Progressive hybridisation between Late Devonian mafic-intermediate and felsic magmas in the Meguma Zone of Nova Scotia, Canada

Two felsic plutons of Late Devonian (385–370 Ma) age in the Meguma Zone of southwestern Nova Scotia contain three circa 376 Ma synplutonic mafic-intermediate intrusions that collectively record progressive stages of in situ hybridisation. A 5 m wide spessartite dyke in the Port Mouton Pluton probably underwent rapid cooling and crystallisation immediately after intrusion, which heated and coarsened the adjacent tonalite. An 85 m long sheet of pillowed kersantite (also in tonalite of the Port Mouton Pluton) presumably contained residual magma after quenching and obtained K, P, Ba, Rb, more radiogenic Sr, Zr, Nb, and light REE from the tonalite during magma mingling. The third synplutonic body, a >100 m wide diorite sheet, intrudes granodiorite of the adjacent Shelburne Pluton and has a circa 45 m wide gradational contact of metaluminous hornblende-tonalite. This tonalite dominantly records magma mixing by the transfer of Ti, Mg, Fe, Ca, and V in hornblende, biotite, plagioclase, and (at least in part) apatite xenocrysts derived from dioritic pillows that were originally disaggregated in the granodiorite, probably in response to convection. Scattered data points, unusual “concave-down” variation trends for Al₂O₃, P₂O₅, and Sr, and non-hyperbolic Sr-Nd isotopic characteristics in the tonalite, apparently reflect syn- or post-mixing fractionation and accumulation of xenocrysts from residual magma. Phosphorus may have assisted diffusion of Sr, Zr, Nb, and light REE, and caused premature quenching of the hybrids at Mcleods Cove and Birchtown, during magma mingling and mixing. Received: 1 January 1996 / Accepted: 3 August 1996     

Experimental study of liquid immiscibility in the fluid-magmatic silicate systems containing Ti,Nb, Sr,REE, and Zr

Aluminosilicate alkaline systems containing Ti, REE (La, Ce), Y, Sr, and Nb were studied experimentally at T = 1200 and 1250°C and P = 2 kbar in the presence of aqueous and alkaline fluid. In the fluid-absent experiments with systems containing the same elements, loparite crystals in a silicate matrix were obtained. These systems in the presence of aqueous and alkaline fluid pressure conditions demonstrate an immiscible splitting into two liquids: (1) aluminosilicate matrix and (2) droplets enriched in Ti, REE (La, Ce), Y, Sr, and Nb, which contain silicate admixture and are compositionally close to loparites. According to approximate estimates, the partition coefficients between the melts of the droplets and aluminosilicate matrix (K = C _dr/C _sil) are more than 5 for TiO₂, < 0.35 for SiO₂, 10–20 for Nb₂O₅, > 15 for REE, and from 2.3 to 7.6 for SrO. Obtained unmixing may be of great significance for explaining the genesis of REE-Nb (loparite) deposits. In addition, the experiments demonstrate that Zr may be accumulated together with Ti and REE due to liquid immiscibility of this type. The partition coefficient of ZrO₂ between the melts of droplets and aluminosilicate matrix (K = C _dr/C _sil) according to approximate estimates varies from ∼ 3.5 to 9.     

Geology and genesis of the Toongi rare metal (Zr,Hf, Nb,Ta, Y and REE) deposit,NSW, Australia,and implications for rare metal mineralization in peralkaline igneous rocks

The Toongi Deposit, located in central NSW, Australia, hosts significant resources of Zr, Hf, Nb, Ta, Y and REE within a small (ca. 0.3 km²), rapidly cooled trachyte laccolith. Toongi is part of regional Late Triassic to Jurassic alkaline magmatic field, but is distinguished from the other igneous bodies by its peralkaline composition and economically significant rare metal content that is homogenously distributed throughout the trachyte body. The primary ore minerals are evenly dispersed throughout the rock and include lueshite/natroniobite and complex Na–Fe–Zr–Nb–Y–REE silicate minerals dominated by a eudialyte group mineral (EGM). The EGM occurs in a unique textural setting in the rock, commonly forming spheroidal or irregular-shaped globules, herein called “snowballs”, within the rock matrix. The snowballs are often protruded by aegirine and feldspar phenocrysts and contain swarms of fine aegirine and feldspar grains that often form spiral or swirling patterns within the snowball. Secondary ore minerals include REE carbonates, Y milarite, catapleiite and gaidonnayite that fill fractures and vesicles in the rock. Based on bulk-rock geochemical and Nd isotope data, and thermodynamic modelling of magma fractionation, the alkaline rocks of the region are interpreted to represent extrusive to hyperbyssal products of mantle-derived magma that ponded at mid-crustal levels (ca. 0.3 GPa) and underwent extensive fractionation under low-oxygen fugacity conditions. The high Na₂O, peralkaline nature of the Toongi Deposit trachyte developed via extensive fractionation of an alkali olivine basalt parental magma initially in the mid-crust and subsequently at shallow levels (ca. 0.1 GPa). This extended fractionation under low fO₂ and relatively low H₂O-activity conditions limited volatile release and allowed build-up of rare metal contents to ore grades. We speculate that the ore minerals may have originally formed from rare metal-rich sodic-silicate melt that formed immiscible globules (subsequently crystallized to EGM) in the magma shortly before emplacement and rapid cooling. Subsequent hydrothermal alteration caused relatively limited and localized remobilization of some ore metals into fractures and vesicles in the rock.     

The geochemical and genetic role of organic substances in postmagmatic derivatives of alkaline plutons

Solid bituminous substances (SBS) are common components of the late hydrothermal mineral assemblages of peralkaline pegmatites. SBS are formed in a reductive setting as a result of progressive sorption of minor carbon-bearing molecules (CO, CO₂, CH₄, C₂H₆, C₂H₄, etc.), their polymerization, transformation into aromatic compounds (reformation), and selective oxidation on microporous zeolite-like Ti-, Nb-, and Zrsilicates serving as sorbents and catalysts. The oxygen-bearing aromatic compounds with hydrophile functional groups (−OH, −C=O, −COOH, −COO) act as complexing agents with respect to Th, REE, U, Zr, Ti, Nb, Ba, Sr, Ca, resulting in transfer of these bitumenophile elements under low-temperature hydrothermal conditions in the form of water-soluble macroassociates of the micelle type. Th, REE, and to a lesser extent, U, Zr, Ti, and Nb concentrate at the late stage of the hydrothermal process as microphases impregnating SBS or macroscopic segregations of Th and REE minerals. At the final stage, homogeneous SBS break down into organic (partly together with Ca, Sr, Ba, and Pb) and mineral (with Th, Ln, Y, Ti, Nb, Ca, Na, K, Si) microphases.     

REE constraints on fractionation processes of massive-type anorthosites on the Lofoten Islands, Norway

Summary Rare Earth Element (REE) data of 34 samples of magmatic rocks from the Lofoten Islands in Norway lend support to the derivation of anorthosites, ferrodiorites and jotunites by fractionation and cumulus processes from typical basaltic magma. Both REE concentration and Eu anomalies (expressed as Eu/Eu^*) form continuous linear trends from anorthosite towards gabbro, ferrodiorite and jotunite in discrimination diagrams against molar CaO/Al₂O₃ ratios indicating the predominant accumulation of plagioclase. Eu/Eu^* decreases from about 4 in the cumulates (anorthosites) to around 1 in the fine-grained gabbroic dikes and to below 1 in some ferrodiorites and the jotunite. The various types of ferrodiorites and the jotunite are regarded as residual liquids, in some cases with variable amounts of cumulus plagioclase. The whole fractionation series from gabbro towards anorthosites and ferrodiorites can be observed in a single intrusion. With increasing fractionation, the REE patterns generally change from flat, slightly LREE-enriched or LREE-depleted to steep and strongly LREE-enriched. These changes and the REE abundances are mainly controlled by the abundance of apatite. Temporally and spatially related mangerites and charnockites form a trend from low-SiO₂ mangerites with Eu/Eu^* > 1 to intermediate-SiO₂ acidic mangerites with Eu/Eu^* ≈ 1 and charnockites with Eu/Eu^* < 1. Accordingly, the low-SiO₂ mangerites are interpreted as alkali feldspar-rich cumulates and the charnockites as residual liquids derived from the acidic mangerites. The mangerites with Eu/Eu^* around 1 have patterns similar to those of some highly evolved ferrodiorites possibly indicating a genetic link. Received December 12, 1999; revised version accepted November 15, 2000     

Interaction of magma with sedimentary wall rock and magnetite ore genesis in the Panzhihua mafic intrusion,SW China

In southwestern China, several large magmatic Fe–Ti–V oxide ore deposits are hosted by gabbroic intrusions associated with the Emeishan flood basalts. The Panzhihua gabbroic intrusion, a little deformed sill that contains a large titanomagnetite deposit at its base, concordantly intrudes late-Proterozoic dolostones. Mineralogical and chemical studies of the contact aureole in the footwall dolostones demonstrate that the metamorphism was largely isochemical but released large quantities of CO₂ as the rocks were converted to marble and skarns during intrusion of the gabbroic magma. Petrological modelling of the crystallization of the intrusion, using H₂O-poor Emeishan basalt as parent magma, shows that under normal conditions, Fe–Ti oxides crystallize at a late stage, after the crystallization of abundant olivine, clinopyroxene and plagioclase. In order for titanomagnetite to separate efficiently to form the ore deposit, this mineral must have crystallized earlier and close to the liquidus. We propose that CO₂-rich fluids released during decarbonatization of sedimentary floor rocks passed up through the magma. Redox equilibria calculations show that when magma with the composition of Emeishan basalt is fluxed by a CO₂-rich gas phase, its equilibrium oxygen fugacity (fO₂) increases from the fayalite–magnetite–quartz buffer (FMQ) to FMQ + 1.5. From experimental constraints on magnetite saturation in basaltic magma under controlled fO₂, such an oxidizing event would allow magnetite to crystallize near to the liquidus, leading to the formation of the deposit.     

Ore geochemistry,zircon mineralogy,and genesis of the Sakharjok Y-Zr deposit,Kola Peninsula,Russia

The Sakharjok Y-Zr deposit in Kola Peninsula is related to the fissure alkaline intrusion of the same name. The intrusion ∼7 km in extent and 4–5 km² in area of its exposed part is composed of Neoarchean (2.68–2.61 Ma) alkali and nepheline syenites, which cut through the Archean alkali granite and gneissic granodiorite. Mineralization is localized in the nepheline syenite body as linear zones 200–1350 m in extent and 3–30 m in thickness, which strike conformably to primary magmatic banding and trachytoid texture of nepheline syenite. The ore is similar to the host rocks in petrography and chemistry and only differs from them in enrichment in zircon, britholite-(Y), and pyrochlore. Judging from geochemical attributes (high HSFE and some incompatible element contents (1000–5000 ppm Zr, 200–600 ppm Nb, 100–500 ppm Y, 0.1–0.3 wt % REE, 400–900 ppm Rb), REE pattern, Th/U, Y/Nb, and Yb/Ta ratios), nepheline syenite was derived from an enriched mantle source similar to that of contemporary OIB and was formed as an evolved product of long-term fractional crystallization of primary alkali basaltic melt. The ore concentrations are caused by unique composition of nepheline syenite magma (high Zr, Y, REE, Nb contents), which underwent subsequent intrachamber fractionation. Mineralogical features of zircon-the main ore mineral—demonstrate its long multistage crystallization. The inner zones of prismatic crystals with high ZrO₂/HfO₂ ratio (90, on average) grew during early magmatic stage at a temperature of 900–850°C. The inner zones of dipyramidal crystals with average ZrO₂/HfO₂ = 63 formed during late magmatic stage at a temperature of ∼500°C. The zircon pertaining to the postmagmatic hydrothermal stage is distinguished by the lowest ZrO₂/HfO₂ ratio (29, on average), porous fabric, abundant inclusions, and crystallization temperature below 500°C. The progressive decrease in ZrO₂/HfO₂ ratio was caused by evolution of melt and postmagmatic solution. The metamorphic zircon rims relics of earlier crystals and occurs as individual rhythmically zoned grains with an averaged ZrO₂/HfO₂ ratio (45, on average) similar to that of the bulk ore composition. The metamorphic zircon is depleted in uranium in comparison with magmatic zircon, owing to selective removal of U by aqueous metamorphic solutions. Zircon from the Sakharjok deposit is characterized by low concentrations of detrimental impurities, in particular, contains only 10–90 ppm U and 10–80 ppm Th, and thus can be used in various fields of application.     

Hydration vs. oxidation: Modelling implications for Fe–Ti oxide crystallisation in mafic intrusions, with specific reference to the Panzhihua intrusion, SW China

Recent work on the Panzhihua intrusion has produced two separate models for the crystallisation of the intrusion:（1） low-Ti,high CaO and low H₂O（0.5 wt.%） parent magma（equivalent to Emeishan low-Ti basalt） at FMQ;and（2） high-Ti,low CaO and higher H₂O（>1.5 wt.%） parent magma（equivalent to Emeishan high-Ti basalt） at FMQ + 1.5.Modelling of these parent magma compositions produces significantly different results. We present here detailed f（O₂） and H₂O modelling for average compositions of both Emeishan high-Ti and low-Ti ferrobasalts in order to constrain the effects on crystallisation sequences for Emeishan ultra-mafic -mafic layered intrusions.Modelling is consistent with numerous experimental studies on ferro-basaltic magmas from other localities（e.g.Skaergaard intrusion）.Modelling is compared with the geology of the Panzhihua intrusion in order to constrain the crystallisation of the gabbroic rocks and the Fe-Ti oxides ore layers.We suggest that the gabbroic rocks at the Panzhihua intrusion can be best explained by crystallisation from a parent magma similar to that of the high-Ti Emeishan basalt at moderate H₂O contents（0.5-1 wt.%） but at the lower end of TiO₂ content for typical high-Ti basalts（2.5 wt.%TiO₂）. Distinct silicate disequilibrium textures in the Fe-Ti oxide ore layers suggest that an influx of H₂O may be responsible for changing the crystallisation path.An increase in H₂O during crystallisation of gabbroic rocks will result in the depression of silicate liquidus temperatures and resultant disequilibrium with the liquid.Continued cooling of the magma with high H₂O then results in precipitation of Mt-Uv alone. The H₂O content of parent magmas for mafic layered intrusions associated with the ELIP is an important variable.H₂O alters the crystallisation sequence of the basaltic magmas so that at high H₂O and f（O₂） Mt -Uv crystallises earlier than plagioclase and clinopyroxene.Furthermore,the addition of H₂O to an anhydrous magma can explain silicate disequilibrium texture observed in the Fe-Ti oxide ore layers.     

http://www.sciencedirect.com/science/article/pii/S1674987113000078

A sequence of gabbros showing isotropic,layered and fine-grained textures is exposed in the Nalaqing mine at the southern tip of the～260 Ma Panzhihua intrusion,SW China.The field relations,structure,texture and mineralogy of the rocks indicate that the sequence represents the transition between the Lower zone and Middle zone of the intrusion.Isotropic gabbros characteristic of the Lower zone pass upward to layered gabbros of the Middle zone through a～5 m-thick microgabbro sheet,within and close to which small-scaled, concordant Fe-Ti oxide ore horizons are identified.Strong fractionation between HFSE and REE in a subset of samples is ascribed to cumulus titanomagnetite into which HFSE are preferentially incorporated over REE,as reflected in the parallel relations between Nb/La,Hf/Sm and Ti/Ti^*.Both the isotropic and layered gabbros display cumulate textures and have similar mineral compositions(Mg^# of clinopyroxene =～76-79 and An_59-61),isotopic compositions[(⁸⁷Sr/⁸⁶Sr)i = 0.7044-0.7045 andε_Nd（t） = +2.4 to +3.9]and trapped liquid contents inferred from Zr abundance（～17-34 ppm）.However,there are substantial variations in elemental abundances（V,Cr and PGE） and ratios（Ti/V,La/Yb,Ba/Y and Cu/Pd） between the two types of gabbros,features that cannot be explained by cumulate formation from a common magma in a closed system.The microgabbros generally resemble high-Ti Emeishan basalts in major element compositions,but their low trace element abundances indicate some lost of residual liquid is inevitable despite rapid nucleation and cooling.Combined with available data and observations,we propose a model involving in-situ crystallization,followed by magma recharge and closed-system fractionation to explain the formation of texturally distinctive gabbros at Nalaqing and the evolution of the lower part of the Panzhihua intrusion.     

Petrogenesis and source characteristics of metatholeiites from the Archean Ramagiri schist belt, eastern part of Dharwar craton, India

The N–S trending, 2–4 km wide Ramagiri schist belt is made up of three blocks dominated by metavolcanic rocks, separated and surrounded by granitic rocks of distinct characteristics. The metavolcanic rocks are tholeiitic in composition and are very similar in their major element composition as well as in their abundances of some trace elements. However, the rare earth elements (REE) require distinct sources. The rocks of the amphibolite facies eastern block have LREE depleted REE patterns ([Ce/Yb] = 0.7–0.9), requiring derivation from depleted mantle-like sources. The greenschist facies metatholeiitic rocks of the central block have LREE enriched REE patterns ([Ce/Yb] = 3–6), reflecting the nature of their source(s). The Nd isotopic data require that the LREE enriched nature could not have been attained significantly prior to its melting. The fine-grained, upper greenschist facies metatholeiites of the western block have flat to slightly LREE depleted patterns ([Ce/Yb] = 0.8–0.95). Minor fractional crystallization of rock forming minerals may relate a few samples to each other among samples from each of the three blocks. Different extents of partial melting of distinct mantle sources have played a dominant role in the generation of the parent magmas to the central versus eastern and western block metatholeiites. The geochemical data suggest that the mantle sources were non-lherzolitic, and that these sources may have seen previous episodes of melt addition and extraction prior to melting that gave rise to the parent melts to the rocks ∼2750 Ma ago. The REE data indicate that while the sources of the eastern and western block rocks were similar to depleted mantle (ɛ_{Nd( i )} about +2), the source of the central block rocks (ɛ_{Nd( i )} about +3.5) were enriched in large ion lithophile element (LILE)-rich fluids/melts probably derived from subducting oceanic crust. This and other trace element signatures point to magma extraction in tectonic settings similar to modern island arcs. Subsequent to magma emplacement and crystallization, all the three suites of rocks were affected by interaction with low-temperature, crustal derived fluids (ɛ_{Nd 2750Ma} of about −8 to −12), probably during the accretion of the three blocks of the belt in the present form. The inferred source characteristics, tectonic setting of magma generation and the crustal fluid processes seem to suggest that Phanerozoic-style tectonic processes may have been important in the generation of Archean crust in the Dharwar craton. Received: 31 July 1995 / Accepted: 12 May 1997     

Geochemical Characteristics of Cenozoic Basaltic High-K Volcanic Rocks from Maguan Area, Eastern Tibet

The major element, trace element and Nd-Sr isotopic composition of Cenozoic basaltic volcanic rocks from the Maguan area, eastern Tibet, indicates that the volcanic rocks are enriched in alkalis, especially K (K2O up to 3.81%) and depleted in Ti (TiO2 = 1.27%-2.00%). These rocks may be classified as two groups, based on their Mg# numbers: one may represent primary magma (Mg# numbers from 68 to 69), and the other, the evolved magma(Mg# numbers from 49 to 57). Their REE contents are very high (∑REE = 155.06-239.04μg/g). Their REE distribution patterns are of the right-inclined type, characterized by LREE enrichment [(La/Yb)N =12.0-19.2], no Ce anomaly (Ce/Ce*=1.0), and weak negative Eu anomaly (Eu/Eu*=0.9). The rocks are highly enriched in Rb, Sr and Ba (59.5-93.8μg/g, 732-999 μg/g, and 450-632 g/g, respectively), high in U and Th (1.59-2.31μg/g and 4.73-8.16 μg/g, respectively), and high in Nb, Ta, Zr and Hf (70-118 μg/g,3.72-5.93 μg/g, 215-381 μg/g, and 5.47-9.03 μg/g, respectively). In the primitive mantle-normalized incompatible element spidergram, Nb, Ta, Zr, Hf and P show positive anomalies, whereas Ba, Ti and Y show negative anomalies. The 87Sr/86Sr ratios range from 0. 704029 to 0.704761; 143Nd/144Nd from 0. 512769 to 0. 512949; and εNd from 2.6 to 6.1. These geochemical features might suggest that the potential source of the basaltic high-K volcanic rocks in the Maguan area is similar to the OIB-source mantle of Hawaii and Kergeulen volcanic rocks.     

Geochemistry of intrusive rocks associated with the Latir volcanic field,New Mexico,and contrasts between evolution of plutonic and volcanic rocks

Plutonic rocks associated with the Latir volcanic field comprise three groups: 1) 25 Ma high-level resurgent plutons composed of monzogranite and silicic metaluminous and peralkaline granite, 2) 23–25 Ma syenogranite, and alkali-feldspar granite intrusions emplaced along the southern caldera margin, and 3) 19–23 Ma granodiorite and granite plutons emplaced south of the caldera. Major-element compositions of both extrusive and intrusive suites in the Latir field are broadly similar; both suites include high-SiO₂ rocks with low Ba and Sr, and high Rb, Nb, Th, and U contents. Moreover, both intermediateto siliciccomposition volcanic and plutonic rocks contain abundant accessory sphene and apatite, rich in rare-earth elements (REE), as well as phases in which REE's are essential components. Strong depletion in Y and REE contents, with increasing SiO₂ content, in the plutonic rocks indicate a major role for accessory mineral fractionation that is not observed in volcanic rocks of equivalent composition. Considerations of the rheology of granitic magma suggest that accessory-mineral fractionation may occur primarily by filter-pressing evolved magmas from crystal-rich melts. More limited accessory-mineral crystallization and fractionation during evolution of the volcanic magmas may have resulted from markedly lower diffusivities of essential trace elements than major elements. Accessory-mineral fractionation probably becomes most significant at high crystallinities. The contrast in crystallization environments postulated for the extrusive and intrusive rocks may be common to other magmatic systems; the effects are particularly pronounced in highly evolved rocks of the Latir field. High-SiO₂ peralkaline porphyry emplaced during resurgence of the Questa caldera represents non-erupted portions of the magma that produced the Amalia Tuff during caldera-forming eruption. The peralkaline porphyry continues compositional and mineralogical trends found in the tuff. Amphibole, mica, and sphene compositions suggest that the peralkaline magma evolved from metaluminous magma. Extensive feldspar fractionation occurred during evolution of the peralkaline magmas, but additional alkali and iron enrichment was likely a result of high halogen fluxes from crystallizing plutons and basaltic magmas at depth.     

Geochemistry and petrogenesis of a peralkaline granite complex from the Midian Mountains, Saudi Arabia

A zoned intrusion with a biotite granodiorite core and arfvedsonite granite rim represents the source magma for an albitised granite plug near its eastern margin and radioactive siliceous veins along its western margin. A study of selected REE and trace elements of samples from this complex reveals that the albitised granite plug has at least a tenfold enrichment in Zr, Hf, Nb, Ta, Y, Th, U and Sr, and a greatly enhanced heavy/light REE ratio compared with the peralkaline granite. The siliceous veins have even stronger enrichment of these trace elements, but a heavy/light REE ratio and negative eu anomaly similar to the peralkaline granite. It is suggested that the veins were formed from acidic volatile activity and the plug from a combination of highly fractionated magma and co-existing alkaline volatile phase. The granodiorite core intrudes the peralkaline granite and has similar trace element geochemistry. The peralkaline granite is probably derived from the partial melting of the lower crust in the presence of halide-rich volatiles, and the granodiorite from further partial melting under volatile-free conditions.     

Crystallization of loparite in alkaline fluid-magmatic systems (from experimental and mineralogical data)

We studied loparite-containing rocks (lujaurites, juvites, foyaite-juvites, etc.) sampled from a complex of differentiated rocks and, partly, from a complex of eudialytic lujaurites of the Lovozero alkaline massif. Zoned crystals of loparite (the zoning is due to variations in Ti, Nb, REE, Sr, and Th contents) were examined by microprobing. We also carried out experimental studies of loparite formation in complex silicate–salt systems including sodium carbonate, chloride, fluoride, or sulfate at 400–1200 °C and 1–2 kbar. They show that the composition of loparites depends on the physicochemical conditions of their formation (fluid composition) and that natural loparite can crystallize in a wide range of temperatures. The produced loparite crystals are zoned as a result of variations in Ti, Nb, La, Ce, Y, Ca, and Sr contents, which is probably related to the kinetic specifics of crystallization. Their zoning is similar to that of loparites of the Lovozero massif.     

The REE-Ti mineral chevkinite in comenditic magmas from Gran Canaria,Spain: a SYXRF-probe study

The REE-Ti silicate chevkinite has been recognised previously in Miocene ignimbrites from Gran Canaria, and in correlative offshore syn-ignimbrite turbidites. We have estimated the partition coefficients of REE, Y, Zr and Nb for chevkinite and co-existing peralkaline rhyolitic (comendite) glass using synchrotron-XRF-probe analyses (SYXRF) in order to evaluate the role of this mineral in the REE budget of felsic peralkaline magmas. The Zr/Nb ratio of the chevkinite is 1.55–1.7, strongly contrasting with Zr/Nb of 6.5 in the associated glass. Zr shows a three-fold enrichment in chevkinite relative to the residual melt, whereas Nb is enriched by a factor >10. The enrichment of Ce and La in chevkinite is even more significant, namely 19 wt(%) Ce and 12 wt(%) La, compared to 236 ppm Ce and 119 ppm La in the glass. Chevkinite/glass ratios are 988±30 for La, 806±30 for Ce, 626±30 for Pr, 615±40 for Nd, 392±50 for Sm, 225±30 for Eu, 142±25 for Gd, 72±20 for Dy. For trace elements, we derived Kd_TE of 74±25 for Y, >8 for Hf, >50 for Th, 15±5 for Nb and 3.55±0.4 for Zr. Mineral/glass ratios for co-existing titanite are 28±10 for La, 86±20 for Ce, 98±30 for Pr, 134±35 for Nd, 240±50 for Sm, 50±20 for Eu, 96±25 for Gd, 82±25 for Dy, 99±30 for Y, 45±10 for Nb and 3±0.5 for Zr. Based on these data, the removal of only 0.05 wt% of chevkinite from a magma with initially 300 ppm Ce would deplete the melt by 93 ppm to yield 207 ppm Ce in the residual liquid. Chevkinite thus appears, when present, to be the controlling mineral within the LREE budget of evolved peralkaline magmas.Editorial responsibility: I. Parsons

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Plagioclase of Hawaiian tholeiitic and alkalic magma parentages: distinctions based on REE, Sr, Ba, Hf, and Ta

Summary ?To enhance the ability to distinguish tholeiitic from alkalic magma parentages by mineral compositions, I determined trace-element abundances in plagioclase separated from xenolithic gabbros of Mauna Kea volcano. These gabbros have origins in tholeiitic and alkalic magmas of the Hamakua postshield stage of Mauna Kea volcanism. Chondrite-normalized rare-earth element (REE) patterns for plagioclase show that highly calcic plagioclase, ≥ An₇₈, from alkalic magma has greater light-REE/heavy-REE (LREE/HREE) ratios than less calcic plagioclase, An_64–75, from tholeiitic magma (ratios, 22–33 vs < 20), suggesting that higher LREE/HREE ratios are inherent to plagioclase of alkalic magmas. However, with compositional evolution (i.e., to lower An), plagioclase REE patterns are of limited use for distinguishing tholeiitic from alkalic parentage because LREE/HREE ratios within each group increase and overlap in the range of ∼ 20–90. Sr, Ba, Hf, and Ta can also discern parentages as their abundances in plagioclase largely reflect abundances inherent to their parental magmas. The best expressions for identifying parentage use Sr abundances (Sr vs An; vs Ce/Yb; vs Sr/Ce), although Hf, Ba, and Ta abundances vs An and vs Ce/Yb are also useful – the distinctions due to tholeiitic plagioclase having relatively low Sr (∼ 500–1000 ppm), Ba (< 100 ppm), Hf (< 0.10 ppm), and Ta (< 0.05 ppm). These relationships help to distinguish between the effects of differentiation on trace-element abundances in plagioclase and their abundances owed to intrinsic concentrations in their magmas. They create compositional fields for tholeiitic and alkalic parentages that remain graphically separated even though differentiation may have enriched the plagioclase in incompatible elements.

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Zusammenfassung ?Plagioklas aus tholeitischen und alkalischen Magmen von Hawaii: Unterscheidung aufgrund von REE, Sr, Ba, Hf und Ta Um die M?glichkeit der Unterscheidung tholeitischer von alkalischer Magmaherkunft durch Mineralzusammensetzungen zu verbessern, habe ich die Spurenelementverteilung in Plagioklasen, die von xenolithischen Gabbros des Mauna Kea Vulkans abgetrennt wurden, untersucht, Diese Gabbros entstammen tholeitischen und alkalischen Magmen des Hamakua “Post-Schild” Stadiums des Mauna Kea Vulkanismus. Chondritisch normalisierte Seltene Erd (SEE) Verteilungs-Muster für Plagioklase zeigen, dass stark kalzische Plagioklase, > An₇₈, aus alkalischen Magmen h?here leichte SEE/schwere SEE (LSEE/HSEE) Verh?ltnisse zeigen, als weniger kalzische Plagioklase, An_64–75 aus tholeitischem Magma (Verh?ltniszahlen 22–33 gegenüber < 20). Dies weist darauf hin, dass h?here LSEE/HSEE-Verh?ltnisse typisch für Plagioklase aus alkalischen Magmen sind. Im Zuge der Evolution der Zusammensetzungen (d.h. zu niedrigeren An-Werten hin), sind die SEE Verteilungsmuster von Plagioklasen weniger hilfreich um tholeitische von alkalischer Herkunft zu unterscheiden. Dies ist deshalb so, weil die Verh?ltniszahlen innerhalb jeder Gruppe zunehmen und im Bereich von 20–90 überlappen. Sr, Ba, Hf und Ta k?nnen auch dazu dienen, um die Herkunft der Plagioklase zu definieren, da ihre H?ufigkeit gro?teils auf H?ufigkeiten, die für die Ursprungsmagmen typisch sind, zurückgehen. Die besten Herkunft-Parameter sind die Sr H?ufigkeiten (Sr vs An; vs Ce/Yb; vs Sr/Ce), obwohl die H?ufigkeit von Hf, Ba und Ta gegen An und gegen Ce/Yb auch nützlich sind. Diese Unterscheidungen gehen darauf zurück, dass tholeitische Plagioklase relativ niedrige Sr (∼ 500–1000 ppm), Ba (< 500 ppm) Hf (< 0.10 ppm) und Ta (< 0.5 ppm) führen. Diese Beziehungen erleichtern die Unterscheidung zwischen den Auswirkungen der Differenzierung auf die Spurenelement-Verteilungsmuster in Plagioklasen und auf ihre H?ufigkeiten, die auf die intrisischen Konzentrationen in den Ursprungsmagmen zurückgehen. Sie definieren charakteristische Felder für tholeitische und für alkalische Herkunft, die graphisch separiert bleiben, auch wenn die Gehalte der Plagioklase an inkompatiblen Elementen durch Differenzierung zugenommen haben mag.

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Received July 22, 1999;revised version accepted December 7, 1999     

Volatile control of contrasting trace element distributions in peralkaline granitic and volcanic rocks

Anomalous enrichments of Zr (>500 ppm), Zn (> 100 ppm), Nb (>25 ppm), Y (>60 ppm), Th (>20 pm), U (> 5 ppm), LREE (>230 ppm) and HREE (>35ppm), and high Rb/Sr (>5) characterize peralkaline granites, in contrast to their peraluminous and calc-alkaline equivalents. Within the peralkaline suite, comenditic and pantelleritic volcanics exhibit two- to five-fold increases in the concentrations of these trace elements over comagmatic granites. These cannot be explained by crystal- liquid fractionation processes, and require the evolution of a sodium-enriched fluid. Corresponding trace element increases in the granites in areas of alkali metasomatism support this argument, and reflect the partial confinement of this volatile phase within the high-level magma chambers. REE studies in particular might eventually allow an evaluation of the role of Cl⁻ versus F⁻ and CO₃-complexing in the evolution of the volatile fluid.     

Partition coefficients of Nb and Ta between rutile and anhydrous haplogranite melts

Partition coefficients (D) for Nb and Ta between rutile and haplogranite melts in the K₂O-Al₂O₃-SiO₂ system have been measured as functions of the K₂O/Al₂O₃ ratio, the concentrations of Nb₂O₅ and Ta₂O₅, the temperature, in air and at 1 atmosphere pressure. The Ds increase in value as the K^* [K₂O/(K₂O + Al₂O₃)] molar ratio continuously decreases from highly peralkaline [K^* ∼ 0.9] to highly peraluminous [K^* ∼ 0.35] melts. The D values increase more dramatically with a unit decrease in K^* in peraluminous melts than in peralkaline melts. This compositional dependence of Ds can be explained by the high activity of NbAlO₄ species in peraluminous melts and the high activity of KONb species (or low activity of NbAlO₄ species) in peralkaline melts. A coupled substitution, Al⁺³ + Nb⁺⁵ (or Ta⁺⁵) = 2Ti⁺⁴, accounts for the Ds of Nb (Ta) being much greater in peraluminous melts than in peralkaline melts because this substitution allows Nb (Ta) to enter into the rutile structure more easily. The Ds of Ta between rutile and melt are greater than those of Nb at comparable concentrations because the molecular electronic polarizability of Ta is weaker than that of Nb. The Nb⁺⁵ with a large polarizing power forms a stronger covalent bond with oxygen than Ta⁺⁵ with a small polarizing power. The formation of the strong bond, Nb-O, distorts the rutile structure more severely than the weak bond, Ta-O; therefore, it is easier for Ta to partition into rutile than for Nb. These results imply that the utilization of the Nb/Ta ratio in liquid as a petrogenetic indicator in granitic melts must be done with caution if rutile (or other TiO₂-rich phases) is a liquidus phase. The crystallization of rutile will increase the Nb/Ta ratio of the residual liquid because the Ds of Ta between rutile and melts are greater than those of Nb. Received: 28 December 1998 / Accepted 27 September 1999     

Geochemistry and petrogenesis of radioactive Palaeoproterozoic granitoids of Kinwat crystalline inlier,Nanded and Yeotmal districts,Maharashtra

Kinwat crystalline inlier exposes Palaeoproterozoic granitoids belonging to the northern extensions of younger phase of Peninsular gneissic complex (PGC) within Deccan Trap country in Eastern Dharwar Craton (EDC) and bounded in south by a major NW-SE trending lineament (Kaddam fault). Geochemically, the Kinwat granitoids are similar to high-K, calc-alkaline to shoshonite magnesian granitoids and subdivided into two major groups, i.e. felsic group (pink and grey granites) and intermediate to felsic group (hybrid granitoids). The felsic group (∼67–74% SiO₂) shares many features with Neoarchaean to Palaeoproterozoic high potassic granites of PGC such as higher LILE and LREE content and marked depletion in Eu, P and HFSE, especially Nb, Ti, relative to LILE and LREE. The hybrid granitoids (∼58–67% SiO₂) have comparatively higher Ca, Mg and Na contents and slightly lower REE content than the granitoids of felsic group. Both, felsic and hybrid granitoids are metaluminous to weakly peraluminous and belong to highly fractionated I-type suite as evidenced by negative correlation of SiO₂ with MgO, FeO^t, CaO, Na₂O, Al₂O₃, whereas K₂O, Rb and Ba show sympathetic relationship with SiO₂. Moderate to strong fractionated REE patterns (Ce/Yb_N: ∼54–387) and strong negative Eu anomalies (Eu/Eu*: 0.13–0.41) are quite apparent in these granitoids. The geochemical characteristics together with mineralogical features such as presence of biotite±hornblende as the dominant ferromagnesian mineral phases point towards intracrustal magma source, i.e. derivation of magma by partial melting of probably tonalitic igneous protolith at moderate crustal levels for felsic granites, whereas hybrid granitoids appear to be products of juvenile mantle-crust interaction, in an active continental margin setting.     

云南朱布镁铁-超镁铁岩体地球化学特征及成因机理探讨

云南朱布镁铁-超镁铁岩体赋存中型铜镍铂族元素矿床,侵位于元谋群片岩和花岗片麻岩中,岩体垂直分异明显,自下而上为橄榄岩、橄辉岩、辉石岩、辉长岩等相带.矿体以底部“边缘矿”为主,上部有呈透镜状产出的少量“上悬矿”.本文报道了朱布岩体主元素、微量元素、铂族元素(PGE)和 Sr-Nd 同位素组成新的测试结果.分析表明朱布岩体具有拉斑玄武质岩浆分异演化趋势,富集 LREE 的分布模式,弱的Nb 异常和较明显的 Sr 负异常,并与峨眉山大火成岩省(ELIP)苦橄岩相类似,暗示两者可能存在成因上的联系.朱布岩体的铂族元素相对分布模式为“Pt-Pd”富集型,原始地幔标准化曲线向左陡倾.较高的(87Sr/86Sr)i (0.7096~0.7107)和较低的εNd(t)(-3.1~-2.3),表明朱布岩浆受到了地壳物质不同程度的混染.通过岩浆演化过程反演,得出其母岩浆性质为苦橄质,并估算地壳混染程度在3%~20%之间,发现在 R (岩浆与熔离硫化物的比例)值为1000~5000时比较吻合朱布样品中硫化物的实际测定值,证实了朱布岩体可能为开放系统的岩浆房,经过多级富集过程,先熔出的硫化物从后续多期次岩浆中吸收了大量 PGE,岩浆房中同时存在堆晶和岩浆演化,分别形成了底层橄榄岩和上部的辉长岩,中间过渡为橄辉岩和辉石岩