Petrography,chemical composition,and Raman spectra of chrome spinel: Constraints on the diamond potential of the No. 30 pipe kimberlite in Wafangdian,North China Craton

Conventional diamond exploration seldom searches directly for diamonds in rock and soil samples. Instead, it focuses on the search for indicator minerals like chrome spinel, which can be used to evaluate diamond potential. Chrome spinels are preserved as pristine minerals in the early Paleozoic (∼465 Ma), hydrothermally altered, Group I No. 30 pipe kimberlite that intruded the Neoproterozoic Qingbaikou strata in Wafangdian, North China Craton (NCC). The characteristics of the chrome spinels were investigated by petrographic observation (BSE imaging), quantitative chemical analysis (EPMA), and Raman spectral analysis. The results show that the chrome spinels are mostly sub-rounded with extremely few grains being subhedral, and these spinels are macrocrystic, more than 500 µm in size. The chrome spinels also have compositional zones: the cores are classified as magnesiochromite as they have distinctly chromium-rich (Cr₂O₃ up to 66.56 wt%) and titanium-poor (TiO₂ < 1 wt%) compositions; and the rims are classified as magnetite as they have chromium-poor and iron-rich composition. In the cores of chrome spinels, compositional variations are controlled by Al³⁺-Cr³⁺ isomorphism, which results in a strong Raman spectra peak (A_1g mode) varying from 690 cm⁻¹ to 702.9 cm⁻¹. In the rims of chrome spinel, compositional variations result in the A_1g peak varying from 660 cm⁻¹ to 672 cm⁻¹. The morphology and chemical compositions indicate that the chrome spinels are mantle xenocrysts. The cores of the spinel are remnants of primary mantle xenocrysts that have been resorbed, and the rims were formed during kimberlite magmatism. The compositions of the cores are used to evaluate the diamond potential of this kimberlite through comparison with the compositions of chrome spinels from the Changmazhuang and No. 50 pipe kimberlites in the NCC. In MgO, Al₂O₃ and TiO₂ versus Cr₂O₃ plots, the chrome spinels from the Changmazhuang and No. 50 pipe kimberlites are mostly located in the diamond stability field. However, only a small proportion of chrome spinels from No. 30 pipe kimberlite have same behavior, which indicates that the diamond potential of the former two kimberlites is greater than that of the No. 30 pipe kimberlite. This is also supported by compositional zones in the spinel grains: there is with an increase in Fe³⁺ in the rims, which suggests that the chrome spinels experienced highly oxidizing conditions. Oxidizing conditions may have been imparted by fluids/melts that have a great influence on diamond destruction. Here, we suggest that chrome spinel compositions can be a useful tool for identifying the target for diamond potential in the North China Craton.     

Geochemistry of platinum-group elements and mineral composition in chromitites and associated rocks from the Abdasht ultramafic complex,Kerman, Southeastern Iran

The Abdasht complex is a major ultramafic complex in south-east Iran (Esfandagheh area). It is composed mainly of dunite, harzburgite, podiform chromitites, and subordinate lherzolite and wehrlite. The podiform chromitites display massive, disseminated, banded and nodular textures. Chromian spinels in massive chromitites exhibit a uniform and restricted composition and are characterized by Cr# [= Cr / (Cr + Al)] ranging from 0.76 to 0.77, Mg# [= Mg/(Mg + Fe^2 +)] from 0.63 to 0.65 and TiO₂ < 0.2 wt.%. These values may reflect crystallization of the chromian spinels from boninitic magmas. Chromian spinels in peridotites exhibit a wide range of Cr# from 0.48 to 0.86, Mg# from 0.26 to 0.56 and very low TiO₂ contents (averaging 0.07 wt.%). The Fe^3 +# is very low, (< 0.08 wt.%) in the chromian spinel of chromitites and peridotites of the Abdasht complex which reflects crystallization under low oxygen fugacities.The distribution of platinum group elements (PGE) in Abdasht chromitites displays a high (Os + Ir + Ru)/(Rh + Pt + Pd) ratio with strongly fractionated chondrite-normalized PGE patterns typical of ophiolitic chromitites. Moreover, the Pd/Ir value, which is an indicator of PGE fractionation, is very low (< 0.1) in the chromitites.The harzburgite, dunite and lherzolite samples are highly depleted in PGE contents relative to chondrites. The Pd_N/Ir_N ratios in dunites are unfractionated, averaging 0.72, whereas the harzburgites and lherzolites show slightly positive slopes PGE spidergrams, together with a small positive Ru anomaly, and their Pd_N/Ir_N ratio averages 2.4 and 2.3 respectively. Moreover, the PGE chondrite and primitive mantle normalized patterns of harzburgite, dunite and lherzolite are relatively flat which are comparable to the highly depleted mantle peridotites.The mineral chemistry data and PGE geochemistry indicate that the Abdasht chromitites and peridotites were generated from a melt with boninitic affinity under low oxygen fugacity in a supra-subduction zone setting. The composition of calculated parental melts of the Abdasht chromitites is consistent with the differentiation of arc-related magmas.     

Compositional signatures of SSZ-type peridotites from the northern Vourinos ultra-depleted upper mantle suite,NW Greece

The northern Vourinos massif, located in the Dinarides-Hellenides mountain belt in the Balkan Peninsula, forms a section of the so-called Neotethyan ophiolitic belt in the Alpine-Himalayan orogenic system. It is comprised mainly of a well-preserved mantle sequence, dominated by voluminous massive harzburgite with variable clinopyroxene and olivine modal abundances, accompanied by subordinate coarse- and fine-grained dunite. The harzburgite rock varieties are characterized by high Cr# [Cr/(Cr + Al)] values in Cr-spinel (0.47–0.74), elevated Mg# [Mg/(Mg + Fe²⁺)] in olivine (0.90–0.93), low Al₂O₃ content in clinopyroxene (≤1.82 wt.%) and low average bulk-rock concentrations of CaO (0.52 wt.%) and Al₂O₃ (0.40 wt.%), which are indicative of their refractory nature. In addition, dunite-type rocks display even more depleted compositions, containing Cr-spinel and olivine with higher Cr# (0.76–0.84) and Mg# (0.91–0.94), respectively. They also display extremely low average abundances of CaO (0.13 wt.%) and Al₂O₃ (0.15 wt.%). The vast majority of the studied peridotites are also strongly depleted in REE. Simple batch and fractional melting models are not sufficient to explain their ultra-depleted composition. Whole-rock trace element abundances of the northern Vourinos mantle rocks can be modeled by up to 22–31% closed-system non-modal dynamic melting of an assumed primitive mantle (PM) source having spinel lherzolite composition. The highly depleted compositional signatures of the investigated peridotites indicate that they have experienced hydrous melting in the fore-arc mantle region above a SSZ. This intense melting event was responsible for the release of arc-related melts from the mantle. These melts reacted with the studied peridotites causing incongruent melting of pyroxenes followed by considerable olivine and Cr-spinel addition in terms of cryptic metasomatism. This later metasomatic episode has obscured any geochemical fingerprints indicative of an early mantle melting event in a MOR setting. The lack of any MOR-type peridotites in the northern Vourinos depleted mantle suite is quite uncommon for SSZ-type Neotethyan ophiolites.     

Serpentinized Peridotites at the North Part of the Wadi Allaqi District (Egypt): Implications for the Tectono-Magmatic Evolution of Fore-arc Crust

The Neoproterozoic Allaqi-Heiani suture （800-700 Ma） in the south Eastern Desert of Egypt is the northernmost linear ophiolitic belt that defines an arc-arc suture in the Arabian- Nubian shield （ANS）. The Neoproterozoic serpentinized peridotites represent a distinct lithology of dismembered ophiolites along the Allaqi-Heiani suture zone. The alteration of peridotites varies, some contain relicts of primary minerals （Cr-spinel and olivine） and others are extremely altered, especially along thrusts and shear zones, with development of talc, talc-carbonate and quartz-carbonate. The fresh cores of the chromian spinels are rimmed by ferritchromite and Cr- magnetite. The fresh chromian spinels have high Cr# （0.62 to 0.79）, while Mg# shows wider variation （0.35-0.59）. High Cr# in the relict chromian spinels and Fo content in the primary olivines indicate that they are residual peridotites after extensive partial melting. The studied ophiolitic upper mantle peridotites are highly depleted and most probably underwent high degrees of partial melting at a supra-subduction zone setting. They can be produced by up to -20%-22% dynamic melting of a primitive mantle source. The mineralogical and geochemical features of the studied rocks reflect that the mantle peridotites of the north part of the Wadi Allaqi district are similar to the fore-arc peridotites of a supra-subduction zone.     

Coexistence of the moderately refractory and fertile mantle beneath the eastern Central Asian Orogenic Belt

Relative to the North China Craton, the subcontinental lithospheric mantle (SCLM) beneath the Central Asian Orogenic Belt is little known. Mantle-derived peridotite xenoliths from the Cenozoic basalts in the Xilinhot region, Inner Mongolia, provide samples of the lithospheric mantle beneath the eastern part of the belt. The xenoliths are predominantly lherzolites with minor harzburgites, and can be subdivided into three groups, based on the REE patterns of clinopyroxenes. Group 1 peridotites (LREE-enriched), with low modal Cpx (3–7%), high Mg^# in olivine (> 90.6) and Cr^# in spinel (> 43.8), low whole-rock CaO + Al₂O₃ contents (1.62–3.22 wt.%) and estimated temperatures of 1043–1126 °C, represent moderately refractory SCLM that has experienced carbonatite-related metasomatism. Group 2 peridotites (LREE-depleted), with high modal Cpx (9–13%), low Mg^# in olivine (< 90.6) and Cr^# in spinel (< 20.0), high whole-rock CaO + Al₂O₃ contents (4.93–6.37 wt.%) and estimated temperatures of 814–970 °C, show affinity with Phanerozoic fertile SCLM that has undergone silicate-related metasomatism. Group 3 peridotites (convex-upward REE patterns), show wide ranges of olivine-Mg^# (88.4–90.6), spinel-Cr^# (11.5–47.6), and modal Cpx (3–14%) that overlap Groups 1 and 2. Their spinels have high TiO₂ contents (> 0.41 wt.%), implying involvement of reactions between melt and peridotites. The estimated temperatures of Group 3 (1033–1156 °C) are similar to those of Group 1. We suggest that the pre-existing moderately refractory lithospheric mantle (i.e., Group 1) beneath the eastern part of the Central Asian Orogenic Belt was strongly penetrated by upwelling asthenospheric material, and the cooling of this material produced fertile lithospheric mantle (i.e., Group 2). The present lithospheric mantle of this area consists of interspersed volumes of younger fertile and older more refractory lithosphere, with the fertile type dominating the shallower levels of the mantle.     

Structural and magnetic microinhomogeneities in accessory spinel of the system Fe2+(Cr2–xFex3+)O4 from the Kytlym massif (Urals platinum-bearing belt)

The microstructure and magnetic properties of accessory Fe–Cr-spinels from the Kytlym massif of the Urals platinum-bearing belt were studied. Atypical Fe–Cr-spinels in the form of magnetic microareas in grains of primary nonmagnetic Fe–Cr-spinel have been revealed for the first time in the bed dunites of the Kytlym multiphase concentrically zoned massif, North Urals. These spinels are responsible for the magnetic properties of the dunites. It has been established that the microareas are separations in solid solution Fe²⁺(Cr_2–xFe_x³⁺)O₄, which are enriched in Fe^3 + and are probably an intermediate product of the transformation of primary accessory Fe-Cr-spinel during the formation of the dunite massif. These are magnetic microphases with particular chemical composition, cation distribution, and corresponding reversed crystal lattice, which determine the main magnetic properties of the microarea: the magnitude and direction of magnetization vector and Curie temperature. The formation of this earlier unknown type of magnetic Fe–Cr-spinel is probably conjugate with the formation and concentration of PGE mineralization in the bed dunites of the Kytlym platinum-bearing massif. The presence of such magnetization carriers in rocks and ores must be taken into account in geophysical research at the Urals chromite and platinum–chromite deposits.     

Alteration patterns of chromian spinels from La Cabaña peridotite,south-central Chile

La Cabaña peridotite is part of a dismembered ophiolite complex located within the metamorphic basement of the Coastal Cordillera of south-central Chile, and is the only location in Chile were Cr-spinels have been described so far. The La Cabaña peridotite is part of the Western Series unit, which comprises meta-sedimentary rocks, metabasites, and serpentinized ultramafic rocks. This unit has been affected by greenschist-facies metamorphism with reported peak PT conditions of 7.0–9.3 kbar and 380°–420 °C. Within La Cabaña peridotite Cr-spinels are present in two localities: Lavanderos and Centinela Bajo. In Lavanderos, Cr-spinel occurs in small chromitite pods and as accessory/disseminated grains with a porous or spongy texture in serpentinite, whereas in Centinela Bajo Cr-spinel is present as accessory zoned grains in partly serpentinized dunites, and in chromitite blocks. All Cr-spinels display variable degrees of alteration to Fe²⁺-rich chromite with a variation trend of major elements from chromite to Fe²⁺-rich chromite similar to those observed in other locations, i.e., an increase in Fe₂O₃ and FeO, a decrease in Al₂O₃ and MgO. Cr₂O₃ content increases from chromite to Fe²⁺-rich chromite in chromitite pods from Lavanderos and chromitite blocks from Centinela Bajo, but decreases in ferrian chromite zones in accessory grains from Centinela Bajo. The minor element (Ti, V, Zn, Ni) content is mostly low and does not exceed 0.4 wt.%, with the exception of MnO (<0.9 wt.%), which shows a correspondence with increasing degree of alteration. Cr# (Cr/Cr?+?Al) versus Mg# (Mg/Mg?+?Fe²⁺) and Fe³⁺/Fe³⁺+Fe²⁺ versus Mg# plots are used to illustrate the Cr-spinel alteration process. Overall, the Cr-spinels from Lavanderos (chromitite pods and disseminated grains) exhibit Cr# values ranging from 0.6 to 1.0, Mg# (Mg/Mg?+?Fe²⁺) below 0.5, and (Fe³⁺/Fe³⁺+Fe²⁺) <0.4. Cr-spinels from chromitites in Centinela Bajo have Cr# and Mg# values that range from 0.65 to 1.0, and 0.7-0.3, respectively, and (Fe³⁺/Fe³⁺+Fe²⁺)?3+/Fe³⁺+Fe²⁺) ratio is less than 0.4 in chromite cores and Fe²⁺-rich chromite, and >0.5 in ferrian chromite and Cr-magnetite. Interpretation of the data obtained and Cr-spinel textures indicate that the alteration of Cr-spinel is a progressive process that involves in its initial stages the reaction of chromite with olivine under water-saturated conditions to produce clinochlore and Fe²⁺-rich chromite. During this stage the chromite can also incorporate Ni, Mn, and/or Zn from the serpentinization fluids. As alteration progresses, Fe²⁺-rich chromite loses mass resulting in the development of a spongy texture. In a later stage and under more oxidizing conditions Fe³⁺ is incorporated in chromite/Fe²⁺-rich chromite shifting its composition to an Fe³⁺-rich chromite (i.e., ferrian chromite). Depending on the fluid/rock and Cr-spinel/silicate ratios, Cr-magnetite can also form over Fe²⁺-rich chromite and/or ferrian chromite as a secondary overgrowth. The compositional changes observed in Cr-spinels from La Cabaña reflect the initial stages of alteration under serpentinization conditions. Results from this study show that the alteration of Cr-spinels is dependent on temperature. The degree and extent of alteration (formation of Fe²⁺-rich and/or ferrian chromite) are controlled by the redox nature of the fluids, the Cr-spinel/silicate and the fluid/rock ratios.     

Peridotite-chromitite complexes in the Eastern Desert of Egypt: Insight into Neoproterozoic sub-arc mantle processes

The Neoproterozoic peridotite-chromitite complexes in the Central Eastern Desert of Egypt, being a part of the Arabian-Nubian Shield, are outcropped along the E–W trend from Wadi Sayfayn, Wadi Bardah, and Jabal Al-Faliq to Wadi Al-Barramiyah, from east to west. Their peridotites are completely serpentinized, and the abundance of bastite after orthopyroxene suggests harzburgite protoliths with subordinate dunites, confirmed by low contents of Al₂O₃, CaO and clinopyroxene (< 3 vol%) in bulk peridotites. The primary olivine is Fo89.3–Fo92.6, and the residual clinopyroxene (Cpx) in serpentinites contains, on average, 1.1 wt% Al₂O₃, 0.7 wt% Cr₂O₃, and 0.2 wt% Na₂O, similar in chemistry to that in Izu-Bonin-Marian forearc peridotites. The wide range of spinel Cr-number [Cr/(Cr + Al)], 0.41–0.80, with low TiO₂ (0.03 wt%), MnO (0. 3 wt%) and Y_Fe [(Fe^3 +/(Cr + Al + Fe^3 +) = 0.03 on average)] for the investigated harzburgites-dunites is similar to spinel compositions for arc-related peridotites. The partial melting degrees of Bardah and Sayfayn harzburgites range mainly from 20 to 25% and 25 to 30% melting, respectively; this is confirmed by whole-rock chemistry and Cpx HREE modelling (~ 20% melting). The Barramiyah peridotite protoliths are refractory residues after a wide range of partial melting, 25–40%, where more hydrous fluids are available from the subducting slab. The Neoproterozoic mantle heterogeneity is possibly ascribed mainly to the wide variations of partial melting degrees in small-scale areas, slab-derived inputs and primordial mantle compositions. The Sayfayn chromitites were possibly crystallized from island-arc basaltic melts, followed by crystallization of Barramiyah chromitites from boninitic melt in the late stage of subduction. The residual Cpx with a spoon-shape REE pattern is rich in both LREE and fluid-mobile elements (e.g., Pb, B, Li, Ba, Sr), but poor in HFSE (e.g., Ta, Nb, Zr, Th), similar to Cpx in supra-subduction zone (SSZ) settings, where slab-fluid metasomatism is a prevalent agent. The studied chromitites and their host peridotites represent a fragment of sub-arc mantle, and originated in an arc-related setting. The systematic increase in the volume of chromitite pods with the increasing of their host-peridotite thickness from Northern to Southern Eastern Desert suggests that the thickness of wall rocks is one factor controlling the chromitite size. The factors controlling the size of Neoproterozoic chromitite pods are the thickness, beside the composition, of the host refractory peridotites, compositions and volumes of the supplied magmas, the amount of slab-derived fluids, and possibly the partial melting degree of the host peridotites.     

Chrome-spinels in serpentinites and talc carbonates of the El Ideid-El Sodmein District, central Eastern Desert, Egypt: their metamorphism and petrogenetic implications

Serpentinites and talc-carbonate rocks of El Ideid-El Sodmein District (ISD), central Eastern Desert, Egypt, contain variably altered chrome-spinels. Back-scattered electron images and electron microprobe analyses of chrome-spinels and associated silicates are made to evaluate their textural and compositional variations with metamorphism. In most cases the chrome-spinel crystals are concentrically zoned with unaltered cores through transitional zone of ferritchromit to Cr-magnetite toward the rims. In talc-carbonate rocks chrome-spinels are extensively altered to Cr-magnetite. Compared to cores, the metamorphic rims are enriched in Cr# (0.83–1.0 vs. 0.58–0.63 for rims and cores, respectively) and impoverished in Mg# (0.05–0.29 vs. 0.57–0.63), due to Mg–Fe and Al(Cr)–Fe³⁺ exchange with the surrounding silicates during regional metamorphism rather than serpentinization process. Textural and compositional features of the chrome-spinels suggest transitional greenschist-amphibolite up to lower amphibolite facies metamorphism (at 500–600 °C), which is isofacial with the country rocks. The common preservation of unaltered chrome-spinel cores in the serpentinites, contrary to talc-carbonate rocks, implies that full equilibration has not been attained due to small metamorphic fluid–rock ratio. Microprobe analyses profile across a concentrically zoned grain confirms the presence of two compositional (miscibility?) gaps; one between chrome-spinel core and ferritchromit zone; and another one between ferritchromit zone and Cr-magnetite outer rim.Chrome-spinel cores do not appear to have re-equilibrated completely with the metamorphic spinel rims and surrounding silicates, indicating relic magmatic composition not affected by metamorphism. Core compositions suggest an ophiolitic origin and derivation by high degrees of melting of reduced, depleted harzburgite to dunite mantle peridotites in an oceanic supra-subduction zone (marginal-basin) tectonic environment.     

Chromitites from the Luanga Complex,Carajás,Brazil: Stratigraphic distribution and clues to processes leading to post-magmatic alteration

The Neoarchean (ca. 2.75 Ga) Luanga Complex, located in the Carajás Mineral Province in Brazil, is a medium-size layered intrusion consisting, from base to top, of ultramafic cumulates (Ultramafic Zone), interlayered ultramafic and mafic cumulates (Transition Zone) and mafic cumulates (Mafic Zone). Chromitite layers in the Luanga Complex occur in the upper portion of interlayered harzburgite and orthopyroxenite of the Transition Zone and associated with the lowermost norites of the Mafic Zone. The stratigraphic interval that hosts chromitites (∼150 meters thick) consists of several cyclic units interpreted as the result of successive influxes of primitive parental magma. The compositions of chromite in chromitites from the Transition Zone (Lower Group Chromitites) have distinctively higher Cr# (100Cr/(Cr + Al + Fe³⁺)) compared with chromite in chromitites from the Mafic Zone (Upper Group Chromitites). Chromitites hosted by noritic rocks are preceded by a thin layer of harzburgite located 15–20 cm below each chromitite layer. Lower Cr# in chromitites hosted by noritic rocks are interpreted as the result of increased Al₂O₃ activity caused by new magma influxes. Electron microprobe analyses on line transverses through 35 chromite crystals indicate that they are rimmed and/or extensively zoned. The composition of chromite in chromitites changes abruptly in the outer rim, becoming enriched in Fe³⁺ and Fe²⁺ at the expense of Mg, Cr, Al, thus moving toward the magnetite apex on the spinel prism. This outer rim, characterized by higher reflectance, is probably related to the metamorphic replacement of the primary mineralogy of the Luanga Complex. Zoned chromite crystals indicate an extensive exchange between divalent (Mg, Fe²⁺) cations and minor to none exchange between trivalent cations (Cr³⁺, Al³⁺ and Fe³⁺). This Mg-Fe zoning is interpreted as the result of subsolidus exchange of Fe²⁺ and Mg between chromite and coexisting silicates during slow cooling of the intrusion. A remarkable feature of chromitites from Luanga Complex is the occurrence of abundant silicate inclusions within chromite crystals. These inclusions show an adjacent inner rim with higher Cr# and lower Mg# (100 Mg/(Mg + Fe²⁺)) and Al# (100Al/(Cr + Al + Fe³⁺)). This compositional shift is possibly due to crystallization from a progressively more fractionated liquid trapped in the chromite crystal. Significant modification of primary cumulus composition of chromite, as indicated in our study for the Luanga Complex, is likely to be common in non-massive chromitites and the rule for disseminated chromites in mafic intrusions.     

西藏罗布莎蛇绿岩中不同产出的纯橄岩及成因探讨

罗布莎蛇绿岩中的纯橄岩有三种产出情况,除了与豆荚状铬铁矿伴生的薄壳状纯橄岩外,还有产在方辉橄榄岩底部被认为是堆晶岩的厚层状纯橄岩和方辉橄榄岩中的透镜状纯橄岩。厚层状纯橄岩约700～1000m厚,以橄榄石富镁(Fo93～95),单斜辉石低铝富镁(Al2O30.47%～0.85%,Mg#95～97),铬尖晶石高铬低镁(Cr#值平均77,Mg#平均51)为特征。该纯橄岩中的浸染状铬铁矿也是高铬低镁型,但Mg#值(平均59)高于厚层状纯橄岩的副矿物铬尖晶石。薄壳状纯橄岩与厚层状纯橄岩成分相近,其橄榄石Fo92～94,单斜辉石Al2O3<1%和Mg#95～97;铬尖晶石的Cr#值平均71,Mg#值平均52。与薄壳状纯橄岩伴生的块状铬铁矿为高镁高铬型,但Mg#值(平均68)相对更高些,Cr#值平均79。透镜状纯橄岩的特征是橄榄石Fo(91～92)和铬尖晶石Cr#(60左右)均低于前两类纯橄岩,但单斜辉石的Al2O3(1.41%～1.71%)则高于前两者。透镜状纯橄岩的矿物成分与方辉橄榄岩重叠,两者为渐变过渡关系。研究对比表明,罗布莎厚层状纯橄岩不同于经典的蛇绿岩的超镁铁质堆晶岩,认为将其成因解释为拉斑玄武质熔体与地幔橄榄岩的反应较为合理。透镜状纯橄岩与方辉橄榄岩存在成生联系,可能是地幔橄榄岩高度部分熔融的产物,或熔体和方辉橄榄岩在原位发生反应的产物;薄壳状纯橄岩成因与厚层状纯橄岩相同,但与其相伴的块状铬铁矿是否由拉斑玄武质熔体与方辉橄榄岩反应形成,值得商榷。     

地幔橄榄岩捕掳体中尖晶石筛状边的成因

山东的无棣大山和栖霞方山是两个以霞石岩为主的新生代火山,含有大量的地幔橄榄岩捕掳体,橄榄岩捕掳体中的尖晶石常见黑色反应边。在BSE图像上,这些反应边根据结构的不同又可以进一步分为两种:筛状边和均一边。有时两种反应边在同一颗尖晶石中共存并相互过渡。尖晶石捕掳晶和捕掳体中与寄主岩直接接触的尖晶石常发育均一边;发育筛状边的尖晶石则一般不直接与寄主岩接触,但位于捕掳体的边缘。尖晶石的筛状边呈多孔状,为富Cr尖晶石或铬铁矿。筛状边成分上与核部(Cr_2O_3=7.52%~36.75%,Cr#=7.80~44.20,Mg#=44.70~74.48)区别明显,具有高的Cr_2O_3含量(23.42%~65.96%)、Cr#值(78.97~92.49)以及低的Mg#值(17.22~43.02)。另外,筛状边相对其核部(TiO 2=0.00%~0.53%,MnO=0.04%~0.35%)还显示偏高的TiO 2(0.20%~3.60%)和MnO(0.29%~1.93%)。在筛状边附近存在富Al_2O_3(8.00%~17.57%)和MgO(17.89%~26.02%)的玻璃。尖晶石的均一边无孔洞但多发育裂理,成分上与核部突变,并以富TiO 2(20.90%~6.64%)和FeO T(70.79%~53.92%)为特征,最外部为钛磁铁矿。均一边具有明显的成分分带,表现为由内至外TiO 2、FeO T含量逐渐增高,Al_2O_3(0.04%~16.34%)、Cr_2O_3(0.77%~25.69%)和MgO(0.50%~7.16%)含量逐渐降低。尖晶石的两种反应边与寄主岩密切的空间关系说明其成因与寄主岩浆有关。虽然尖晶石筛状边的Cr#值(79.0~92.5)明显高于核部(7.8~44.2),但是其相对核部偏高的TiO 2和MnO含量,以及显著降低的Mg#值均与单纯的部分熔融趋势不吻合。根据尖晶石两种反应边的结构特征、成分特征和相互的空间关系,我们认为筛状边与均一边是岩浆与尖晶石反应不同阶段的产物。当橄榄岩捕掳体被岩浆捕获后,由于成分上的不均衡两者之间将发生溶解反应。反应过程中,尖晶石中不同元素向熔体迁移的速率区别明显,其中Cr是最难熔的元素也是迁移最慢的元素。在反应的初始阶段,由于易溶组份Al、Mg等元素随熔体迁出,尖晶石发育筛状边,并同时伴随Cr#值的显著升高和Mg#值的显著降低。此时,寄主岩浆中的Ti、Mn等元素也部分扩散进入筛状边中的残留尖晶石。如果熔体足够多,反应得以持续进行,筛状边中的Cr最终也将被熔体带走。在反应产生的混合熔体中金属氧化物最早达到饱和并结晶。随着反应的持续进行,结晶出的矿物将继续生长、变粗,并相互连接,直至孔洞消失形成均一边。同时伴随着矿物的不断结晶,溶解界面上的熔体成分也不断变化,从而使均一边具有明显的成分分带。在橄榄岩捕掳体内部,由于渗进捕掳体中的岩浆有限,渗透岩浆与尖晶石之间的反应多限于早期阶段,反应产物为筛状边。在捕掳体边缘,与寄主岩浆直接接触的尖晶石由于参与反应的岩浆量足够多,因此一般产生反应的终端产物———均一边。     

Nano-mineralogy and -geochemistry of high-grade diasporic karst-type bauxite from Parnassos-Ghiona mines,Greece

In the present work, a combination of various techniques is utilized for the study of nano-mineralogy and -geochemistry of high-grade karst-type bauxite (Al-rich and Fe-depleted samples; Al₂O₃ ca. 80 wt.%) from the Parnassos-Ghiona mines located in Greece. Initial characterization using PXRD and electron microscopy in microscale and mesoscale (SEM-EDS including STEM mode), proved the presence of “Fe-Cr-Ti-containing diaspore”, anatase and minor rutile. The study by means of ⁵⁷Fe Mössbauer spectroscopy, in correlation with magnetic susceptibility measurements and, complemented, with Synchrotron-based spectroscopies at the microscale (SR micro-XRF and micro-XANES/-EXAFS), indicated that Fe³⁺, in contrast to ^[6]Cr³⁺, is not exclusively a component of the diaspore structure. While Cr^3 + substitutes Al^3 + in octahedral sites of diaspore (^[6]Cr³⁺ ↔ ^[6]Al³⁺), the electron microscopy in nanoscale (TEM-EDS & EELS) revealed that Fe exists in the form of peculiar Fe³⁺-bearing nanominerals (most likely maghemite-type phases) between 25 and 45 nm in size, in addition to the Fe³⁺ ions substituting Al³⁺ in the diaspore structure. Moreover, it was proven that TiO₂ polymorph mineral nanoparticles, particularly rounded anatase mesocrystals and nanocrystals and individual needle-shaped rutiles, are dispersed into the diaspore matrix. Thus, diaspore in the studied bauxite concerns -in fact- a distinct Fe³⁺-Cr³⁺-AlOOH low-T authigenic phase, demonstrated for the first time in literature. On the other hand, the observed TiO₂ mineral nanoparticles (formed, together with diaspore, during diagenesis) and Fe nanominerals (formed during epigenesis) were hitherto unknown not only for the allochthonous karst-type bauxite deposits of Greece, but also for the overall bauxite deposits, worldwide.     

Lithium elemental and isotopic variations in rock-melt interaction

Despite the occurrence of highly variable lithium (Li) elemental distribution and isotopic fractionation in mantle mineral, the mechanism of Li heterogeneity and fractionation remains a controversial issue. We measured Li contents and isotopic compositions of olivine and clinopyroxene xenocrysts and phenocrysts from kamafugite host lavas, as well as minerals in melt pockets occurring as metasomatic products in peridotite xenoliths from the Western Qinling, central China. The olivine xenocrysts in the kamafugites show compositional zonation. The cores have high Mg# (100 × Mg/(Mg+Fe); 91.0–92.2) and Li abundances (5.63–21.7 ppm), low CaO contents (≤0.12 wt%) and low δ⁷Li values (−39.6 to −6.76‰), which overlap with the compositional ranges of the olivines in the melt pockets as well as those in peridotite xenoliths. The rims of the olivine xenocrysts display relatively low Mg# (85.9–88.2), high CaO contents (0.19–0.38 wt%) and high δ⁷Li values (18.3–26.9‰), which are comparable to the olivine phenocrysts (Mg#: 86.4–87.1; CaO: 0.20–0.28 wt%; Li: 12.4–36.8 ppm; δ⁷Li: 18.1–26.0‰) and the silicate-melt metasomatized olivines. The clinopyroxene phenocrysts and clinopyroxenes in the melt pockets have no distinct characteristics with respect to the Li abundances and δ⁷Li values, but show higher and lower CaO contents, respectively, than the clinopyroxenes from silicate and carbonatite metasomatized samples. These features indicate that Li concentration and isotopic signatures of the cores of the xenocrysts recorded carbonatite melt-peridotite reaction (carbonatite metasomatism) at mantle depth, and the variations in the rims probably resulted from xenocryst–host magma interaction during ascent. Our results reveal that the interaction with carbonatite and silicate melts gave rise to an increase in Li abundance in minerals of peridotite xenoliths at mantle depth or during transportation. In terms of δ⁷Li, the carbonatite and silicate melts produced remarkably contrasting δ⁷Li variations in olivine. Based on the systematic variations of Li abundances and Li isotopes in olivines, we suggest that the δ⁷Li value of olivine is a more important indicator than that of clinopyroxene in discriminating carbonatite and silicate melt interaction agents with peridotites.     

Chromite typology and composition characterized through multispectral specular reflectance

Determination of multispectral specular reflectance is an important tool for ore identification in reflected light microscopy, and may be used for automated characterization of ores. However, reflectance values can be affected by compositional variations in a way that is seldom understood. The aim of the present work is to investigate this problem in chromite, an ore whose composition may show typically large natural variations as member of the spinel family, and whose relatively high reflectance variations are apparently unpredictable. For this research, eighteen samples of chromian spinel covering a large range of compositions in the base of the Hagerthy prism were selected for microprobe analysis and reflectance measure on polished sections. The samples belong to a variety of deposits and types (ultramafic massif, ophiolitic, and metamorphosed types: Ojén and Ronda Massifs, Spain; Mayarí, Moa-Baracoa, Camagüey and Sagua de Tánamo, Cuba; Golyamo Kemenyane, Avren and Yakovitsa, Bulgaria). The specular reflectances are characterized as multispectral values, measured at thirteen intervals (50 nm each) in the VNIR region (Visible and Near-Infrared: 400–1000 nm), using the automated CAMEVA System.The relationship between compositional and reflectance values is studied by multivariate analysis and subsequently tested on independent samples. For this purpose, the samples have been grouped in two sets: a larger population of fifteen samples constitutes the initial data set for mathematical processing, while a selection of three samples of widely differing compositions is used to test the resulting functions, so as to gain a critical appraisal of their validity.The results obtained show that the specular reflectance of chromite depends on composition and can be used to estimate compositional parameters, as #Cr = Cr/(Cr + Al) or #Mg = Mg/(Mg + Fe²⁺), but this relationship is complex and does not allow simple direct determinations, due to the multiplicity of possible changes and coupled substitutions (e.g. Al–Cr–Fe³⁺, or Mg-Fe²⁺, Ni, Zn, Ti …) in the chromian spinel family. On the other hand, the relationship of chromite composition with deposit type is also detectable through the reflectance values, but with a higher uncertainty. Reflectance increases with increasing Cr and Fe³⁺ contents in all cases, but the relationship of reflectance with Mg seems to be specific of the deposit type: while reflectance increases with increasing #Mg in the Ojén chromites, it shows the opposite behaviour in podiform chromites. Although these results should be regarded as preliminary until further studies on larger sample populations can be achieved, they are suggestive of possible practical applications for exploration, e. g. to approach Cr-spinel compositions or chromite deposit typology, early in an exploration campaign, by inexpensive reflected light determination of specular reflectance in a few samples.     

Base metal mineral segregation and Fe-Mg exchange inducing extreme compositions of olivine and chromite from the Xiadong Alaskan-type complex in the southern part of the Central Asian Orogenic Belt

The Xiadong Alaskan-type complex shares much in common with typical Alaskan-type complexes worldwide, while showing some unique features in terms of mineral compositions. Olivine from the Xiadong dunites is characterized by extremely high Fo component of 91.7–96.7 and anomalously negative correlation of Fo with NiO, while chromite is featured by high 100 × Fe³⁺/(Fe³⁺ + Cr + Al) (>70), high 100 × Fe²⁺/(Fe²⁺ + Mg) (>70), high 100 × Cr/(Cr + Al) (>90), low MnO (<0.6 wt%) and TiO₂ contents (<0.5 wt%). To investigate these particular features, we conducted petrographic observation and mineral composition analyses for the Xiadong dunite. A number of Fe and/or Ni sulfides and alloys occurring as inclusions in olivine and chromite indicate that base metal mineral segregation took place prior to crystallization of olivine and chromite and probably induced Fe and Ni depletions in olivine. The FeO and MgO variations in profile analyses from chromite to adjacent olivine are compatible with Fe-Mg exchange. The diffusion mechanism of Fe from olivine to chromite and Mg from chromite to olivine may have elevated both Fo of olivine and 100 × Fe²⁺/(Mg + Fe²⁺) ratio of chromite and further enhanced the decoupling of Fo and NiO in olivine. We thus suggest that base metal mineral segregation and Fe-Mg exchange play important roles in the extreme compositions of the Xiadong dunite. The Ni depletion of olivine and degree of Fe-Mg exchange between olivine and chromite may be used as indicators of mineralization in mafic-ultramafic intrusions.     

Chemical variations of abyssal peridotites in the central Oman ophiolite: Evidence of oceanic mantle heterogeneity

Basal peridotites above the metamorphic sole outcropped around Wadi Sarami in the central Oman ophiolite give us an excellent opportunity to understand the spatial extent of the mantle heterogeneity and to examine peridotites−slab interactions. We recognized two types of basal lherzolites (Types I and II) that change upward to harzburgites. Their pyroxene and spinel compositions display severely variations at small scales over < 0.5 km, and encompass the entire abyssal peridotite trend; clinopyroxenes (Cpxs) show wide ranges of Al₂O₃, Na₂O, Cr₂O₃ and TiO₂ contents. Primary spinels show a large variation of Cr# [= Cr/(Cr + Al)] from 0.04 to 0.53, indicating various degrees of partial melting. Trace-element compositions of peridotites and their pyroxenes also show a large chemical heterogeneity in the base of the Oman mantle section. This heterogeneity mainly resulted from variations of partial-melting degrees due to the change of a mantle thermal regime and a distance from the spreading ridge or the mantle diapir. It was overlapped with subsolidus modification during cooling and fluid metasomatism prior and/or during emplacement. The studied peridotites are enriched in Rb, Cs, Ba, Sr and LREE due to fluid influx during detachment and emplacement stages. Chondrite (CI)-normalized REE patterns for pyroxenes are convex upward with strong LREE depletion due to their residual origin, similar to abyssal peridotites from a normal ridge segment. The Cpxs are enriched in fluid mobile elements (e.g., B, Li, Cs, Pb, Rb) and depleted in HFSE (Ta, Nb, Th, Zr) + LREE, suggesting no effect of melt refertilization. Their HREE contents, combined with spinel compositions, suggest two melting series with 1–5% melting for type II lherzolites, 3– < 10% melting for type I lherzolites and ~ 15% for harzburgites. Hornblendes are enriched in fluid-mobile elements relative to HFSE + U inherited from their precursor Cpx. The clinopyroxenite lens crosscuts the basal lherzolites, forming small-scale (< 5 cm) mineralogical and chemical heterogeneities. It was possibly formed from fractional crystallization of interstitial incremental melt that formed during decompression melting of a normal MORB mantle source. The studied peridotites possibly represent a chemical heterogeneity common to the mantle at an oceanic spreading center.     

Platinum group minerals in podiform chromitites of the Bou Azzer ophiolite, Anti Atlas, Central Morocco

Summary The Neoproterozoic Bou Azzer ophiolite complex hosts numerous, small lenticular bodies of massive and disseminated chromite. Metallurgical-grade high-Mg and high-Cr spinels (cores with 48–62 wt% Cr₂O₃) reveal complex alteration patterns of successive Cr and Mn enrichment and loss of Al towards the rims, while the Mg# ratios [(Mg/(Mg + Fe²⁺)] remain almost constant. Concentration patterns of platinum-group elements are typical for ophiolitic chromitite poor in sulfides, with predominance of the IPGE, variable Rh, and low Pt and Pd. The most abundant platinum-group mineral is Rh-bearing laurite that occurs either included in spinel or in silicate matrix, whereas Os-Ir-Ru alloy is always included in spinel. Laurite inclusions reveal complex intergrowth textures with Rh-Ru-Pt rich alloy, and with Rh-rich sulfide. Most laurites display trends to sulfur-poor compositions leading to local formation of very fine-grained Ru-Os-Ir alloy phases. Ni-Co-Fe sulfides, arsenides and sulfarsenides devoid of PGE are associated with the alteration of chromite. Textural position and chemical composition of the base metal inclusions, as well as comparison of alteration features between chromite and accessory chromian spinel in the Co-Ni-As ores of the Bou Azzer ophiolite indicate a close connection. It is suggested that hydrothermal fluids percolated through the marginal zones of the ophiolite belt during greenschist facies metamorphism and deposited Ni-Co-Fe arsenides, sulfarsenides and minor sulfides as accessories within altered chromitites, and also in structurally favourable zones as Ni-Co-As ores. Author’s address: Dr. Frank Melcher, Federal Institute for Geosciences and Natural Resources, Stilleweg 2, 30655 Hannover, Germany     

Serpentinization-driven extension in the Ronda mantle slab (Betic Cordillera,S. Spain)

We investigate the stress regimes acting during serpentinization and faulting of the largest known subcontinental lithospheric peridotite body, namely the Ronda peridotites (Betic Cordillera, S. Spain). Petrological and structural analyses on serpentinites grown along fault planes crosscutting the peridotite slab, reveal that they were developed during three superposed stress tensors: the oldest one (E1) is characterized by NW–SE sub-horizontal compression; the intermediate one consists in NE–SW to ENE–WSW extension with orthogonal compression (E2); and the youngest one (E3) shows a sub-vertical maximum stress axis and NW–SE sub-horizontal extension. During serpentinization, maximum and minimum stress axes flip between a NW–SE horizontal position and a vertical one in the whole peridotite body (E1 and E3), while E2 represents an intermediate stress stage. Field relationships and previous petrological and geochronological data indicate that serpentinization and associated stress tensors are coeval with intrusive leucogranite dikes crosscutting the peridotites, thus constraining these processes to 19–22 Ma and occurring at upper continental crust depths (P < 4 kbar). Gravity data reveal that the average density of the Ronda mantle slab (~ 2.7–2.8 g/cm³) shows a negligible contrast with the surrounding crustal rocks, thus suggesting that the peridotite body is serpentinized in a great proportion. Our preferred tectonic model to account for the evolution of the Ronda peridotites in the upper crust considers that E1 compression was linked to the collision of the Alborán continental domain with the Iberian passive margin during the Gibraltar Arc formation. Subsequently, the sudden onset of extension recorded within the peridotite slab (E2 and E3) was favored by serpentinization-driven buoyancy.     

New evidence of mantle heterogeneity beneath the Hyblean Plateau (southeast Sicily,Italy) as inferred from noble gases and geochemistry of ultramafic xenoliths

We analyzed major and trace elements, Sr and Nd isotopes in ultramafic xenoliths in Miocenic age Hyblean diatremes, along with noble gases of CO₂-rich fluid inclusions hosted in the same products. The xenoliths consist of peridotites and pyroxenites, which are considered to be derived from the upper mantle. Although the mineral assemblage of peridotites and their whole-rock abundance of major elements (e.g., Al₂O₃ = 0.8–1.5 wt.%, TiO₂ = 0.03–0.08 wt.%) suggest a residual character of the mantle, a moderate enrichment in some incompatible elements (e.g., La_N/Yb_N = 9–14) highlights the presence of cryptic metasomatic events. In this context a deep silicate liquid is considered the metasomatizing agent, which is consistent with the occurrence of pyroxenites as veins in peridotites. Both the Zr/Nb and ¹⁴³Nd/¹⁴⁴Nd ratios of the investigated samples reveal two distinct compositional groups: (1) peridotites with Zr/Nb ≈ 4 and ¹⁴³Nd/¹⁴⁴Nd ≈ 0.5129, and (2) pyroxenites with Zr/Nb ≈ 20 and ¹⁴³Nd/¹⁴⁴Nd ≈ 0.5130. The results of noble-gas analyses also highlight the difference between the peridotite and pyroxenite domains. Indeed, the ³He/⁴He and ⁴He/⁴⁰Ar* ratios measured in the fluid inclusions of peridotites (respectively 7.0–7.4 ± 0.1 Ra and 0.5–8.2, where Ra is the atmospheric ³He/⁴He ratio of 1.38 × 10^? 6) were on average lower than those for the pyroxenites (respectively 7.2–7.6 Ra and 0.62–15). This mantle heterogeneity is interpreted as resulting from a mixing between two end-members: (1) a peridotitic layer with ³He/⁴He ≈ 7 Ra and ⁴He/⁴⁰Ar* ≈ 0.4, which is lower than the typical mantle ratio (~ 1–4) probably due to melt extraction events, and (2) metasomatizing mafic silicate melts that gave rise to pyroxenites characterized by ³He/⁴He ≈ 7.6 Ra, with a variable ⁴He/⁴⁰Ar* due to degassing processes connected with the ascent of magma at different levels in the peridotite wall rock. The complete geochemical data set also suggests two distinct mantle sources for the xenolithic groups highlighted above: (1) a HIMU (high-μ)-type source for the peridotites and (2) a DM (depleted mantle)-type source for the pyroxenites.