Platinum-group elements distribution and spinel composition in podiform chromitites and associated rocks from the upper mantle section of the Neoproterozoic Bou Azzer ophiolite, Anti-Atlas, Morocco

The distribution of platinum-group elements (PGEs), together with spinel composition, of podiform chromitites and serpentinized peridotites were examined to elucidate the nature of the upper mantle of the Neoproterozoic Bou Azzer ophiolite, Anti-Atlas, Morocco. The mantle section is dominated by harzburgite with less abundant dunite. Chromitite pods are also found as small lenses not exceeding a few meters in size. Almost all primary silicates have been altered, and chromian spinel is the only primary mineral that survived alteration. Chromian spinel of chromitites is less affected by hydrothermal alteration than that of mantle peridotites. All chromitite samples of the Bou Azzer ophiolite display a steep negative slope of PGE spidergrams, being enriched in Os, Ir and Ru, and extremely depleted in Pt and Pd. Harzburgites and dunites usually have intermediate to low PGE contents showing more or less unfractionated PGE patterns with conspicuous positive anomalies of Ru and Rh. Two types of magnetite veins in serpentinized peridotite, type I (fibrous) and type II (octahedral), have relatively low PGE contents, displaying a generally positive slope from Os to Pd in the former type, and positive slope from Os to Rh then negative from Rh to Pd in the latter type. These magnetite patterns demonstrate their early and late hydrothermal origin, respectively. Chromian spinel composition of chromitites, dunites and harzburgites reflects their highly depleted nature with little variations; the Cr# is, on average, 0.71, 0.68 and 0.71, respectively. The TiO₂ content is extremely low in chromian spinels, <0.10, of all rock types. The strong PGE fractionation of podiform chromitites and the high-Cr, low-Ti character of spinel of all rock types imply that the chromitites of the Bou Azzer ophiolite were formed either from a high-degree partial melting of primitive mantle, or from melting of already depleted mantle peridotites. This kind of melting is most easily accomplished in the supra-subduction zone environment, indicating a genetic link with supra-subduction zone magma, such as high-Mg andesite or arc tholeiite. This is a general feature in the Neoproterozoic upper mantle.     

古老大陆岩石圈地幔再循环与蛇绿岩中铬铁矿床成因

不同地区、不同时代蛇绿岩中不同类型铬铁矿岩的Re-Os同位素研究表明,在铬铁矿石或围岩中均存在极度亏损的具有大陆岩石圈地幔属性的物质。新疆达拉布特古生代蛇绿岩带中萨尔托海富Al铬铁矿岩的Os同位素组成为0.1109～0.1256,对应的模式年龄为3.5～0.6Ga;西藏班公湖—怒江中生代蛇绿岩带中东巧富Cr铬铁矿石及围岩Os同位素组成介于0.1175～0.1261,对应的模式年龄为1.5～0.1Ga;雅鲁藏布江中生代蛇绿岩带中罗布莎富Cr铬铁矿岩的Os同位素变化范围为0.1038～0.1266,对应的模式年龄为3.37～0.28Ga,而该带中不含矿的泽当二辉橄榄岩的Os同位素组成为0.1256～0.1261,没有古老大陆岩石圈地幔属性的物质存在,与新特提斯洋地幔Os组成较为接近。推测在蛇绿岩形成过程中,古老大陆岩石圈地幔参与循环有利于形成铬铁矿床,明确提出"熔体与古老大陆岩石圈地幔反应成矿"的假说,指出蛇绿岩带中存在的古老微陆块可能是找矿的指示标志。     

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。     

Platinum‐Group Elements Geochemistry and Chromian Spinel Composition in Podiform Chromitites and Associated Peridotites from the Cheshmeh‐Bid Deposit,Neyriz, Southern Iran: Implications for Geotectonic Setting

Dunite and serpentinized harzburgite in the Cheshmeh-Bid area, northwest of the Neyriz ophiolite in Iran, host podiform chromitite that occur as schlieren-type, tabular and aligned massive lenses of various sizes. The most important chromitite ore textures in the Cheshmeh-Bid deposit are massive, nodular and disseminated. Massive chromitite, dunite, and harzburgite host rocks were analyzed for trace and platinum-group elements geochemistry. Chromian spinel in chromitite is characterized by high Cr~#(0.72-0.78), high Mg~#(0.62–0.68) and low TiO_2(0.12 wt%-0.2 wt%) content. These data are similar to those of chromitites deposited from high degrees of mantle partial melting. The Cr~# of chromian spinel ranges from 0.73 to 0.8 in dunite, similar to the high-Cr chromitite, whereas it ranges from 0.56 to 0.65 in harzburgite. The calculated melt composition of the high-Cr chromitites of the Cheshmeh-Bid is 11.53 wt%–12.94 wt% Al_2O_3, 0.21 wt%–0.33 wt% TiO_2 with FeO/MgO ratios of 0.69-0.97, which are interpreted as more refractory melts akin to boninitic compositions. The total PGE content of the Cheshmeh-Bid chromitite, dunite and harzburgite are very low(average of 220.4, 34.5 and 47.3 ppb, respectively). The Pd/Ir ratio, which is an indicator of PGE fractionation, is very low(0.05–0.18) in the Cheshmeh-Bid chromitites and show that these rocks derived from a depleted mantle. The chromitites are characterized by high-Cr~#, low Pd + Pt(4–14 ppb) and high IPGE/PPGE ratios(8.2–22.25), resulting in a general negatively patterns, suggesting a high-degree of partial melting is responsible for the formation of the Cheshmeh-Bid chromitites. Therefore parent magma probably experiences a very low fractionation and was derived by an increasing partial melting. These geochemical characteristics show that the Cheshmeh-Bid chromitites have been probably derived from a boninitic melts in a supra-subduction setting that reacted with depleted peridotites. The high-Cr chromitite has relatively uniform mantle-normalized PGE patterns, with a steep slope, positive Ru and negative Pt, Pd anomalies, and enrichment of PGE relative to the chondrite. The dunite(total PGE = 47.25 ppb) and harzburgite(total PGE =3 4.5 ppb) are highly depleted in PGE and show slightly positive slopes PGE spidergrams, accompanied by a small positive Ru, Pt and Pd anomalies and their Pdn/Irn ratio ranges between 1.55–1.7 and 1.36-1.94, respectively. Trace element contents of the Cheshmeh-Bid chromitites, such as Ga, V, Zn, Co, Ni, and Mn, are low and vary between 13–26, 466–842, 22-84, 115–179, 826–-1210, and 697–1136 ppm, respectively. These contents are compatible with other boninitic chromitites worldwide. The chromian spinel and bulk PGE geochemistry for the Cheshmeh-Bid chromitites suggest that high-Cr chromitites were generated from Cr-rich and, Ti-and Al-poor boninitic melts, most probably in a fore-arc tectonic setting related with a supra-subduction zone, similarly to other ophiolites in the outer Zagros ophiolitic belt.     

Using platinum-group elements and Au geochemistry to constrain the genesis of podiform chromitites and associated peridotites from the Soghan mafic–ultramafic complex,Kerman, Southeastern Iran

The podiform chromite deposit of the Soghan mafic–ultramafic complex is one of the largest chromite deposits in south-east Iran (Esfandagheh area). The Soghan complex is composed mainly of dunite, harzburgite, lherzolite, pyroxenite, chromitite, wehrlite and gabbro. Olivine, orthopyroxene, and to a lesser extent clinopyroxene with highly refractory nature, are the primary silicates found in the harzburgites and dunites. The forsterite content of olivine is slightly higher in dunites (Fo₉₄) than those in harzburgites (Fo₉₂) and lherzolites (Fo₈₉). Chromian spinel mainly occurs as massive chromitite pods and as thin massive chromitite bands together with minor disseminations in dunites and harzburgites. Chromian spinels in massive chromitites show very high Cr-numbers (80–83.6), Mg-numbers (62–69) and very low TiO₂ content (averaging 0.17 wt.%) for which may reflect the crystallization of chromite from a boninitic magma. The Fe^3 +-number is very low, down to < 0.04 wt.%, in the chromian spinel of chromitites and associated peridotites of the Soghan complex.PGE contents are variable and range from 80 to 153 pbb. Chromitites have strongly fractionated chondrite-normalized PGE patterns, which are characterized by enrichments in Os, Ir and Rh relative to Pt and Pd. Moreover, the Pd/Ir value which is an indicator of PGE fractionation ranges from < 0.08 to 0.24 in chromitite of the Soghan complex. These patterns and the low PGE abundances are typical of ophiolitic chromitites and indicating a high degree of partial melting (about 20–24%) of the mantle source. Moreover, the Pd_N/Ir_N ratios in dunites are unfractionated, averaging 1.2, whereas the harzburgites and lherzolites show slightly positive slopes PGE spidergrams, together with a small positive Ru and Pd anomaly, and their Pd_N/Ir_N ratio averages 1.98 and 2.15 respectively.The mineral chemistry data and PGE geochemistry, along with the calculated parental melts in equilibrium with chromian spinel of the Soghan chromitites indicate that the Soghan complex was generated from an arc-related magma with boninitic affinity above a supra-subduction zone setting.     

Platinum group elements zoning and mineralogy of chromitites from the cumulate sequence of the Nurali massif (Southern Urals, Russia)

The Nurali lherzolite massif is one of the dismembered ophiolite bodies associated with the Main Uralian Fault (Southern Urals, Russia). It comprises a mainly lherzolitic mantle section, an ultramafic clinopyroxene-rich cumulate sequence (Transition Zone), and an amphibole gabbro unit.The cumulate section hosts small chromitite bodies at different stratigraphic heights within the sequence. Chromitite bodies from three different levels along a full section of the cumulate sequence and two from other localities were investigated. They differ in the host lithology, chromitite texture and composition, and PGE content and mineralogy. Chromitites at the lowest level, which are hosted by clinopyroxenite, form cm-scale flattened lenses. They have high Cr# and low Mg# chromites and are enriched in Pt and Pd relative to Os and Ir. At a higher, intermediate level, the chromitites are hosted by dunite. They form meter thick lenses, contain low Cr# and high Mg# chromites, have high PGE contents (up to 26,700 ppb), and are enriched in Os, Ir and Ru relative to Pt and Pd, reflecting a mineralogy dominated by laurite–erlichmanite and PGE–Fe alloys. At the highest level are chromitites hosted by olivine–enstatite rocks. These chromitites have high Cr# and relatively low Mg# chromites and very low PGE content, with laurite as the dominant PGE mineral.The platinum group minerals (PGMs) show extreme zoning, with compositions ranging from erlichmanite to almost pure laurite and from Os-rich to Ru-rich alloys, with variable and irregular zoning patterns.Two chromitite bodies up to 6 km from the main sequence can be correlated with the latter based on geochemistry and mineralogy, implying that the variations in chromitite geochemistry are due to processes that operated on the scale of the massif rather than those that operated on the scale of the outcrop.Pertsev et al. [Pertsev, A.N., Spadea, P., Savelieva, G.N., Gaggero, L., 1997. Nature of the transition zone in the Nurali ophiolite, Southern Urals. Tectonophysics 276, 163–180.] propose that the Transition Zone formed by solidification of a series of small magma bodies that partially overlapped in time and space. The magmas formed by successive partial melting of the underlying mantle. We suggest that this process determined the changing PGE geochemistry of the successive batches of magma. The PGE distribution fits a model of selected extraction from the mantle, where monosulphide solid solution–sulphide liquid equilibrium was attained until complete melting of the monosulphide solid solution. Later and localized variations in fS₂ resulted in the formation of different PGMs with complex zoning patterns.     

Chemical homogeneity of high-Cr chromitites as indicator for widespread invasion of boninitic melt in mantle peridotite of Bir Tuluha ophiolite,Northern Arabian Shield,Saudi Arabia

The Bir Tuluha ophiolite is one of the most famous chromitite-bearing occurrences in the Arabian Shield of Saudi Arabia, where chromitite bodies are widely distributed as lensoidal pods of variable sizes surrounded by dunite envelopes, and are both enclosed within the harzburgite host. The bulk-rock geochemistry of harzburgites and dunites is predominately characterized by extreme depletion in compatible trace elements that are not fluid mobile (e.g., Sr, Nb, Ta, Hf, Zr and heavy REE), but variable enrichment in the fluid-mobile elements (Rb and Ba). Harzburgites and dunites are also enriched in elements that have strong affinity for Mg and Cr such as Ni, Co and V. Chromian spinels in all the studied chromitite pods are of high-Cr variety; Cr-ratio (Cr/(Cr + Al) atomic ratio) show restricted range between 0.73 and 0.81. Chromian spinels of the dunite envelopes also show high Cr-ratio, but slightly lower than those in the chromitite pods (0.73–0.78). Chromian spinels in the harzburgite host show fairly lower Cr-ratio (0.49–0.57) than those in dunites and chromitites. Platinum-group elements (PGE) in chromitite pods generally exhibit steep negative slopes of typical ophiolitic chromitite PGE patterns; showing enrichment in IPGE (Os, Ir and Ru), over PPGE (Rh, Pt and Pd). The Bir Tuluha ophiolite is a unimodal type in terms of the presence of Ru-rich laurite, as the sole primary platinum-group minerals (PGM) in chromitite pods. These petrological features indicates that the Bir Tuluha ophiolite was initially generated from a mid-ocean ridge environment that produced the moderately refractory harzburgite, thereafter covered by a widespread homogeneous boninitic melt above supra-subduction zone setting, that produced the high-Cr chromitites and associated dunite envelopes. The Bir Tuluha ophiolite belt is mostly similar to the mantle section of the Proterozoic and Phanerozoic ophiolites, but it is a “unimodal” type in terms of high-Cr chromitites and PGE-PGM distribution.     

The effect of metasomatism on the Cr-PGE mineralization in the Finero Complex, Ivrea Zone, Southern Alps

The magmatic metasomatism that was responsible for producing chromitite–dunite bodies in the unusual phlogopite peridotite of the Finero Complex in Permian to Triassic times also influenced the Cr-platinum group elements (PGE) mineralization. At least the end stages of this metasomatism are recorded in compositional zoning of chromite grains in the podiform chromitite. Metasomatic melt, with or without vapor, reacted with chromite to produce core-to-rim Cr enrichment of extant chromite grains and was concurrent with pyroxene crystallization. Under conditions of lower melt/rock ratio, metasomatism resulted in core-to-rim Al enrichment in chromite and crystallization of amphibole between chromite and clinopyroxene. This early, high-temperature metasomatism is unrelated to the later and pervasive K-metasomatism that crystallized phlogopite and was associated with the intrusion of clinopyroxenite dikes that cut the peridotite. Much later, serpentinization of olivine locally depleted chromite in Al and enriched it in Fe and formed minor amounts of magnetite.The PGE, which are present mainly as laurite inclusions in chromite, were remobilized by the early metasomatism. This resulted in substantial variation in the PGE contents of chromitites and imposed a characteristic PGE pattern in which chondrite-normalized Os, Ir, Ru and Rh contents are high but Pt and Pd contents are low. The slopes of PGE chondrite-normalized concentration patterns are systematically related to absolute PGE abundance and to rock mode. Chromitites with low modal orthopyroxene, clinopyroxene, and amphibole exhibit negative PGE slopes and contain relatively high PGE concentrations, whereas chromitites rich in these silicate minerals have positive slopes and low PGE contents.     

Geodynamic implications of ophiolitic chromitites in the La Cabaña ultramafic bodies,Central Chile

Chromitites (>80% volume chromite) hosted in two ultramafic bodies (Lavanderos and Centinela Bajo) from the Palaeozoic metamorphic basement of the Chilean Coastal Cordillera were studied in terms of their chromite composition, platinum-group element (PGE) abundances, and Re-Os isotopic systematics. Primary chromite (Cr# = 0.64–0.66; Mg# = 48.71–51.81) is only preserved in some massive chromitites from the Centinela Bajo ultramafic body. This chemical fingerprint is similar to other high-Cr chromitites from ophiolite complexes, suggesting that they crystallized from arc-type melt similar to high-Mg island-arc tholeiites (IAT) and boninites in supra-subduction mantle. The chromitites display enrichment in IPGE (Os, Ir, Ru) over PPGE (Rh, Pt, Pd), with PGE concentrations between 180 and 347 ppb, as is typical of chromitites hosted in the mantle of supra-subduction zone (SSZ) ophiolites. Laurite (RuS₂)-erlichmanite (OsS₂) phases are the most abundant inclusions of platinum-group minerals (PGM) in chromite, indicating crystallization from S-undersaturated melts in the sub-arc mantle. The metamorphism associated with the emplacement of the ultramafic bodies in the La Cabaña has been determined to be ca. 300 Ma, based on K-Ar dating of fuchsite. Initial ¹⁸⁷Os/¹⁸⁸Os ratios for four chromitite samples, calculated for this age, range from 0.1248 to 0.1271. These isotopic compositions are well within the range of chromitites hosted in the mantle section of other Phanaerozoic ophiolites. Collectively, these mineralogical and geochemical features are interpreted in terms of chromite crystallization in dunite channels beneath a spreading centre that opened a marginal basin above a supra-subduction zone. This implies that chromitite-bearing serpentinites in the metamorphic basement of the Coastal Cordillera are of oceanic-mantle origin and not oceanic crust as previously suggested. We suggest that old subcontinental mantle underlying the hypothetical Chilenia micro-continent was unroofed and later altered during the opening of the marginal basin. This defined the compositional and structural framework in which the protoliths of the meta-igneous and meta-sedimentary rocks of the Eastern and Western Series of the Chilean Coastal Cordillera basement were formed.     

大洋地幔橄榄岩-铬铁矿中的金刚石和深地幔再循环

全球多地蛇绿岩型地幔橄榄岩和铬铁矿中发现微粒金刚石,并在中国西藏南部和俄罗斯乌拉尔北部的蛇绿岩铬铁矿中发现原位产出的金刚石,认为是地球上金刚石的一种新的产出类型,不同于金伯利岩型金刚石和超高压变质型金刚石。它们与呈斯石英假象的柯石英、高压相的铬铁矿和青松矿等高压矿物以及碳硅石和单质矿物等强还原矿物伴生,指示蛇绿岩中的这些矿物组合形成于深度150~300 km或者更深的地幔。金刚石具有很轻的C同位素组成（δ13C-18‰~-28‰）,并出现多种含Mn矿物和壳源成分包裹体。研究认为它们曾是早期深俯冲的地壳物质,达到>300 km深部地幔或地幔过渡带后,经历了熔融并产生新的流体,后者在上升过程中结晶成新的超高压、强还原矿物组合,通过地幔对流或地幔柱作用被带回到浅部地幔,由此建立了一个俯冲物质深地幔再循环的新模式。蛇绿岩型地幔橄榄岩和铬铁矿中发现金刚石等深部矿物,质疑了蛇绿岩铬铁矿形成于浅部地幔的已有认识,引发了一系列新的科学问题,提出了新的研究方向。      

Palladium and gold mineralization in podiform chromitite at Kraubath, Austria

Summary ?We report, for the first time, the occurrence of five palladium-rich, one palladium bearing and two gold-silver minerals from podiform chromitites in the Eastern Alps. Minerals identified include braggite, keithconnite, stibiopalladinite, potarite, mertieite II, Pd-bearing Pt-Fe alloy, native gold and Ag-Au alloy. They occur in heavy mineral concentrates produced from two massive podiform chromitite samples (unaltered and highly altered) of the Kraubath ultramafic massif, Styria, Austria. Distribution patterns of platinum-group elements (PGE) in these chromitites show considerable differences in the behaviour of the less refractory PGE (PPGE-group: Rh, Pt, Pd) compared to the refractory PGE (IPGE-group: Os, Ir, Ru). PPGE are more enriched in chromitite showing pronounced alteration features. The unaltered chromitite displays a negatively sloped chondrite-normalised PGE pattern similar to typical ophiolitic-podiform chromitite. Except for the Pd- and Au-Ag minerals that are generally rare in ophiolites, about 20 other platinum-group minerals (PGM) have been discovered. They include PGE-sulphides (laurite, erlichmanite, kashinite, bowieite, cuproiridsite, cuprorhodsite, unnamed Ir-rich variety of ferrorhodsite, unnamed Ni-Fe-Cu-Rh- and Ni-Fe-Cu-Ir-Rh monosulphides), PGE alloys (Pt-Fe, Ir-Os, Os-Ir and Ru-Os-Ir), PGE-sulpharsenides (irarsite, hollingworthite, platarsite, ruarsite and a number of intermediate species), sperrylite and a Ru-rich oxide (?). Three PGM assemblages have been recognised and attributed to different processes ranging from magmatic to hydrothermal and weathering-related. Pd-rich minerals are characteristic of both chromitite types, although their chemistry and relative proportions vary considerably. Keithconnite, braggite and Pd-bearing ferroan platinum, together with a number of PGE-sulphides (mainly laurite-erlichmanite) and alloys, are typical only of the unaltered podiform chromitite (assemblage I). Euhedral mono- and polyphase PGM grains in the submicron to 100 μm range show features of primary magmatic assemblages. The diversity of PGM in these assemblages is unusual for ophiolitic environments. In assemblage II, laurite-erlichmanite is intergrown with and overgrown by PGE-sulpharsenides; other minerals of assemblage I are missing. Potarite, stibiopalladinite, mertieite II, native gold and Ag-Au alloys, as well as PGE-sulpharsenides, sperrylite and base metal arsenides and sulphides are characteristic for the highly altered chromitite (assemblage III). They occur either interstitial to chromite in association with metamorphic silicates, in chromite rims or along cracks, and are thus interpreted as having formed by remobilization of PGE by hydrothermal processes during polyphase regional metamorphism. Received August 3, 2000;/revised version accepted December 28, 2000     

西藏雅鲁藏布江缝合带东段泽当豆荚状铬铁矿特征

泽当蛇绿岩位于雅鲁藏布江缝合带东段,岩体由地幔橄榄岩、辉长辉绿岩、辉石岩、火山岩等组成。地幔橄榄岩主要为方辉橄榄岩、纯橄岩和二辉橄榄岩。在方辉橄榄岩中发现7处豆荚状铬铁矿,矿石类型主要有致密块状和浸染状。出露地表的长度0.5~3m,厚0.2~1m。矿体的延伸方向为北西向,与岩体展布的方向一致,铬铁矿的Cr~#=67.9~88.5,属于高铬型铬铁矿。泽当地幔橄榄岩岩相学特征以及矿物组合、矿物化学成份及岩相学特征,显示岩体至少存在两次的部分熔融过程,即为早期的MOR构造背景,以及后期SSZ环境的改造。铬铁矿的铂族元素(PGE)以富集Os、Rh、Pd,亏损Ir、Ru、Pt的负斜率分布模式,表明其形成过程中经受后期熔体/流体的改造。对比罗布莎岩体的矿物组合,矿物化学和地球化学等特征,显示泽当豆荚状铬铁矿矿体与典型高铬型具相似性,存在较大的找矿空间。     

豆荚状铬铁矿以及其中铂族元素矿物的成因问题——进展与展望

铂族元素矿物(Platinum Group Mineral:简称PGM)资料的不断积累,丰富了人们对蛇绿岩中豆荚状铬铁矿成因的认识。文章总结近年来有关PGM的新资料和取得的新认识,探讨豆荚状铬铁矿以及其中PGM的成因问题。幔源岩浆结晶过程中,铬铁矿周边熔体减少将诱发那些易氧化的铂族元素(Os、Ir、Ru)在熔体中达到饱和状态,并结晶形成纳米级PGM。在地幔熔体中,随着硫逸度升高,PGM微粒与熔体中的硫反应并逐渐长大。多期次的熔体抽提和熔体-岩石反应事件,可以在地幔源区通过逐步降低硫逸度、促进含铂族元素的贱金属硫化物分解,形成PGM以及铂族元素合金。低硫逸度环境更有利于PGM的形成和保存。在变质环境或流体环境中,这些PGM往往会与流体反应,造就了PGM矿物的多样性。原生PGM与变质流体反应并发生原地去硫化作用,可以形成次生的PGM环边或者纳米级PGM包体。铬铁矿的多阶段蚀变/再平衡过程可以导致PGM溶解—沉淀—均一化,并扰动Os同位素体系。不同类型矿石在有限空间伴生的现象以及它们所具有显著差异的地球化学特征,说明蛇绿岩是不同地幔组分的机械混杂。随着俯冲板片,铬铁矿团块被拖曳到地幔深部,并通过地幔对流重新出现在扩张中心附近,最终混杂在蛇绿岩中。发生循环的铬铁矿团块因此可以与新生铬铁矿及其围岩伴生在同一蛇绿混杂岩中。     

In situ Re–Os isotopic analysis of platinum-group minerals from the Mayarí-Cristal ophiolitic massif (Mayarí-Baracoa Ophiolitic Belt,eastern Cuba): implications for the origin of Os-isotope heterogeneities in podiform chromitites

Chromitite pods in the Mayarí-Cristal ophiolitic massif (eastern Cuba) were formed in the Late Cretaceous when island arc tholeiites and MORB-like back-arc basin basalts reacted with residual mantle peridotites and generated chromite-rich bodies enclosed in dunite envelopes. Platinum-group minerals (PGM) in the podiform chromitites exhibit important Os-isotope heterogeneities at the kilometric, hand sample and thin section scales. ¹⁸⁷Os/¹⁸⁸Os calculated at the time of chromitite crystallization (~90 Ma) ranges between 0.1185 and 0.1295 (γOs = −7.1 to +1.6, relative to enstatite chondrite), and all but one PGM have subchondritic ¹⁸⁷Os/¹⁸⁸Os. Grains in a single hand sample have initial ¹⁸⁷Os/¹⁸⁸Os that spans from 0.1185 to 0.1274, and in one thin section it varies between 0.1185 and 0.1232 in two PGM included in chromite which are only several millimeters apart. As the Os budget of a single micrometric grain derives from a mantle region that was at least several m³ in size, the variable Os isotopic composition of PGM in the Mayarí-Cristal chromitites probably reflects the heterogeneity of their mantle sources on the 10–100 m scale. Our results show that this heterogeneity was not erased by pooling and mingling of individual melt batches during chromitite crystallization but was transferred to the ore deposits on mineral scale. The distribution of the Os model ages calculated for PGM shows four main peaks, at ~100, 500, 750 and 1,000 Ma. These variable Os model ages reflect the presence of different depleted domains in the oceanic (Pacific-related) upper mantle of the Greater Antilles paleo-subduction zone. The concordance between the age of crystallization of the Mayarí-Cristal chromitites and the most recent peak of the Os model age distribution in PGM supports that Os in several grains was derived from fertile domains of the upper mantle, whose bulk Os isotopic composition is best approximated by that of enstatite chondrites; on the other hand, most PGM are crystallized by melts that tapped highly refractory mantle sources.     

Distribution of platinum-group elements and Os isotopes in chromite ores from Mayarí-Baracoa Ophiolitic Belt (eastern Cuba)

The Mayarí-Baracoa ophiolitic belt in eastern Cuba hosts abundant chromite deposits of historical economic importance. Among these deposits, the chemistry of chromite ore is very variable, ranging from high Al (Cr#=0.43–0.55) to high Cr (Cr#=0.60–0.83) compositions. Platinum-group element (PGE) contents are also variable (from 33 ppb to 1.88 ppm) and correlate positively with the Cr# of the ore. Bulk PGE abundances correlate negatively with the Pd/Ir ratio showing that chromite concentrates mainly Os, Ir and Ru which gives rise to the characteristic negatively sloped, chrondrite-normalized PGE patterns in many chromitites. This is consistent with the mineralogy of PGEs, which is dominated by members of the laurite–erlichmanite solid solution series (RuS₂–OsS₂), with minor amounts of irarsite (IrAsS), Os–Ir alloys, Ru–Os–Ir–Fe–Ni alloys, Ni–Rh–As, and sulfides of Ir, Os, Rh, Cu, Ni, and/or Pd. Measured ¹⁸⁷Os/¹⁸⁸Os ratios (from 0.1304 to 0.1230) are among the lower values reported for podiform chromitites. The ¹⁸⁷Os/¹⁸⁸Os ratios decrease with increasing whole-rock PGE contents and Cr# of chromite. Furthermore, γOs values of all but one of the chromitite samples are negative indicating a subchondiritc mantle source. γOs decrease with increasing bulk Os content and decreasing ¹⁸⁷Re/¹⁸⁸Os ratios. These mineralogical and geochemical features are interpreted in terms of chromite crystallization from melts varying in composition from back-arc basalts (Al-rich chromite) to boninites (Cr-rich chromite) in a suprasubduction zone setting. Chromite crystallization occurs as a consequence of magma mixing and assimilation of preexisting gabbro sills at the mantle–crust transition zone. Cr#, PGE abundances, and bulk Os isotopic composition of chromitites are determined by the combined effects of mantle source heterogeneity, the degree of partial melting, the extent of melt-rock interactions, and the local sulfur fugacity. Small-scale (μm to cm) chemical and isotopic heterogeneities in the platinum-group minerals are controlled by the mechanism(s) of chromite crystallization in a heterogeneous environment created by the turbulent regime generated by successive inputs of different batches of melt.     

Petrological and mineralogical studies of Pan-African serpentinites at Bir Al-Edeid area, central Eastern Desert, Egypt

The studied serpentinites occur as isolated masses, imbricate slices of variable thicknesses and as small blocks or lenses incorporated in the sedimentary matrix of the mélange. They are thrusted over the associated island arc calc-alkaline metavolcanics and replaced by talc-carbonates along shear zones. Lack of thermal effect of the serpentinites upon the enveloping country rocks, as well as their association with thrust faults indicates their tectonic emplacement as solid bodies. Petrographically, they are composed essentially of antigorite, chrysotile and lizardite with subordinate amounts of carbonates, chromite, magnetite, magnesite, talc, tremolite and chlorite. Chrysotile occurs as cross-fiber veinlets traversing the antigorite matrix, which indicate a late crystallization under static conditions. The predominance of antigorite over other serpentine minerals indicates that the serpentinites have undergone prograde metamorphism or the parent ultramafic rocks were serpentinized under higher pressure. The parent rocks of the studied serpentinites are mainly harzburgite and less commonly dunite and wehrlite due to the prevalence of mesh and bastite textures. The serpentinites have suffered regional metamorphism up to the greenschist facies, which occurred during the collisional stage or back-arc basin closure, followed by thrusting over a continental margin. The microprobe analyses of the serpentine minerals show wide variation in SiO₂, MgO, Al₂O₃, FeO and Cr₂O₃ due to different generations of serpentinization. The clinopyroxene relicts, from the partly serpentinized peridotite, are augite and similar to clinopyroxene in mantle-derived peridotites. The chromitite lenses associated with the serpentinites show common textures and structures typical of magmatic crystallization and podiform chromitites. The present data suggest that the serpentinites and associated chromitite lenses represent an ophiolitic mantle sequence from a supra-subduction zone, which were thrust over the continental margins during the collisional stage of back-arc basin.     

Early Palaeozoic sub-arc chromitite-bearing peridotite in the Kudi ophiolite on the westernmost Tibetan Plateau

ABSTRACT

A chromite deposit was discovered in the Kudi ophiolite in the Palaeozoic western Kunlun orogenic belt. Chromite forms elongated (<2 m in width) and banded chromitite bodies (<0.1 m in width for each band) in dunite and podiform chromitite bodies (<1.5 m in width) in harzburgite. Dunite is classified into two types. Type I dunite hosting massive and banded chromitites shows low Fo in olivine (88.1–90.9), moderate Cr^# [=Cr/(Cr + Al), 0.47–0.56] in chromite, and a positively sloped primitive mantle-normalized platinum group elements (PGE) pattern, suggesting that it is a cumulate of a mafic melt. Harzburgite and type II dunite show olivine with high Fo (>91.1) and chromite with moderate to high Cr^# (0.44–0.61), and flat to negatively sloped primitive mantle-normalized PGE patterns, indicating that they are residual mantle peridotite after partial melting. Chromite in all three types of chromitites has relatively uniform moderate values Cr^# ranging from 0.43 to 0.56. Massive chromitite contains euhedral chromite with high TiO₂ (0.40–0.43 wt.%) and has a positively sloped primitive mantle-normalized PGE pattern, suggesting that it represents a cumulate of a melt. Rocks containing disseminated and banded chromite show overall low total PGE, < 117 ppb, and a negatively sloped primitive mantle-normalized PGE pattern. Chromite grains in these two types of occurrences are irregular in shape and enclose olivine grains, suggesting that chromite formed later than olivine. We suggest that chromite-oversaturated melt penetrated into the pre-existing dunite and crystallized chromite. The oxygen fugacity (fO₂ values of chromitites and peridotites are high, ranging from FMQ+0.8 (0.8 logarithmic unit above the fayalite-magnetite-quartz buffer) to FMQ+2.3 for chromitites and from FMQ+0.9 to FMQ+2.8 for peridotites (dunite and harzburgite). The mineral compositions and high fO₂ values as well as estimated parental magma compositions of the chromitites suggest that the Kudi ophiolite formed in a sub-arc setting.     

Podiform Chromitites in the Luobusa Ophiolite (Southern Tibet): Implications for Melt-Rock Interaction and Chromite Segregation in the Upper Mantle

The Luobusa ophiolite in the Indus—Yarlung Zangbo sutureof southern Tibet hosts the largest known chromite deposit inChina. The podiform chromitites occur in a well-preserved mantlesequence consisting of harzburgite with abundant lenses of dunite.The harzburgites have relatively uniform bulk-rock compositionswith mg-numbers [100 Mg/(Mg + Fe)] ranging from 89 to 91 andshow flat, unfractionated, chondrite-normalized platinum groupelement (PGE) patterns. Their accessory chromite varies widelyin cr-number [100Cr/(Cr + Al)] (18–66). These rocks areessentially residua left after extraction of mid-ocean ridgebasalt (MORB)-type magmas. The podiform chromitites displaynodular, massive, disseminated and banded textures and typicallyhave dunite envelopes that grade into the surrounding harzburgiteand diopsidic harzburgite with increasing pyroxene contents.They consist of relatively uniform chromite with high cr-numbers(74–82), have strongly fractionated, chondrite-normalizedPGE patterns with enrichment in Os, Ir and Ru relative to Rh,Pt and Pt, and are believed to have formed from a boniniticmagma produced by a second stage of melting. Dunites containaccessory chromite intermediate in composition between thoseof harzburgite and chromitite and are believed to be the productsof reaction between new boninitic magmas and old MORB-type peridotites.The melt-rock reaction removed pyroxene from the peridotitesand precipitated oli-vine, forming dunite envelopes around thechromitite pods. The melts thus became more boninitic in compositionand chromite saturated, leading to precipitation of chromitealone. The interplay of melt-rock interaction, chromite fractionationand magma mixing should lead to many fluctuations in melt composition,producing both massive and disseminated chromitites and phaselayering within individual podiform bodies observed in the Luobusaophiolite. KEY WORDS: boninitic magmas; dunite envelope; melt—rock interaction; MORB peridotities; podiform chromitites ^*Corresponding author. Present address: Department of Geology, Laurentian University, Sudbury, Ont, Canada P3E 2C6.     

Diversity of platinum-group mineral assemblages in banded and podiform chromitite from the Kraubath ultramafic massif,Austria: evidence for an ophiolitic transition zone?

We report highly unusual platinum-group mineral (PGM) assemblages from geologically distinct chromitites (banded and podiform) of the Kraubath massif, the largest dismembered mantle relict in the Eastern Alps. The banded chromitite has a pronounced enrichment of Pt and Pd relative to the more refractory platinum-group elements (PGEs) of the IPGE group (Os, Ir, Ru), similar to crustal sections of ophiolites. On the contrary, the podiform chromitite displays a negatively sloping chondrite-normalised PGE pattern typical of ophiolitic podiform chromitite. The chemical composition of chromite varies from Cr# 73-77 in the banded type to 81-86 in the podiform chromitite. Thirteen different PGMs and one gold-rich mineral are first observed in the banded chromitite. The dominant PGM is sperrylite (53% of all PGMs), which occurs in polyphase assemblages with an unnamed Pt-base metal (BM) alloy and Pd-rich minerals such as stibiopalladinite, mayakite, mertieite II, unnamed Pd-Rh-As and Pd(Pt)-(As,Sb) minerals. This banded type also contains PGE sulphides (about 7%) represented by a wide compositional range of the laurite-erlichmanite series and irarsite (8%). Os-Ir alloy, geversite, an unnamed Pt-Pd-Bi-Cu phase and tetrauricupride are present in minor amounts. By contrast, the podiform chromitite, which yielded 21 different PGMs, is dominated by laurite (43% of all PGMs) which occurs in complex polyphase assemblages with PGE alloys (Ir-Os, Os-Ir, Pt-Fe), PGE sulphides (kashinite, bowieite, cuproiridsite, cuprorhodsite, unnamed (Fe,Cu)(Ir,Rh)₂S₄, braggite, unnamed BM-Ir and BM-Rh sulphides) and Pd telluride (keithconnite). A variety of PGE sulpharsenides (33%) including irarsite, hollingworthite, platarsite, ruarsite and a number of intermediate species have been identified, whereas sperrylite and stibiopalladinite are subordinate (2%). The occurrence of such a wide variety of PGMs from only two, 2.5-kg chromitite samples is highly unusual for an ophiolitic environment. Our novel sample treatment allowed to identify primary PGM assemblages containing all six PGEs in both laurite-dominated podiform chromitite as well as in uncommon sperrylite-dominated banded chromitite. We suggest that the geologically, geochemically and mineralogically distinct banded chromitite from Kraubath characterises the transition zone of an ophiolite, closely above the mantle section hosting podiform chromitite, rather than being representative of the crustal cumulate pile.     

中国铬铁矿的铂族元素分布特征

用NiS溶解和Te沉淀方法富集铂族元素（PGE），制成镍扣，再溶解于浓HCl中，使PGE和Te一起沉淀。制备的样品溶液在ELAN－5000型电感耦合等离子质谱仪（ICP－MS）上分析PGE。中国铬铁矿矿石，包括蛇绿岩套中的豆荚状铬铁矿床、非层状侵入体铬铁矿，计13个矿床（化）样品，其PGE模式表明，主要呈RU正异常模式，个别不同模式是由母岩不同以及铂族元素矿化叠加引起的。铬铁矿的PGE模式不取决于铬铁矿的化学成分，而取决于其母岩性质以及形成温度和铂族元素的熔点。