ysterberg–Planknek fault of the northern/Potgietersrus limb of the Bushveld Complex is presented, displaying features that were not available for publication in the past and are considered contributing to the complexity of this region. The northern limb is known for the Platreef, atypical mafic lithologies in sections of the layered sequence and the unusual development of the ultramafic Lower Zone as satellite bodies or offshoots at the base of the intrusion. The outcrop and suboutcrop pattern of Lower Zone Grasvally body and its relation to the surrounding geology of Main Zone, Critical Zone, and floor rocks is described. The extent of the base metal sulfide (BMS) and platinum-group element (PGE)-mineralized cyclic unit 11 of the Drummonlea harzburgite–chromitite sub zone is shown. Only that which is considered to be the equivalents of the mafic Upper Critical Zone has thus far been traced south of Potgietersrus/Mokopane. The Platreef is traced from the farm Townlands and further northwards. The presence of Platreef proper south of Potgietersrus/Mokopane appears to be speculative. However, Merensky Reef, UG 2, and equivalent layers outcrop or were intersected to the south of the town. The Kleinmeid Syncline comprising Main Zone/Critical Zone layers and its structure is discussed. The lateral lithological transfomation of the Merensky Reef/UG 2 and equivalent layers south of the Ysterberg–Planknek fault to Platreef north of this fault is recorded. Attenuation of both the Main Zone and Upper Zone is observed from the northwest towards the town and resulted in only the lower units being developed. The lateral change of Main Zone and Upper Zone lithologies from the northwest towards the town is described. The PGE and BMS economic potential south of the town are briefly tabulated.     

Element mapping the Merensky Reef of the Bushveld Complex

The Merensky Reef hosts one of the largest PGE resources globally.It has been exploited for nearly 100 years, yet its origin remains unresolved.In the present study, we characterised eight samples of the reef at four localities in the western Bushveld Complex using micro-X-ray fluorescence and field emission scanning electron microscopy.Our results indicate that the Merensky Reef formed through a range of diverse processes.Textures exhibited by chromite grains at the base of the reef are consistent with supercooling and in situ growth.The local thickening of the Merensky chromitite layers within troughs in the floor rocks is most readily explained by granular flow.Annealing and deformation textures in pyroxenes of the Merensky pegmatoid bear testament to recrystallisation and deformation.The footwall rocks to the reef contain disseminations of PGE rich sulphides as well as olivine grains with peritectic reaction rims along their upper margins suggesting reactive downward flow of silicate and sulphide melts.Olivine-hosted melt inclusions containing Cl-rich apatite, sodic plagioclase, and phlogopite suggest the presence of highly evolved, volatile-rich melts.Pervasive reverse zonation of cumulus plagioclase in the footwall of the reef indicates dissolution or partial melting of plagioclase, possibly triggered by flux of heat, acidic fluids, or hydrous melt.Together, these data suggest that the reef formed through a combination of magmatic, hydrodynamic and hydromagmatic processes.     

Trace-element study and age dating of zircon from chromitites of the Bushveld Complex (South Africa)

The layered Bushveld Complex hosts a number of chromitite layers, which were found to contain significant amounts of zircon grains compared with adjacent silicate rocks. Cathodoluminescent-dark, partially metamict cores and transparent rims of composite zircon grains were analyzed for trace elements with SIMS and LA-ICPMS techniques. The cores are enriched in REE, Y, Th and U and are characterized by distinctly flatter REE patterns in contrast to those of the rims and transparent homogenous crystals. Zircon from the different stratigraphic units has specific Th/U ratios, the highest of which (1.5–4) occurs in a Merensky Reef zircon core. The Ti content of Bushveld zircon ranges from 12 to 52 ppm correlating to a crystallization temperature range of 760–930 °C. The geochemical characteristics of the first zircon generation are consistent with its high-temperature crystallization as the first major U, Th and REE acceptor from a highly-evolved residue of the high-Mg basalt magma, whereas the rims and coreless crystals have crystallized from percolating intercumulus liquid of new influx of the same magma. U-Pb SHRIMP dating of zircon cores and rims does not reveal a distinguishable difference between their ages indicating the absence of inherited zircon. Concordia ages of 2,051?±?9 Ma (2σ, MSWD?=?0.1) and 2,056?±?5 Ma (2σ, MSWD?=?0.05) for zircons from the Merensky Reef and the Upper Platreef located equally near the top of the Critical Zone are in agreement with published ages for the Merensky Reef. Zircon from the deeper-seated Lower Group, Middle Group and Lower Platreef chromitites yields younger concordia ages that may reflect prolonged late-stage volatile activity.     

Platinum-group element distribution in base-metal sulfides of the Merensky Reef from the eastern and western Bushveld Complex, South Africa

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.     

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     

Laser ablation ICP-MS study of platinum-group elements in sulphides from the Platreef at Turfspruit,northern limb of the Bushveld Complex,South Africa

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.