Columbite solubility in granitic melts: consequences for the enrichment and fractionation of Nb and Ta in the Earth's crust

The behaviour of niobium and tantalum in magmatic processes has been investigated by conducting MnNb₂O₆ and MnTa₂O₆ solubility experiments in nominally dry to water-saturated peralkaline (aluminium saturation index, A.S.I. 0.64) to peraluminous (A.S.I. 1.22) granitic melts at 800 to 1035 °C and 800 to 5000 bars. The attainment of equilibrium is demonstrated by the concurrence of the solubility products from dissolution, crystallization, Mn-doped and Nb- or Ta-doped experiments at the same pressure and temperature. The solubility products of MnNb₂O₆ (K_sp ^Nb) and MnTa₂O₆ (K_sp ^Ta) at 800 °C and 2 kbar both increase dramatically with alkali contents in water-saturated peralkaline melts. They range from 1.2 × 10⁻⁴ and 2.6 × 10⁻⁴ mol²/kg², respectively, in subaluminous melt (A.S.I. 1.02) to 202 × 10⁻⁴ and 255 × 10⁻⁴ mol²/kg², respectively, in peralkaline melt (A.S.I. 0.64). This increase from the subaluminous composition can be explained by five non-bridging oxygens being required for each excess atom of Nb⁵⁺ or Ta⁵⁺ that is dissolved into the melt. The K_sp ^Nb and K_sp ^Ta also increase weakly with Al content in peraluminous melts, ranging up to 1.7 × 10⁻⁴ and 4.6 × 10⁻⁴ mol²/kg², respectively, in the A.S.I. 1.22 composition. Columbite-tantalite solubilities in subaluminous and peraluminous melts (A.S.I. 1.02 and 1.22) are strongly temperature dependent, increasing by a factor of 10 to 20 from 800 to 1035 °C. By contrast columbite-tantalite solubility in the peralkaline composition (A.S.I. 0.64) is only weakly temperature dependent, increasing by a factor of less than 3 over the same temperature range. Similarly, K_sp ^Nb and K_sp ^Ta increase by more than two orders of magnitude with the first 3 wt% H₂O added to the A.S.I. 1.02 and 1.22 compositions, whereas there is no detectable change in solubility for the A.S.I. 0.64 composition over the same range of water contents. Solubilities are only slightly dependent on pressure over the range 800 to 5000 bars. The data for water-saturated sub- and peraluminous granites have been extrapolated to 600 °C, conditions at which pegmatites and highly evolved granites may crystallize. Using a melt concentration of 0.05 wt% MnO, 70 to 100 ppm Nb or 500 to 1400 ppm Ta are required for manganocolumbite and manganotantalite saturation, respectively. The solubility data are also used to model the fractionation of Nb and Ta between rutile and silicate melts. Predicted rutile/melt partition coefficients increase by about two orders of magnitude from peralkaline to peraluminous granitic compositions. It is demonstrated that the γNb₂O₅/γTa₂O₅ activity coefficient ratio in the melt phase depends on melt composition. This ratio is estimated to decrease by a factor of 4 to 5 from andesitic to peraluminous granitic melt compositions. Accordingly, all the relevant accessory phases in subaluminous to peraluminous granites are predicted to incorporate Nb preferentially over Ta. This explains the enrichment of Ta over Nb observed in highly fractionated granitic rocks, and in the continental crust in general. Received: 9 August 1996 / Accepted: 26 February 1997     

Evolution and REE geochemistry of Huangsha-Tieshanlong ore-bearing granite

Our studies show that the granite bodies (γ ₅ ^{2 − 1} and γ ₅ ³ ) which constitute the Huangsha-Tieshanlong composite granitic intrusion in Jiangxi are characterized by their similarities in mineral assemblage, petrochemistry, trace element and REE distribution pattern. The values of ΣREE, ΣLREE, ΣHREE, ΣCe/ΣY, δEu and La/Yb apparently decrease from γ ₅ ^{2 − 1a} to γ ₅ ^{2 − 1b} , γ ₅ ³ and γ ₅ ³ . It is shown that the early Yenshanian W(Ta, Nb)-bearing granite (γ ₅ ^{2 − 1} ) and late Yenshanian Ta, Nb-bearing granite (γ ₅ ³ ) may have been derived from the differentiation and evolution of granitic magmas due to repeated remelting of the crust and their earlier and later intrusion. Although the earlier (γ ₅ ^{2 − 1b} and later (γ ₅ ³ ) albitized Ta, Nb-bearing granites show some obvious differences in REE content, their δEu values and La/Yb ratios are similar to each other. Therefore, it may be concluded that the early and late Ta, Nb-bearing granites were derived from a congenetic magma.     

Ammonium in granites and its petrogenetic significance

Ammonium is present as a trace constituent in all granites, with an average concentration of 45 ppm (NH₄⁺), equivalent to 35 ppm of elemental N. It shows wide variations related to petrography and region, but the only significant correlation between ammonium and other geochemical parameters is that it is most abundant in peraluminous granites and least abundant in peralkaline granites. These variations can be related to (a) the amount of sedimentary material in the magmatic source region, and (b) redox conditions in the source region. The ammonium content of granitic magmas can also be modified by fractionation or contamination. Hydrothermal alteration has a major effect on the ammonium content of granitic rocks, and variation due to this cause may exceed the magmatic variation. Most hydrothermally altered granites are enriched in ammonium as a result of the transfer of ammonium from sedimentary country rocks by the hydrothermal fluids.     

Nature of the crust in Maine,USA: evidence from the Sebago batholith

 Neodymium and lead isotope and elemental data are presented for the Sebago batholith (293±2 Ma), the largest exposed granite in New England. The batholith is lithologically homogeneous, yet internally heterogeneous with respect to rare earth elements (REE) and Nd isotopic composition. Two-mica granites in the southern/central portion of the batholith (group 1) are characterized by REE patterns with uniform shapes [Ce_N/Yb_N (chondrite normalized) = 9.4–19 and Eu/Eu* (Eu anomaly) = 0.27–0.42] and ɛ _Nd(t) = −3.1 to −2.1. Peripheral two-mica granites (group 2), spatially associated with stromatic and schlieric migmatites, have a wider range of total REE contents and patterns with variable shapes (Ce_N/Yb_N = 6.1–67, Eu/Eu* = 0.20–0.46) and ɛ _Nd(t) = −5.6 to −2.8. The heterogeneous REE character of the group 2 granites records the effects of magmatic differentiation that involved monazite. Coarse-grained leucogranites and aplites have kinked REE patterns and low total REE, but have Nd isotope systematics similar to group 2 granites with ɛ _Nd(t) = −5.5 to −4.7. Rare biotite granites have steep REE patterns (Ce_N/Yb_N = 51–61, Eu/Eu* = 0.32–0.84) and ɛ _Nd(t) = −4.6 to −3.8. The two-mica granites have a restricted range in initial Pb isotopic composition (²⁰⁶Pb/²⁰⁴Pb = 18.41–18.75; ²⁰⁷Pb/²⁰⁴Pb = 15.60–15.68; ²⁰⁸Pb/²⁰⁴Pb = 38.21–38.55), requiring and old, high U/Pb (but not Th/U) source component. The Nd isotope data are consistent with magma derivation from two sources: Avalon-like crust (ɛ _Nd>−3), and Central Maine Belt metasedimentary rocks (ɛ _Nd<−4), without material input from the mantle. The variations in isotope systematics and REE patterns are inconsistent with models of disequilibrium melting which involved monazite. Received: 8 December 1995 / Accepted: 29 April 1996     

Geochemistry and geodynamic significance of the rare-earth mineralized Paleoproterozoic Longwangzhuang granite on the southern margin of the North China Craton

The Longwangzhuang granite pluton occurs on the southern margin of the North China Craton and consists mainly of biotite syenogranite with aegirine granite being locally distributed.The granites are characterized by high silicon and alkaline contents(SiO2=72.17%-76.82%,K2O+Na2O=8.28%-10.22%,K2O/Na2O>>1),AI(agpaitic index) =0.84-0.95,DI=95-97,ASI(aluminum saturation index)=0.96-1.13,and very high Fe* number(FeO*/(FeO*+Mg)=0.90-0.99),thus the granites are assigned to the metaluminous to weakly peraluminous,alkalic to calc-alkalic ferroan A-type granites.The granites are rich in large ion lithophile elements(LILE),especially high in REE concentrations(REE+Y=854×10-6-1572×10-6);whereas the enrichment of high strength field elements(Nb,Ta,Zr,Hf) is obviously less than that of LILEs,exhibiting mild depletions on trace element spider plots;and the rocks are significantly depleted in Ba,Sr,Ti,and Pb.The low εNd(t) values(-4.5--7.2) and high model ages(2.3-2.5 Ga) of the granites as well as the low εHf(t) values(-1.11--5.26) and high Hf model ages(THf1= 2.1-2.3 Ga,THf2=2.4-2.6 Ga) of zircons from the biotite syenogranite suggest that the granites were probably derived from an enriched mantle source.The zircons from the biotite syenogranite are mainly colorless transparent crystals exhibiting well-developed oscillatory zoning on the cathodoluminescence images with a LA-ICPMS zircon U-Pb age of 1602.1±6.6 Ma(MSWD=0.48).Petrochemical,trace elements,as well as Nd and Hf isotopic compositions of the rocks demonstrate that the granites were formed in a within-plate extensional tectonic regime possibly related to the breakup of the Columbia supercontinent.The granites were most likely formed through extreme fractional crystallization of alkali basaltic magma resulted from partial melting of the mantle,which was fertilized by recycling crustal rocks triggered by the delamination of lithospheric mantle and lower crust following the ～1.8 Ga collision and amalgamation of the North China Craton which is part of the Columbia supercontinent.However,contamination of neo-Archean to Paleoproterozoic crustal rocks during the ascent and emplacement of the magma could not be excluded.Being the youngest known anorogenic magmatism on the southern margin of the North China Craton related to Columbia breakup,it might represent the break off of the North China Craton from Columbia supercontinent at the end of Paleoproterozoic.     

The melt inclusion record from the rhyolitic Kos Plateau Tuff (Aegean Arc)

The >60 km³ rhyolitic Kos Plateau Tuff provides an exceptional probe into the behavior of volatile components in highly evolved arc magmas: it is crystal-rich (30–40 vol% crystals), was rapidly quenched by the explosive eruptive process, and contains abundant homogeneous melt inclusions in large quartz crystals. Several methods for measuring major, trace and volatile element concentrations (SIMS, FTIR, Raman spectroscopy, electron microprobe, LA–ICPMS) were applied to these melt inclusions. We found a ~2 wt% range of H₂O contents (4.5–6.5 wt% H₂O, measured independently by SIMS, FTIR, and Raman spectroscopy) and relatively low CO₂ concentrations (15–140 ppm measured by FTIR, with most analyses <100 ppm). No obvious correlations between H₂O, CO₂, major and trace elements are observed. These observations require a complex, protracted magma evolution in the upper crust that included: (1) vapor-saturated crystallization in a chamber located between 1.5 and 2.5 kb pressure, (2) closed-system degassing (with up to 10 vol% exsolved gas) as melts percolated upwards through a vertically extensive mush zone (2–4 km thick), and (3) periodic gas fluxing from subjacent, more mafic and more CO₂-rich magma, which is preserved as andesite bands in pumices. These processes can account for the range of observed H₂O and CO₂ values and the lack of correlation between volatiles and trace elements in the melt inclusions.     

Therm odynamics of Diagenetic Fluid and Fluid／Mineral Reactions in the Eogene Xingouzui Formation,Oil Field T,Jianghan Basin

This study focuses on the thermodynamics of diagenetic fluid from the Eogene Xingouzui Formation which represents the most important reservoir in Field Oil T in the Jianghan Basin. The measured homogenization temperatures (110–139 °C) of fluid inclusions in diagenetic minerals fell within the range of 67 –155 °C at the middle diagenetic stage. The pressure of diagenetic fluid is estimated at 10.2 –56 MPa. The activity of ions in the fluid shows a tendency of Ca²⁺ > Mg²⁺ > Na⁺ > K⁺ > Fe³⁺ > Fe²⁺ for cations, and HCO ₃ ⁻ > SO ₄ ²⁻ > F⁻ > Cl⁻ > CO ₃ ²⁻ for anions. For the gaseous facies, there is a tendency of CO₂> CO> H₂S> CH₄> H₂. According to the thermodynamic calculations, the pH and Eh of the fluid are 5.86–6.47 and −0.73–−0.64V, respectively. As a result of the interaction between such a diagenetic fluid and minerals in the sediments, feldspars were dissolved or alterated by other minerals. The clay mineral kaolinite was instable and hence was replaced by illite and chloritoid. This project was jointly funded by the National Natural Science Foundation of China (49133080) and the Open Laboratory of Ore Deposit Geochemistry, Institute of Geochemistry, Chinese Academy of Sciences.     

Trace element incorporation into quartz: A combined study by ICP-MS, electron spin resonance, cathodoluminescence, capillary ion analysis, and gas chromatography

Pegmatite quartz from different occurrences in Norway and Namibia was investigated by a combination of ICP-MS, Electron Spin Resonance (ESR), Capillary Ion Analysis (CIA) and Gas Chromatography (GC) to quantify trace elements in very low concentrations and to determine their position in the quartz structure.The studied quartz samples show similar geochemical characteristics with low contents of most trace elements. Remarkable are the elevated concentrations of Al (36-636 ppm), Ti (1.6-25.2 ppm), Ge (1.0-7.1 ppm), Na (5.2 to >50 ppm), K (1.6 to >100 ppm) and Li (2.1-165.6 ppm). These elements are preferentially incorporated into the quartz lattice on substitutional (Al, Ti, Ge) and interstitial (Li, Na, K) positions. Li⁺ was found to be the main charge compensating ion for Al, Ge and Ti, whereas some ppm of Na and K may also be hosted by fluid inclusions. Ti may be incorporated as substitutional ion for Si or bound on mineral microinclusions (rutile). The results of the ESR measurements show that there may be a redistribution of alkali ions during irradiation. The diamagnetic [AlO₄/M⁺]⁰ center transforms into the paramagnetic [AlO₄]⁰ center, whilst the compensating ions diffuse away and may be captured by the diamagnetic precursor centers of [GeO₄]⁰ and [TiO₄]⁰ to form paramagnetic centers ([TiO₄/Li⁺]⁰, [GeO₄/Li⁺]⁰).In general, fluid inclusions in pegmatite quartz can be classified as H₂O-CO₂-NaCl type inclusions with water as the predominant volatile. Among the main elements hosted by fluid inclusions in quartz are Na, K, NH₄, Ca, Mg and the anionic complexes Cl⁻, NO₃⁻, HCO₃⁻ and SO₄²⁻. Gas analysis of trapped fluids shows volatile components in the following order of abundance: H₂O > CO₂ > N₂(+) ≥ CH₄ > COS > C₂ and C₃ hydrocarbons. Additionally, traces of Co, Ni, Zn, Pb, and Cu were detected by CIA in fluid inclusions of some samples. There are indications that the REE and Rb are also bound in fluid inclusions, however, the concentrations of these elements are too low to be measured by CIA. Assuming that the REE preferentially occur in fluid inclusions, the typical chondrite normalized REE distribution patterns with tetrad effects and a distinct negative Eu anomaly would reflect the composition of the mineralizing fluid.For a number of elements, especially those with extremely low concentrations, the “type” of incorporation in quartz could not directly be determined. We conclude that these ions either are too large to substitute for the small Si⁴⁺ ion or they are not soluble in the mineralizing fluids to be hosted by fluid inclusions. Some of these elements, which are concentrated in the specific mineralization of certain pegmatites, are not present in elevated concentrations in the paragenetic pegmatite quartz itself. This was observed, for instance, for Be, Cs and Rb in the Li (Be-Cs-Rb) pegmatites of Rubicon or for Nb and Ta for Nb-Ta bearing pegmatites from Norway. It may be concluded that the concentrations of these trace elements in quartz do not reflect the mineralization and that these elements thus, cannot be used as petrogenetic indicator.     

Geologic relationships and mineralization of peralkaline/alkaline granite-syenite of the Zargat Na＇ am ring complex, Southeastern Desert, Egypt

The Zargat Na’ am ring complex crops out 90 km NW of Shalatin City in the Southeastern Desert of Egypt. The ring complex forms a prominent ridge standing high above the surrounding mafic-ultramafic hills. It is cut by two sets of joints and faults which strike predominantly NNW-SSE and E-W, and is injected by dikes, porphyritic alkaline syenites, and felsite porphyries. It consists of alkali syenites, alkali quartz syenites, and peralkaline arfvedsonite-bearing granitic and pegmatitic dikes and sills. The complex is characterized locally by extreme enrichments in REEs, wolframite and rare, high field strength metals (HFSM), such as Zr and Nb. The highest concentrations (1.5 wt% Zr, 0.25 wt% Nb, 0.6 wt% Σ REEs) occur in aegirine-albite aplites that formed around arfvedsonite pegmatites. Quartzhosted melt inclusions in arfvedsonite granite and pegmatite provide unequivocal evidence that the peralkaline compositions and rare metal enrichments are primary magmatic features. Glass inclusions in quartz crystals also have high concentrations of incompatible trace elements including Nb (750 ￠ 10⁻⁶), Zr (2500 × 10⁻⁶) and REEs (1450 × 10⁻⁶). The REEs, Nb and Zr compositions of the aegirine-albite aplites plot along the same linear enrichment trends as the melt inclusions, and Y/Ho ratios mostly display unfractionated, near-chondritic values. The chemical and textural features of the aegirine-albite aplites are apparently resultant from rapid crystallization after volatile loss from a residual peralkaline granitic melt similar in composition to the melt inclusions.     

Origin and timing of the post-Variscan gabbro–granite complex of Porto (Western Corsica)

The post-Variscan complex of Porto consists of metaluminous to slightly peraluminous A-type biotite granites mingled with gabbro-dioritic rocks, and late dykes with basaltic to trachyandesitic composition. U-Pb zircon dating by LA-ICP-MS on two mafic intrusive samples constrains the time of the gabbro–granite crystallisation at 281 ± 3 Ma and 283 ± 2 Ma. Hornblende ⁴⁰Ar-³⁹Ar ages from a late trachyandesite dyke date the dyking event at 280 ± 2 Ma, which is within error the U-Pb zircon ages of the intrusives. Biotite granites show variable major and trace element compositions and similar initial ε_Nd (−0.3 to +0.9). Whole rock chemistry variations and trace element compositions of plagioclase and allanite indicate that the granites are genetically linked, essentially through fractional crystallisation of feldspars and minor allanite. On the basis of whole-rock chemistry e.g. initial ε_Nd +4.9 to +1.7 and trace element clinopyroxene compositions, we have ascertained that the mafic intrusives and basic dykes formed from isotopically depleted mantle source-derived melts with similar trace element signature. These basic melts experienced slightly different evolutionary histories, controlled by fractional crystallisation and crustal contamination, mainly by the acid magma that gave rise to the associated biotite granites, but also by the enclosing older Variscan granitoids. U-Pb zircon data suggest that the Porto complex was affected by hydrothermal fluid circulation at 259 ± 9 Ma.     

Factors controlling copper solubility and chalcopyrite deposition in the Sungun porphyry copper deposit, Iran

The Sungun porphyry copper deposit is hosted in a Diorite/granodioritic to quartz-monzonitic stock that intruded Eocene volcanosedimentary and Cretaceous carbonate rocks. Copper mineralization is associated mainly with potassic alteration and to a lesser extent with sericitic alteration. Based on previously published fluid inclusion and isotopic data by Hezarkhani and Williams-Jones most of the copper is interpreted to have deposited during the waning stages of orthomagmatic hydrothermal activity at temperatures of 400 to 300 °C. These data also indicate that the hydrothermal system involved meteoric waters, and boiled extensively. In this work, thermodynamic data are used to delineate the stability fields of alteration and ore assemblages as a function of fS₂, fO₂ and pH. The solubility of chalcopyrite was evaluated in this range of conditions using recently published experimental data. During early potassic alteration (>450 °C), Copper solubility is calculated to have been >50 000 ppm, whereas the copper content of the initial fluid responsible for ore deposition is estimated, from fluid inclusion data, to have been 1200–3800 ppm. This indicates that initially the fluid was highly undersaturated with respect to chalcopyrite, which agrees with the observation that veins formed at T > 400 °C contain molybdenite but rarely chalcopyrite. Copper solubility drops rapidly with decreasing temperature, and at 400 °C is approximately 1000 ppm, within the range estimated from fluid inclusion data, whereas at 350 °C it is only 25 ppm. These calculations are consistent with observations that the bulk of the chalcopyrite deposited at Sungun is hosted by veins formed at temperatures of 360 ± 60 °C. Other factors that, in principle, may reduce chalcopyrite solubility are increases in pH, and decreases in fO₂ and aCl⁻. Our analysis shows, however, that most of the change in pH occurred at high temperature when chalcopyrite was grossly undersaturated in the fluid, and that the direction of change in fO₂ increased chalcopyrite solubility. We propose that the Sungun deposit formed mainly in response to the sharp temperature decrease that accompanied boiling, and partly as a result of the additional heat loss and decrease in aCl⁻, which occurred as a result of mixing of acidic Cu-bearing magmatic waters with cooler meteoric waters of lower salinity. Received: 8 July 1998 / Accepted: 8 April 1999     

Study on the Physical and Chemical Conditions of Ore Formation of Hetai Ductile Shear Zone—Hosted Gold Deposit and Discovery of Melt Inclusions

The Hetai ductile shear zone-hosted gold deposit occurs in the deep-seated fault mylonite zone of the Sinian-Silurian metamorphic rock series. In this study there have been discovered melt inclusions, fluid-melt inclusions and organic inclusions in ore-bearing quartz veins of the ore deposit and mylonite for the first time. The homogenization temperatures of the various types of inclusions are 160℃, 180 - 350℃, 530℃ and 870℃ for organic inclusions, liquid inclusions, two-phase immiscible liquid inclusions and melt inclusions, respectively. Ore fluid is categorized as the neutral to basic K+ -Ca2+ -Mg2+ -Na+ - SO2- 4-HCO3-Cl- system. The contents of trace gases follow a descending order of H2O＞CO2＞CH4＞(or ＜ ) H2＞CO＞C2H2＞C2I-I6＞O2＞N2.The concentrations of K , Ca2 + ,SO2-4,HCO3-,Cl- H2O and C2H2 in fluid inclusions are related to the contents of gold and the Au/Ag ratios in ores from different levels of the gold deposit. This is significant for deep ore prospecting in the region. Daughter minerals in melt inclusions were analyzed using SEM. Quartz, orthoclase, wollastonite and other silicate minerals were identified. They were formed in different mineral assemblages.This analysis further proves the existence of melt inclusions in ore veins. Sedimentary metamorphic rocks could form silicate melts during metamorphic anatexis and dynamic metamorphism, which possess melt-solution characteristics. Ore formation is related to the multi-stage forming process of silicate melt and fluid.     

Experimental investigation of H2O and Cl− solubilities in F-enriched silicate liquids; implications for volatile saturation of topaz rhyolite magmas

To interpret the degassing of F-bearing felsic magmas, the solubilities of H₂O, NaCl, and KCl in topaz rhyolite liquids have been investigated experimentally at 2000, 500, and ≈1 bar and 700° to 975 °C. Chloride solubility in these liquids increases with decreasing H₂O activity, increasing pressure, increasing F content of the liquid from 0.2 to 1.2 wt% F, and increasing the molar ratio of ((Al + Na + Ca + Mg)/Si). Small quantities of Cl⁻ exert a strong influence on the exsolution of magmatic volatile phases (MVPs) from F-bearing topaz rhyolite melts at shallow crustal pressures. Water- and chloride-bearing volatile phases, such as vapor, brine, or fluid, exsolve from F-enriched silicate liquids containing as little as 1 wt% H₂O and 0.2 to 0.6 wt% Cl at 2000 bar compared with 5 to 6 wt% H₂O required for volatile phase exsolution in chloride-free liquids. The maximum solubility of Cl⁻ in H₂O-poor silicate liquids at 500 and 2000 bar is not related to the maximum solubility of H₂O in chloride-poor liquids by simple linear and negative relationships; there are strong positive deviations from ideality in the activities of each volatile in both the silicate liquid and the MVP(s). Plots of H₂O versus Cl⁻ in rhyolite liquids, for experiments conducted at 500 bar and 910°–930 °C, show a distinct 90° break-in-slope pattern that is indicative of coexisting vapor and brine under closed-system conditions. The presence of two MVPs buffers the H₂O and Cl⁻ concentrations of the silicate liquids. Comparison of these experimentally-determined volatile solubilities with the pre-eruptive H₂O and Cl⁻ concentrations of five North American topaz and tin rhyolite melts, determined from melt inclusion compositions, provides evidence for the exsolution of MVPs from felsic magmas. One of these, the Cerro el Lobo magma, appears to have exsolved alkali chloride-bearing vapor plus brine or a single supercritical fluid phase prior to entrapment of the melt inclusions and prior to eruption. Received: 6 November 1995 / Accepted: 29 January 1998     

The generation of sodic granite magmas, western Palmer Land, Antarctic Peninsula

Subduction-related Mesozoic to Cainozoic granites s.l. in western Palmer Land, Antarctic Peninsula, have similar chemical compositions to Archean tonalite-trondhjemite-granodiorite (TTG) suites, Phanerozoic slab-melts (adakites), and to experimental partial melts of basaltic material in equilibrium with amphibole ± pyroxene ± garnet. They are predominantly sodic, metaluminous and most have Al₂O₃ > 15 wt% and Y < 18 ppm. All are light rare earth element (LREE)-enriched (2 < La/Yb_n <30) and most have small Eu anomalies. They have a wide range of initial ɛNd_(t) (−6.8 to +4.5) and ɛSr_(t) (+293.4 to −3.7), but most Pb isotope compositions deviate by < 0.3% from their mean. The Pb isotope data indicate a crustal component to all the granites, which Sr and Nd isotope variations suggest is pre-Triassic–Triassic. The ²⁰⁷Pb/²⁰⁴Pb_(t) range from 15.602 to 15.666 and appear to preclude a significant Proterozoic, or older, crustal component. The granites have chemical and isotopic compositions that suggest they are not partial melts of subducted oceanic lithosphere, as has been suggested for some Archean and Phanerozoic TTG magmas. We conclude that they were produced by mixing between basaltic-andesitic arc magmas, partial melts of juvenile basaltic lower crust and pre-Triassic crust. The low H(heavy)REE+Y content of some of the granites requires that garnet was a residual phase in the crust during partial melting, indicating a crustal thickness of >36 km. Between Triassic and Tertiary times the initial ɛNd_(t) of the magmatism increased and ɛSr_(t) decreased, suggesting that new continental crust was produced during this period. Underplating by mafic magma was an important crustal growth mechanism in the arc: the generation of abnormally thick crust, and its subse quent fusion, is considered to be a consequence of ca. ≥ 180 Ma of subduction and associated magmatism in the region. An implication of the model is that dense garnet-amphibolite and eclogite residues from partial melting of the lower crust will accumulate. In theory, the setting was appropriate for such residues to detach from the base of the crust and to sink into the convecting mantle. Such a process would leave the rest of the crust enriched in large ion lithophile elements/LREE, but depleted in HREE+Y. Received: 2 October 1995 / Accepted: 5 January 1997     

Sulfur isotopic systematics of granitoids from southwestern New Brunswick, Canada: implications for magmatic-hydrothermal processes, redox conditions, and gold mineralization

Bulk δ ³⁴S_rock values, sulfur contents, and magnetic susceptibility were determined for 12 gold-related granitoid intrusions in southwestern New Brunswick, the Canadian Appalachians. The sulfur isotope compositions of sulfide minerals in some of the granitoid samples were also analyzed. This new dataset was used to characterize two distinctive groups of granitoids: (1) a Late Devonian granitic series (GS) and (2) a Late Silurian to Early Devonian granodioritic to monzogranitic series (GMS). The GS rocks have a large range in δ ³⁴S values of −7.1‰ to +13‰ with an average of 2.2 ± 5.0‰ (1σ), low bulk-S contents (33 to 7,710 ppm) and low magnetic susceptibility values (<10⁻⁴ SI), consistent with reduced ilmenite-series granites. The GMS rocks have a relatively narrower variation in δ ³⁴S values of −4.4‰ to +7.3‰ with an average 1.2 ± 2.9‰ but with larger ranges in bulk-S contents (45 to 11,100 ppm) and high magnetic susceptibility values (>10⁻³ SI), indicative of oxidized magnetite-series granites. The exceptions for the GMS rocks are the Lake George granodiorite and Tower Hill granite that display reduced characteristics, which may have resulted from interaction of the magmas forming these intrusions with graphite- or organic carbon-bearing sedimentary rocks. The bulk δ ³⁴S values and S contents of the GMS rocks are interpreted in terms of selective assimilation–fractional crystallization (SAFC) processes. Degassing processes may account for the δ ³⁴S values and S contents of some GS rocks. The characteristics of our sulfur isotope and abundance data suggest that mineralizing components S and Au in intrusion-related gold systems are dominantly derived from magmatic sources, although minor contaminants derived from country rocks are evident. In addition, the molar sulfate to sulfide ratio in a granitic rock sample can be calculated from the δ ³⁴S_rock value of the whole-rock sample and the δ ³⁴S_sulfide (or δ ³⁴S_sulfate) value of sulfide and/or sulfate mineral in the sample on the basis of S-isotope fractionation and mass balance under the condition of magmatic equilibrium. This may be used to predict the speciation of sulfur in granitic rocks, which can be a potential exploration tool for intrusion-related gold systems.     

The behavior of trace elements during the chemical evolution of the H2O-, B-, and F-rich granite–pegmatite–hydrothermal system at Ehrenfriedersdorf, Germany: a SXRF study of melt and fluid inclusions

Detailed melt and fluid inclusion studies in quartz hosts from the Variscan Ehrenfriedersdorf complex revealed that ongoing fractional crystallization of the highly evolved H₂O-, B-, and F-rich granite magma produced a pegmatite melt, which started to separate into two immiscible phases at about 720°C, 100 MPa. With cooling and further chemical evolution, the immiscibilty field expanded. Two conjugate melts, a peraluminous one and a peralkaline one, coexisted down to temperatures of about 490°C. Additionally, high-salinity brine exsolved throughout the pegmatitic stage, along with low-density vapor. Towards lower temperatures, a hydrothermal system gradually developed. Boiling processes occurred between 450 and 400°C, increasing the salinities of hydrothermal fluids at this stage. Below, the late hydrothermal stage is dominated by low-salinity fluids. Using a combination of synchrotron radiation-induced X-ray fluorescence analysis and Raman spectroscopy, the concentration of trace elements (Mn, Fe, Zn, As, Sb, Rb, Cs, Sr, Zr, Nb, Ta, Ag, Sn, Ta, W, rare earth elements (REE), and Cu) was determined in 52 melt and 8 fluid inclusions that are representative of distinct stages from 720°C down to 380°C. Homogenization temperatures and water contents of both melt and fluid inclusions are used to estimate trapping temperatures, thus revealing the evolutionary stage during the process. Trace elements are partitioned in different proportions between the two pegmatite melts, high-salinity brines and exsolving vapors. Concentrations are strongly shifted by co ncomitant crystallization and precipitation of ore-forming minerals. For example, pegmatite melts at the initial stage (700°C) have about 1,600 ppm of Sn. Concentrations in both melts decrease towards lower temperatures due to the crystallization of cassiterite between 650 and 550°C. Tin is preferentially fractionated into the peralkaline melt by a factor of 2–3. While the last pegmatite melts are low in Sn (64 ppm at 500°C), early hydrothermal fluids become again enriched with about 800 ppm of Sn at the boiling stage. A sudden drop in late hydrothermal fluids (23 ppm of Sn at 370°C) results from precipitation of another cassiterite generation between 400 and 370°C. Zinc concentrations in peraluminous melts are low (some tens of parts per million) and are not correlated with temperature. In coexisting peralkaline melts and high-T brines, they are higher by a factor of 2–3. Zinc continuously increases in hydrothermal fluids (3,000 ppm at 400°C), where the precipitation of sphalerite starts. The main removal of Zn from the fluid system occurs at lower temperatures. Similarly, melt and fluid inclusion concentrations of many other trace elements directly reflect the crystallization and precipitation history of minerals at distinctive temperatures or temperature windows.     

Rare-earth elements as source indicators of Pan-African granites from Obudu Plateau,Southeastern Nigeria

The rare-earth element （REE） concentrations of representative granite samples from the southeast of the Obudu Plateau, Nigeria, were analyzed with an attempt to determine the signatures of their source, evolutionary history and tectonic setting. Results indicated that the granites have high absolute REE concentrations （190×10^-6-1191×10^-6; av.=549×10^-6） with the chondrite-normalized REE patterns characterized by steep negative slopes and prominent to slight or no negative Eu anomalies. All the samples are also characterized by high and variable concentrations of the LREE （151×10^-6-1169×10^-6; av.= 466×10^-6）, while the HREE show low abundance （4×10^-6-107×10^-6; av.=28×10^-6）. These are consistent with the variable levels of REE fractionation, and differentiation of the granites. This is further supported by the range of REE contents, the chondrite-normalized patterns and the ratios of LaN/YbN （2.30-343.37）, CeN/YbN （5.94-716.87）, LaN/SmN （3.14-11.68） and TbN/YbN （0.58-1.65）. The general parallelism of the REE patterns, suggest that all the granites were comagmatic in origin, while the high Eu/Eu＊ ratios （0.085-2.807; av.=0.9398） indicate high fo2 at the source. Similarly, irregular variations in LaN/YbN, CeN/YbN and Eu/Eu＊ ratios and REE abundances among the samples suggest behaviors that are related to mantle and crustal sources.     

The high PT stability of apatite and Cl partitioning between apatite and hydrous potassic phases in peridotite: an experimental study to 19 GPa with implications for the transport of P,Cl and K in the upper mantle

High PT experiments were performed in the range 2.5–19 GPa and 800–1,500°C using a synthetic peridotite doped with trace elements and OH-apatite or with Cl-apatite + phlogopite. The aim of the study was (1) to investigate the stability and phase relations of apatite and its high PT breakdown products, (2) to study the compositional evolution with P and T of phosphate and coexisting silicate phases and (3) to measure the Cl-OH partitioning between apatite and coexisting calcic amphibole, phlogopite and K-richterite. Apatite is stable in a garnet-lherzolite assemblage in the range 2.5–8.7 GPa and 800–1,100°C. The high-P breakdown product of apatite is tuite γ-Ca₃ (PO₄)₂, which is stable in the range 8–15 GPa and 1,100–1,300°C. Coexisting apatite and tuite were observed at 8 GPa/1,050°C and 8.7 GPa/1,000°C. MgO in apatite increases with P from 0.8 wt% at 2.5 GPa to 3.2 wt% at 8.7 GPa. Both apatite and tuite may contain significant Na, Sr and REE with a correlation indicating 2 Ca²⁺=Na⁺ + REE³⁺. Tuite has always higher Sr and REE and lower Fe and Mg than apatite. Phosphorus in the peridotite phases decreases in the order P_melt ≫ P_grt ≫ P_Mg2SiO4 > P_cpx > P_opx. The phosphate-saturated P₂O₅ content of garnet increases from 0.07 wt% at 2.5 GPa to 1.5 wt% at 12.8 GPa. Due to the low bulk Na content of the peridotite, ^[8]Na^[4]P^[8]M²⁺ ₋₁ ^[4]Si₋₁ only plays a minor role in controlling the phosphorus content of garnet. Instead, element correlations indicate a major contribution of ^[6]M^2+[4]P^[6]M³⁺ ₋₁ ^[4]Si₋₁. Pyroxenes contain ~200–500 ppm P and olivine has 0.14–0.23 wt% P₂O₅ in the P range 4–8.7 GPa without correlation with P, T or X_Mg. At ≥12.7 GPa, all Mg₂SiO₄ polymorphs have <200 ppm P. Coexisting olivine and wadsleyite show an equal preference for phosphorus. In case of coexisting wadsleyite and ringwoodite, the latter fractionates phosphorus. Although garnet shows by far the highest phosphorus concentrations of any peridotite silicate phase, olivine is no less important as phosphorus carrier and could store the entire bulk phosphorus budget of primitive mantle. In the Cl-apatite + phlogopite-doped peridotite, apatite contains 0.65–1.35 wt% Cl in the PT range 2.5–8.7 GPa/800–1,000°C. Apatite coexists with calcic amphibole at 2.5 GPa, phlogopite at 2.5–5 GPa and K-richterite at 7 GPa, and all silicates contain between 0.2 and 0.6 wt% Cl. No solid potassic phase is stable between 5 and 8.7 GPa. Cl strongly increases the solubility of K in hydrous fluids. This may lead to the breakdown of phlogopite and give rise to the local presence in the mantle of fluids strongly enriched in K, Cl, P and incompatible trace elements. Such fluids may get trapped as micro-inclusions in diamonds and provide bulk compositions suitable for the formation of unusual phases such as KCl or hypersilicic Cl-rich mica.     

Chemical composition of nyerereite and gregoryite from natrocarbonatites of Oldoinyo Lengai volcano,Tanzania

Alkali carbonates nyerereite, ideally Na₂Ca(CO₃)₂ and gregoryite, ideally Na₂CO₃, are the major minerals in natrocarbonatite lavas from Oldoinyo Lengai volcano, northern Tanzania. They occur as pheno- and microphenocrysts in groundmass consisting of fluorite and sylvite; nyerereite typically forms prismatic crystals and gregoryite occurs as round, oval crystals. Both minerals are characterized by relatively high contents of various minor elements. Raman spectroscopy data indicate the presence of sulfur and phosphorous as (SO₄)²⁻ and (PO₄)³⁻ groups. Microprobe analyses show variable composition of both nyerereite and gregoryite. Nyerereite contains 6.1–8.7 wt % K₂O, with subordinate amounts of SrO (1.7–3.3 wt %), BaO (0.3–1.6 wt %), SO₃ (0.8–1.5 wt %), P₂O₅ (0.2–0.8 wt %) and Cl (0.1–0.35 wt %). Gregoryite contains 5.0–11.9 wt % CaO, 3.4–5.8 wt % SO₃, 1.3–4.6 wt % P₂O₅, 0.6–1.0 wt % SrO, 0.1–0.6 wt % BaO and 0.3–0.7 wt % Cl. The content of F is below detection limits in nyerereite and gregoryite. Laser ablation ICP-MS analyses show that REE, Mn, Mg, Rb and Li are typical trace elements in these minerals. Nyerereite is enriched in REE (up to 1080 ppm) and Rb (up to 140 ppm), while gregoryite contains more Mg (up to 367 ppm) and Li (up to 241 ppm) as compared with nyerereite.     

Silicate and salt melts in the genesis of the industrial’noe tin deposit: Evidence from inclusions in minerals

The data obtained on melt and fluid inclusions in minerals of granites, metasomatic rocks, and veins with tin ore mineralization at the Industrial’noe deposit in the southern part of the Omsukchan trough, northeastern Russia, indicate that the melt from which the quartz of the granites crystallized contained globules of salt melts. Silicate melt inclusions were used to determine the principal parameters of the magmatic melts that formed the granites, which had temperatures at 760–1020°C, were under pressures of 0.3–3.6 kbar, and had densities of 2.11–2.60 g/cm³ and water concentrations of 1.7–7.0 wt %. The results obtained on the fluid inclusions testify that the parameters of the mineral-forming fluids broadly varied and corresponded to temperatures at 920–275°C, pressures 0.1–3.1 kbar, densities of 0.70–1.90 g/cm³, and salinities of 4.0–75.0 wt % equiv. NaCl. Electron microprobe analyses of the glasses of twelve homogenized inclusions show concentrations of major components typical of an acid magmatic melt (wt %, average): 73.2% SiO₂, 15.3% Al₂O₃, 1.3% FeO, 0.6% CaO, 3.1% Na₂O, and 4.5% K₂O at elevated concentrations of Cl (up to 0.51 wt %, average 0.31 wt %). The concentrations and distribution of some elements (Cl, K, Ca, Mn, Fe, Cu, Zn, Pb, As, Br, Rb, Sr, and Sn) in polyphase salt globules in quartz from both the granites and a mineralized miarolitic cavity in granite were assayed by micro-PIXE (proton-induced X-ray emission). Analyses of eight salt globules in quartz from the granites point to high concentrations (average, wt %) of Cl (27.5), Fe (9.7), Cu (7.2), Mn (1.1), Zn (0.66), Pb (0.37) and (average, ppm) As (2020), Rb (1850), Sr (1090), and Br (990). The salt globules in the miarolitic quartz are rich in (average of 29 globules, wt %) Cl (25.0), Fe (5.4), Mn (1.0), Zn (0.50), Pb (0.24) and (ppm) Rb (810), Sn (540), and Br (470). The synthesis of all data obtained on melt and fluid inclusions in minerals from the Industrial’noe deposit suggest that the genesis of the tin ore mineralization was related to the crystallization of acid magmatic melts. Original Russian Text@ V.B. Naumov, V.S. Kamenetsky, 2006, published in Geokhimiya, 2006, No. 12, pp. 1279–1289.