Trace and platinum-group element geochemistry and the development of the Merensky unit of the Western Bushveld complex

Whole-rock samples of the Merensky Unit were analysed for major elements, Cu, Ni, Cr, Co, Eu, Th, U, Cs, and the platinum-group elements Pt, Pd, Rh, Ir and Au. There is a sympathetic variation of Cu, Ni, Co, and S throughout the sequence. Th and U abundances are highest around the Merensky Reef, and their distribution in the rest of the unit reflects the amount of mesostasis. Eu distribution is governed by primary plagioclase. Pt, Pd, Rh, Ir and Au (PM) are concentrated in the Merensky Reef. The relative proportions throughout the unit are Ir2 enrichment trends; interaction of these trends resulted in the Merensky Reef and its attendant mineralization.     

Crustal contamination and PGE mineralization in the Platreef,Bushveld Complex,South Africa: evidence for multiple contamination events and transport of magmatic sulfides

Diamond drill core traverses across the Platreef were carried out at Tweefontein, Sandsloot, and Overysel in order to establish the relationship between crustal contamination and platinum group element (PGE) mineralization. The footwall rocks are significantly different at each of these sites and consist of banded iron formation and sulfidic shales at Tweefontein, of carbonates at Sandsloot, and of granites and granite gneisses at Overysel. As demonstrated in this study, Platreef rocks are characterized by two stages of crustal contamination. The first contamination event occurred prior to emplacement of the magma and is present in Platreef rocks at all three sites, as well as in the Merensky Reef. This event is readily identified on trace element spidergrams and trace element ratio scattergrams. The second contamination event was induced by interaction of the Platreef magma with the local footwall rocks. It is most easily identified at Tweefontein, where there is a large increase in the FeO content of the Platreef rocks, and at Sandsloot, where there is a large increase in their CaO and MgO contents, relative to Bushveld rocks that are uncontaminated by the local footwall rocks. At Overysel, the second contamination event did not result in pronounced changes in the major element composition of the Platreef rocks, but can be detected in their trace element chemistry. A strong inverse relationship between PGE tenors and S/Se ratios is interpreted to suggest that the PGE-rich sulfides were formed prior to emplacement of the Platreef magmas through assimilation of crustal S and became progressively enriched in the PGE during transport. Rather than promoting S-saturation, interaction of the Platreef magma with the footwall rocks diluted the metal tenors of the sulfides. Although both the Platreef and the Merensky Reef magmas were contaminated by the same crustal contaminant and were probably PGE-rich, they have radically different Pd/Pt ratios. Their Pd/Pt ratios suggest that whereas the Merensky Reef magma became PGE-rich due to dissolution of PGE-rich sulfides segregated from a pre-Merensky magma that had undergone relatively little fractionation prior to reaching S-saturation, the pre-Platreef magma had undergone greater fractionation prior to the sulfide saturation event, thereby increasing its Pd/Pt ratio. We suggest that the magmas that formed the Platreef and Merensky Reef may have simply been carrier magmas for sulfides that had formed elsewhere in the plumbing system of the Bushveld Complex by the interaction of earlier generations of magmas with the crustal rocks that underlie the Complex.     

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     

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     

南非西布什维尔德杂岩体铂、钯、金区域地球化学测量

利用南非勒斯滕堡地区区域地球化学测量水系沉积物和土壤样品,采用化学光谱法测定Pt、Pd和Au三种元素,对该区布什维尔德杂岩体铂、钯和金进行区域地球化学勘查,发现新的铂族矿(带)异常,在主带上部和上部带底部发现新的Pt、Pd和Au的异常带。     

Platinum mineralogy of the driekop mine,South Africa

A detailed microprobe and optical investigation of concentrates from the Driekop platinum mine, South Africa, has resulted in significant additions to, and modifications of, data which one of us (E. F. Stumpfl) has presented in 1961. The concentrates contain 50% iron-bearing platinum, 30% sperrylite (PtAs₂) and geversite (PtSb₂), 15% hollingworthite (RhAsS) and irarsite (IrAsS) and 5% of other platinum group minerals. Two new minerals, (Pt, Pd) (Bi, Sb) and (Pt, Pd)₃Sb₂ have been discovered in the course of this work. Spectral reflectance and microhardness data are given for eight platinum group minerals. The list of new minerals presented in 1961 has been included in Cabri's tabulations (1972). It should now been modified as follows: a phase of composition Pt(Ir, Os)₂As₄ does not exist, the mineral in question is irarsite, frequently associated with hollingworthite. Pd₈CuSb₃ is not a separate mineral species but copper-bearing stibiopalladinite, PtSb is actually (Pt, Pd)₃Sb₂. The Driekop platinum group minerals association is dominated by native platinum, arsenides, antimonides and sulpharsenides. Bismutho-tellurides, which play a significant rôle in the Merensky Reef, have not been detected. Transport and deposition of the platinum group elements is ascribed to the high-temperature aqueous fluids which have formed the dunite pipes.     

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 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.     

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.     

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.     

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。     

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     

河北红石砬铂矿床铂、钯地球化学异常特征

红石砬铂矿地球化学异常组分简单,仅发育Ｐｔ和Ｐｄ的强异常,部分伴生Ａｕ异常,不伴生Ｃｒ、Ｃｏ、Ｃｕ、Ｎｉ、Ｖ、Ａｓ、Ｓｂ、Ａｇ、Ｐｂ等元素异常。岩石、土壤、水系沉积物中Ｐｔ、Ｐｄ的分布和异常模式与铂族矿化特征、矿体剥蚀程度及其表生地球化学行为等有关。矿体出露地表时,Ｐｔ、Ｐｄ呈强异常分布,异常的ｗ（Ｐｔ）／ｗ（Ｐｄ）比值与矿石中ｗ（Ｐｔ）／ｗ（Ｐｄ）比率基本一致;隐伏矿体上方,Ｐｄ有明显的浓集,ｗ（Ｐｔ）／ｗ（Ｐｄ）比值小于地表矿体。表生环境中,Ｐｔ、Ｐｄ可以呈矿物碎屑、可溶态等多种形式迁移,在疏松沉积物中形成异常。因此,以Ｐｔ、Ｐｄ作为直接指示元素,进行地球化学勘查,可以发现这种类型的铂族矿床。     

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.     

Platinum-Group Elements in Sulphide Minerals, Platinum-Group Minerals, and Whole-Rocks of the Merensky Reef (Bushveld Complex, South Africa): Implications for the Formation of the Reef

The concentrations of platinum-group elements (PGE), Co, Re,Au and Ag have been determined in the base-metal sulphide (BMS)of a section of the Merensky Reef. In addition we performeddetailed image analysis of the platinum-group minerals (PGM).The aims of the study were to establish: (1) whether the BMSare the principal host of these elements; (2) whether individualelements preferentially partition into a specific BMS; (3) whetherthe concentration of the elements varies with stratigraphy orlithology; (4) what is the proportion of PGE hosted by PGM;(5) whether the PGM and the PGE found in BMS could account forthe complete PGE budget of the whole-rocks. In all lithologies,most of the PGE (65 up to 85%) are hosted by PGM (essentiallyPt–Fe alloy, Pt–Pd sulphide, Pt–Pd bismuthotelluride).Lesser amounts of PGE occur in solid solution within the BMS.In most cases, the PGM occur at the contact between the BMSand silicates or oxides, or are included within the BMS. Pentlanditeis the principal BMS host of all of the PGE, except Pt, andcontains up to 600 ppm combined PGE. It is preferentially enrichedin Pd, Rh and Co. Pyrrhotite contains, Rh, Os, Ir and Ru, butexcludes both Pt and Pd. Chalcopyrite contains very little ofthe PGE, but does concentrate Ag and Cd. Platinum and Au donot partition into any of the BMS. Instead, they occur in theform of PGM and electrum. In the chromitite layers the whole-rockconcentrations of all the PGE except Pd are enriched by a factorof five relative to S, Ni, Cu and Au. This enrichment couldbe attributed to BMS in these layers being richer in PGE thanthe BMS in the silicate layers. However, the PGE content inthe BMS varies only slightly as a function of the stratigraphy.The BMS in the chromitites contain twice as much PGE as theBMS in the silicate rocks, but this is not sufficient to explainthe strong enrichment of PGE in the chromitites. In the lightof our results, we propose that the collection of the PGE occurredin two steps in the chromitites: some PGM formed before sulphidesaturation during chromitite layer formation. The remainingPGE were collected by an immiscible sulphide liquid that percolateddownward until it encountered the chromitite layers. In thesilicate rocks, PGE were collected by only the sulphide liquid. KEY WORDS: Merensky Reef; Rustenburg Platinum Mine; sulphide; platinum-group elements; image analysis; laser ablation ICP-MS     

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.     

Mobilisation of traffic-derived trace metals from road corridors into coastal stream and estuarine sediments,Cairns, northern Australia

This investigation revealed the presence of traffic-derived metals within road, stream and estuarine sediments collected from a coastal catchment, northern Australia. Studied road sediments displayed variable total metal concentrations (median Cd, Cu, Pb, Pd, Pt, Ni and Zn values: 0.19, 42.6, 67.5, 0.064, 0.104, 36.7 and 698 mg/kg, respectively). The distinctly elevated Zn values are due to abundant tyre rubber shreds (as verified by SEM-EDS and correlation analysis). By comparison to the road sediments, background stream sediments taken upstream from roads have relatively low median Pb, Pd, Pt and Zn concentrations (7.3 mg/kg Pb, 0.01 mg/kg Pd, 0.012 mg/kg Pt, 62 mg/kg Zn). Stream and estuarine sediment samples collected below roads have median values of 21.8 mg/kg Pb, 0.014 mg/kg Pd, 0.021 mg/kg Pt and 71 mg/kg Zn, and exhibit ²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb ratios that appear on a mixing line between the isotopically distinct background stream sediments and the road sediments. Thus, mobilisation of dusts and sediments from road surfaces has resulted in relatively elevated Pb, Pd, Pt and Zn concentrations and non-radiogenic Pb isotope ratios in local coastal stream and estuarine sediments. The investigation demonstrates that traffic-derived metals enter coastal stream and estuary sediments at the fringe of the Great Barrier Reef lagoon.     

3-D Distribution of Sulphide Minerals in the Merensky Reef (Bushveld Complex, South Africa) and the J-M Reef (Stillwater Complex, USA) and their Relationship to Microstructures Using X-Ray Computed Tomography

Large mafic–ultramafic layered intrusions may containlayers enriched in platinum-group elements (PGE). In many cases,the PGE are hosted by disseminated sulphides. We have investigatedthe distribution of the sulphides in three dimensions in twooriented samples of the Merensky Reef and the J-M Reef. Theaim of the study was to test the hypothesis that the sulphidescrystallized from a base metal sulphide liquid that percolatedthrough the cumulate pile during compaction. The distributionof sulphides was quantified using: (1) X-ray computed tomography;(2) microstructural analysis of polished thin sections orientedparallel to the paleovertical; (3) measurement of dihedral anglesbetween sulphides and silicates or oxides. In the Merensky Reefand the J-M Reef, sulphides are connected in three dimensionsand fill paleovertical dilatancies formed during compaction,which facilitated the downward migration of sulphide liquidin the cumulate. In the melanorite of the Merensky Reef, thesulphide content increases from top to bottom, reaching a maximumvalue above the underlying chromitite layer. In the chromititelayers sulphide melt connectivity is negligible. Thus, the chromititemay have acted as a filter, preventing extensive migration ofsulphide melt downwards into the footwall. This could partiallyexplain the enrichment in PGE of the chromitite layer and theobserved paucity of sulphide in the footwall. KEY WORDS: X-ray computed tomography; microstructures; sulphides; Merensky Reef; J-M Reef     

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.     

Cooperite and braggite from the Bushveld Complex: implications for the miscibility gap and identification

Analyses of the Pt-Pd-Ni sulphides cooperite, braggite, and vysotskite reported from worldwide occurrences seem to imply a continuum of compositions between vysotskite and cooperite, with no obvious miscibility gap. This is contrary to the experimentally confirmed miscibility gap between cooperite and braggite, and the established compositional gap between co-existing cooperite and braggite from the Merensky Reef. Although the only unambiguous way of distinguishing between cooperite and braggite is to obtain structural information through X-ray diffraction or equivalent techniques, most identification of Pt-Pd-Ni sulphides is based on microanalytical techniques due to the small grain size of most platinum-group minerals. Ni contents also have to be considered because a classification based on the Pt/Pd ratio alone can be very misleading. Naming of Pt-Pd-Ni sulphide compositions with high Pt contents based on qualitative or semi-quantitative analyses should be avoided. Natural Pt-Pd-Ni sulphides which project into the compositional gap (established by experimental work) cannot be named without supporting structural information. Compositions of grains, which plot inside the gap, are considered to be metastable and to result from the loss of Pd through interaction with hydrothermal fluids.