Origin of the UG2 chromitite layer, Bushveld Complex

Chromitite layers are common in large mafic layered intrusions.A widely accepted hypothesis holds that the chromitites formedas a consequence of injection and mixing of a chemically relativelyprimitive magma into a chamber occupied by more evolved magma.This forces supersaturation of the mixture in chromite, whichupon crystallization accumulates on the magma chamber floorto form a nearly monomineralic layer. To evaluate this and othergenetic hypotheses to explain the chromitite layers of the BushveldComplex, we have conducted a detailed study of the silicate-richlayers immediately above and below the UG2 chromitite and anotherchromitite layer lower in the stratigraphic section, at thetop of the Lower Critical Zone. The UG2 chromitite is well knownbecause it is enriched in the platinum-group elements and extendsfor nearly the entire 400 km strike length of the eastern andwestern limbs of the Bushveld Complex. Where we have studiedthe sequence in the central sector of the eastern Bushveld,the UG2 chromitite is embedded in a massive, 25 m thick plagioclasepyroxenite consisting of 60–70 vol. % granular (cumulus)orthopyroxene with interstitial plagioclase, clinopyroxene,and accessory phases. Throughout the entire pyroxenite layerorthopyroxene exhibits no stratigraphic variations in majoror minor elements (Mg-number = 79·3–81·1).However, the 6 m of pyroxenite below the chromitite (footwallpyroxenite) is petrographically distinct from the 17 m of hangingwall pyroxenite. Among the differences are (1) phlogopite, K-feldspar,and quartz are ubiquitous and locally abundant in the footwallpyroxenite but generally absent in the hanging wall pyroxenite,and (2) plagioclase in the footwall pyroxenite is distinctlymore sodic and potassic than that in the hanging wall pyroxenite(An_45–60 vs An_70–75). The Lower Critical Zone chromititeis also hosted by orthopyroxenite, but in this case the rocksabove and below the chromitite are texturally and compositionallyidentical. For the UG2, we interpret the interstitial assemblageof the footwall pyroxenite to represent either interstitialmelt that formed in situ by fractional crystallization or chemicallyevolved melt that infiltrated from below. In either case, themelt was trapped in the footwall pyroxenite because the overlyingUG2 chromitite was less permeable. If this interpretation iscorrect, the footwall and hanging wall pyroxenites were essentiallyidentical when they initially formed. However, all the modelsof chromitite formation that call on mixing of magmas of differentcompositions or on other processes that result in changes inthe chemical or physical conditions attendant on the magma predictthat the rocks immediately above and below the chromitite layersshould be different. This leads us to propose that the Bushveldchromitites formed by injection of new batches of magma witha composition similar to the resident magma but carrying a suspendedload of chromite crystals. The model is supported by the commonobservation of phenocrysts, including those of chromite, inlavas and hypabyssal rocks, and by chromite abundances in lavasand peridotite sills associated with the Bushveld Complex indicatingthat geologically reasonable amounts of magma can account foreven the massive, 70 cm thick UG2 chromitite. The model requiressome crystallization to have occurred in a deeper chamber, forwhich there is ample geochemical evidence. KEY WORDS: Bushveld complex; chromite; crystal-laden magma; crustal contamination; magma mixing; UG2 chromitite     

豆荚状铬铁矿铂族元素地球化学研究进展

豆荚状铬铁矿是蛇绿岩中特有的一类矿产，按其化学成分可分为高Cr型和高Al型两种。其中的PGE主要以RuS2和Os、Ir、Ru合金等包体形式存在，或以类质同像形式进入铬铁矿晶格。两种类型的铬铁矿均表现出负倾斜型PGE配分模式，其Pt、Pd含量相近；与高Al型铬铁矿相比，高Cr型铬铁矿有更高的Os、Ir、Ru含量，部分豆荚状铬铁矿表现出Pt、Pd相对富集的平坦到正倾斜型PGE配分模式。目前对豆荚状铬铁矿PGE含量及配分模式还缺少一个统一的解释，但其PGE地球化学可为豆荚状铬铁矿的成因及构造背景解释提供更多的信息。     

西藏罗布莎蛇绿岩豆荚状铬铁矿石中的合金成分

从西藏雅鲁藏布江蛇绿岩带的罗布莎豆荚状铬铁矿床中 ,揭示出包含 70～ 80种矿物的一个地幔矿物群 ,其中特别引人注意的是含有多种合金。本文报道了已发现的合金类型和它们的化学成分。这些合金矿物主要通过人工重砂选矿提取的 ,少数合金在矿石光片中可以见到。本文报道的部分合金系有 :Ni(Fe) - C- Cr系 ,W-Cr- Co系 ,Al- Fe- L a系 ,Fe- Si- Ti系 ,Ag- Sn- Si系 ,Ni- Ir- Fe系 ,Fe- Pd- Pt系 ,Fe- Ni- C系。这些碳化物、金属硅以及铁合金等表明它们形成于还原环境 ,然而主岩铬铁矿石则形成于氧化环境 ,认为罗布莎铬铁矿是从玻安质岩浆中结晶的。这样合金矿物可能是外来晶体 ;或者它们形成于地核被后来上升的地幔柱带到浅部 ,包在铬铁矿中 ;或者是滞留在地幔中的成核物质后来被铬铁矿捕获。     

High Pressure Asher Digestion and an Isotope Dilution-ICP-MS Method for the Determination of Platinum-Group Element Concentrations in Chromitite Reference Materials CHR-Bkg, GAN Pt-1 and HHH

New concentration data for Ru, Rh, Pd, Re, Os, Ir and Pt are presented for three chromitite reference materials. A simple and very effective procedure was applied for the measurements. Samples were spiked with enriched isotopes and digested in a HNO₃/HCl (5+2) acid mixture at 300 °C and 125 bar (1.25 × 10⁷ Pa) pressure in a high pressure asher (HPA-S, Anton Paar). The programme settings were changed as a function of mass (0.5, 1, 2 and 4 g) and time (5 and 15 hours). Complete chromitite dissolutions for three digestions at each setting were monitored using XRD analyses of the amorphous residue after digestion. The osmium concentration was determined by sparging the OsO₄ that was formed during digestion into a quadrupole ICP-MS. After drying and re-dissolution of the remaining residue, the other PGEs were separated on-line from their matrix in a simple cation-exchange column that was coupled to the ICP-MS. The concentrations were determined through isotope dilution and external calibration (Rh). By using the on-line separation, we were able to control interference effects (isobaric and molecular), which resulted in highly reproducible data. Replicate measurements of the reference material CHR-Bkg (SARM CRPG-CNRS) with sample masses ranging from 0.5 to 4 g showed very small standard deviations compared to the results from the initial collaborative trials and published data (e.g., 3.2% RSD vs. 32% RSD for Ru). Results for platinum showed the largest scatter, which is currently attributed to the small size of the test portion. In addition to CHR-Bkg, the first results for two chromitite reference materials "platinumore" GAN Pt-1 and "chromiumore" HHH issued by the Central Geological Laboratory of Mongolia are presented.     

Alteration Mechanisms of Chromian-Spinel during Serpentinization at Wadi Sifein Area, Eastern Desert, Egypt

Wadi Sifein podiform chromite deposits, Central Eastern Desert of Egypt, are hosted by fully serpentinized peridotite that is a part of the dismembered Pan‐African ophiolite complexes. Relics of primary minerals and the chemical characters indicate that the ophiolitic rocks were derived from depleted mantle peridotite of harzburgite and subordinate dunite compositions. The mantle rocks were initially formed at a mid‐oceanic ridge and subsequently thrust at a supra‐subduction zone. The chromite mineralization at Wadi Sifein area displays either pod‐shaped bodies with massive and lumpy chromitite appearance or dissemination of chromian‐spinel in serpentinite matrix. The podiform chromitite exhibits a very limited compositional range in terms of Cr# [Cr/(Cr + Al) atomic ratio] and Mg# [Mg/(Mg + Fe) atomic ratio]. The chromian‐spinel, however, frequently displays optical and geochemical zoning. Four zones can be identified from core to edge: inner core representing the original composition of the chromian‐spinel; narrow Cr‐rich ferritchromit zone; wide ferritchromit zone; and outer Cr‐magnetite/magnetite zone. The zonation of chromian‐spinel is interpreted to be a result of serpentinization rather than magmatic or metamorphic processes. The geochemical data obtained from the chromitite and chromian‐spinel was statistically processed using discriminant and R‐mode factor analyses. Two trends, minor and major, were achieved considering the formation of ferritchromit. The minor trend is controlled by the redistribution of trivalent cations, where Cr₂O₃ increased on the expense mainly of Al₂O₃ and to less extent Fe₂O₃ to form zone II during the peak of serpentinization. The major trend of alteration, however, is explained by the exchange between Mg‐Fe²⁺ rather than Cr, Al, and Fe³⁺ to form zone III. Kammererite formation was accompanied the formation of zones III and IV at a 314°C temperature of formation.     

Titanium,Ti, A New Mineral Species from Luobusha,Tibet, China

We describe the new mineral species titanium,ideally Ti,found in the podiform chromitites of the Luobusha ophiolite in Tibet,People’s Republic of China.The irregular crystals range from 0.1 to 0.6 mm in diameter and form an intergrowth with coesite and kyanite.Titanium is silver grey in colour,the luster is metallic,it is opaque,the streak is grayish black,and it is non-fluorescent.The mineral is malleable,has a rough to hackly fracture and has no apparent cleavage.The estimated Mohs hardness is 4,and the calculated density is 4.503 g/cm3.The composition is Ti 99.23-100.00 wt%.The mineral is hexagonal,space group P63 /mmc.Unit-cell parameters are a 2.950(2),c 4.686(1),V 35.32(5) 3,Z = 2.The five strongest powder diffraction lines [d in(hkl)(I/I0)] are: 2.569(010)(32),2.254(011)(100),1.730(012)(16),1.478(110)(21),and 0.9464(121)(8).The species and name were approved by the CNMNC(IMA 2010–044).     

贺根山豆荚状铬铁矿中硅酸盐包体及其地质意义

贺根山豆荚状铬铁矿是典型的高Al型铬铁矿(Cr#=47.8～54.9,Mg#=64.1～73.7),其中的包体以硅酸盐矿物为主(包括橄榄石、斜方辉石、单斜辉石、韭闪石、钠长石).根据包体形状、矿物组合及分布特征可将其划分为三类.第一类包体呈孤立单矿物相,主要包括橄榄石和单斜辉石,第二类包体由平衡共生的单斜辉石和斜方辉石构成,上述两类包体均具有被熔蚀的边,且零星分布在尖晶石中,属于捕虏晶成因.第三类包体属于熔融包体,具有多边形外形,包含复杂的矿物相并密集分布于尖晶石核部.利用尖晶石颗粒内部保存完好的单斜辉石以及单斜辉石和斜方辉石包体估算的温度(1148～1254℃)与压力(490～1290 MPa)表明,贺根山豆荚状铬铁矿矿床的形成深度为16～43 km.熔融包体中含大量钠长石和韭闪石,指示铬铁矿母熔体富集H2 O、Na和Si.与铬铁矿平衡母熔体的Al2 O3含量(15.4％～16.3％)、TiO2含量(0.3％～0.9％)和FeO/MgO比值(0.6～1.1)与低Ti拉斑玄武质熔体的类似.利用尖晶石和橄榄石包体计算获得铬铁矿原始熔体的Mg O含量为～19.8％.贺根山豆荚状铬铁矿经历了深部预富集和浅部成矿两个阶段,其中浅部成矿作用涉及熔体与方辉橄榄岩反应以及演化的熔体与原始熔体混合等过程.     

Alteration of Platinum-Group and Base-Metal Mineral Assemblages in Ophiolite Chromitites from the Dobromirtsi Massif,Rhodope Mountains (Bulgaria)

The Dobromirtsi Ultramafic Massif, located in the Rhodope Mountains (SE Bulgaria), is a portion of a Paleozoic sub-oceanic mantle affected by polyphase regional metamorphism. This massif contains several small, podiform chromitite bodies which underwent the same metamorphic evolution as their host peridotites. Like other ophiolite chromitites, those found in Dobromirtsi carry abundant platinum-group minerals (PGM) and base-metal minerals (BMM). The PGM consist mainly of Ru-, Os-, and Ir-based PGM (laurite RuS₂-erlichmanite OsS₂, Os-Ru-Ir alloys, irarsite [IrAsS], Ru-rich pentlandite, and an unknown Ir-sulfide) but minor Rh- and Pd-based PGM (hollingworthite [RhAsS] and a series of unidentified stannides and sulfantimonides) are also present. In contrast, the BMM are dominated by pentlandite (Ni,Fe)₉S₈, followed by heazlewoodite (Ni₃S₂), breithauptite (NiSb), maucherite (Ni₁₁As₈), godlevskite (Ni₇S₆), gersdorffite (NiAsS), millerite (NiS), undetermined minerals containing Ni, As and Sb, orcelite (Ni_5-XAs₂), awaruite (Ni₃Fe) and chalcopyrite (CuFeS₂). The detailed study of the textural relationships, morphology and composition of the PGM and BMM inclusions indicate the existence of two different PGM-BMM assemblages: (i) a primary or magmatic; and (ii) a secondary related with postmagmatic alteration. The PGM and BMM inclusions in unaltered zones of chromite crystals (mainly laurite-erlichmanite and pentlandite) are considered to be primary magmatic minerals formed under variable temperature (1200–1100°C) and sulfur fugacity (between −2 and −0.5 log fS₂). In contrast, PGM and BMM located along altered edges of chromite and serpentinised silicate matrix are considered to be secondary, formed from or re-equilibrated with altering fluids. Secondary PGM and BMM assemblages are considered as result of the combination of reducing and oxidising events related with regional metamorphism. Under low fO₂ states, fS₂ also drops giving place to the formation of S-poor Ni-rich sulfides and secondary Ru-alloys by desulfurisation of primary S-containing minerals. In contrast, predominance of platinum-group elements and/or base-metal arsenides and sulfarsenides associated with the altered edges of chromite (chromite strongly enriched in Fe₂O₃) is related with the fixing of remobilised PGE (mainly Ir, Rh and Pd) and base-metals (mainly Ni and Fe) when late oxidising fluids supplied As as well as Sb and Sn.