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     

High-precision high field strength element partitioning between garnet, amphibole and alkaline melt from Kakanui, New Zealand

The high field strength elements (HFSE: Zr, Hf, Nb, Ta, and W) are an important group of chemical tracers that are increasingly used to investigate magmatic differentiation processes. Successful modeling of these processes requires the availability of accurate mineral-melt partition coefficients (D). To date, these have largely been determined by ion microprobe or laser ablation-ICP-MS analyses of the run products of high-pressure, high-temperature experiments. Since HFSE are (highly) incompatible, relatively immobile, high-charge, and difficult to ionize, these experiments and their analysis are challenging. Here we explore whether high-precision analyses of natural mineral-melt systems can provide additional constraints on HFSE partitioning.The HFSE concentrations in natural garnet and amphibole and their alkaline host melt from Kakanui, New Zealand are determined with high precision isotope dilution on a multi-collector-ICP-MS. Major and trace element compositions combined with Lu-Hf isotopic systematics and detailed petrographic sample analysis are used to assess mineral-melt equilibrium and to provide context for the HFSE D measurements. The whole-rock nephelinite, ∼1 mm sized amphiboles in the nephelinite, and garnet megacrysts have similar initial Hf isotope ratios with a mean initial ¹⁷⁶Hf/¹⁷⁷Hf_{(34 Ma)} = 0.282900 ± 0.000026 (2σ). In contrast, the amphibole megacrysts are isotopically distinct (¹⁷⁶Hf/¹⁷⁷Hf_{(34 Ma)} = 0.282830 ± 0.000011). Rare earth element D values for garnet megacryst-nephelinite melt and ∼1 mm amphibole-nephelinite melt plotted as a function of ionic radii show classic near-parabolic trends that are in excellent agreement with crystal lattice-strain models. These observations are consistent with equilibrium between the whole-rock nephelinite, the ∼1 mm amphibole grains within the nephelinite and the garnet megacrysts.High-precision isotope dilution results for Zr and Hf in garnet (D_Zr = 0.220 ± 0.007 and D_Hf = 0.216 ± 0.005 [2σ]), and for all HFSE in amphibole are consistent with previous experimental findings. However, our measurements for Nb and Ta in garnet (D_Nb = 0.0007 ± 0.0001 and D_Ta = 0.0011 ± 0.0006 [2σ]) show that conventional methods may overestimate Nb and Ta concentrations, thereby overestimating both Nb and Ta absolute D values for garnet by up to 3 orders of magnitude and underestimating D_Nb/D_Ta by greater than a factor of 100. As a consequence, the role of residual garnet in imposing Nb/Ta fractionation may be less important than previously thought. Moreover, garnet D_Hf/D_W = 17 and D_Nb/D_Zr = 0.003 imply fractionation of Hf from W and Nb from Zr upon garnet crystallization, which may have influenced short-lived ¹⁸²Hf-¹⁸²W and ⁹²Nb-⁹²Zr isotopic systems in Hadean time.     

Partitioning of trace elements between rutile and silicate melts: Implications for subduction zones

Mineral/melt trace element partition coefficients were determined for rutile (TiO₂) for a large number of trace elements (Zr, Hf, Nb, Ta, V, Co, Cu, Zn, Sr, REE, Cr, Sb, W, U, Th). Whilst the high field strength elements (Zr, Hf, Nb, Ta) are compatible in rutile, other studied trace elements are incompatible (Sr, Th, REE). In all experiments we found D_Ta > D_Nb, D_Hf > D_Zr and D_U > D_Th. Partition coefficients for some polyvalent elements (Sb, W, and Co) were sensitive to oxygen fugacity. Melt composition exerts a strong influence on HFSE partition coefficients. With increasing polymerization of the melt, rutile/melt partition coefficients for the high field strength elements Zr, Hf, Nb and Ta increase about an order of magnitude. However, D_Nb/D_Ta and D_Hf/D_Zr are not significantly affected by melt composition. Because D_U ? D_Th, partial melting of rutile-bearing eclogite in subducted lithosphere may cause excesses of ²³⁰Th over ²³⁸U in some island arc lavas, whereas dehydration of subducted lithosphere may cause excesses of ²³⁸U over ²³⁰Th. From our partitioning results we infer partition coefficients for protactinium (Pa) which we predict to be much lower than previously anticipated. Contrary to previous studies, our data imply that rutile should not significantly influence observed ²³¹Pa-²³⁵U disequilibria in certain volcanic rocks.     

Trace element partitioning between apatite and silicate melts

We present new experimental apatite/melt trace element partition coefficients for a large number of trace elements (Cs, Rb, Ba, La, Ce, Pr, Sm, Gd, Lu, Y, Sr, Zr, Hf, Nb, Ta, U, Pb, and Th). The experiments were conducted at pressures of 1.0 GPa and temperatures of 1250 °C. The rare earth elements (La, Ce, Pr, Sm, Gd, and Lu), Y, and Sr are compatible in apatite, whereas the larger lithophile elements (Cs, Rb, and Ba) are strongly incompatible. Other trace elements such as U, Th, and Pb have partition coefficients close to unity. In all experiments we found D_Hf > D_Zr, D_Ta ≈ D_Nb, and D_Ba > D_Rb > D_Cs. The experiments reveal a strong influence of melt composition on REE partition coefficients. With increasing polymerisation of the melt, apatite/melt partition coefficients for the rare earth elements increase for about an order of magnitude. We also present some results in fluorine-rich and water-rich systems, respectively, but no significant influence of either H₂O or F on the partitioning was found. Furthermore, we also present experimentally determined partition coefficients in close-to natural compositions which should be directly applicable to magmatic processes.     

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     

Partitioning and Hydrolysis of Nb and Ta and Their Implications with Regard to Mineralization

K₂NbOF₅ · H₂O and K₂TaF₇ were prepared through melting Nb₂O₅ and Ta₂O₅ respectively with KHF₂ · 2H₂O, followed by recrystallizing. The hydrolysis properties of K₂NbOF₅ and K₂TaF₇ were determined again by using a rapidly quench vessel. As temperature (from 250 to 550 °C) and pressure (from 500 to 1500 bars) increase, the degree of hydrolysis of both K₂NbOF₅ and K₂TaF₇ will increase. Nb- and Ta-fluorine complex compounds are instable in supercritical aqueous fluids. The degree of hydrolysis of both K₂NbOF₅ and K₂TaF₇ decreases with increasing concentration of HF, independent of the concentration of NaF. The partition coefficients of Nb and Ta between granitic melt and fluid phase are less than 0.15, i.e., most of Nb and Ta are left in granitic melt. The partition coefficient of Ta is more dependent on the concentration of HF than that of Nb. The significance of hydrolysis in Nb- and Ta- mineralization is also discussed in the present paper.     

Vanadium and niobium behavior in rutile as a function of oxygen fugacity: evidence from natural samples

Vanadium occurs in multiple valence states in nature, whereas Nb is exclusively pentavalent. Both are compatible in rutile, but the relationship of V–Nb partitioning and dependence on oxygen fugacity (expressed as fO₂) has not yet been systematically investigated. We acquired trace-element concentrations on rutile grains (n = 86) in nine eclogitic samples from the Dabie-Sulu orogenic belt by laser ablation inductively coupled plasma mass spectrometry (LA–ICP–MS) and combined them with published results in order to assess the direct and indirect effects of oxygen fugacity on the partitioning of V and Nb into rutile. A well-defined negative correlation between Nb (7–1,200 ppm) and V concentrations (50–3,200 ppm) was found, documenting a competitive relationship in the rutile crystal that does not appear to be controlled by bulk rock or mineral compositions. Based on the published relationship of ^RtD_V and V valence with ?QFM, we suggest that the priority order of V incorporation into rutile is V⁴⁺ > V³⁺ > V⁵⁺. The inferred Nb–V competitive relationship in rutile from the Dabie-Sulu orogenic belt could be explained by decreasing fO₂ due to dehydration reactions involving loss of oxidizing fluids during continental subduction: The increased proportion of V³⁺ (expressed as V³⁺/∑V) and attendant decrease in ^RtD_V is suggested to lead to an increase in rutile lattice sites available for Nb⁵⁺. A similar effect may be observed under more oxidizing conditions. When V⁵⁺/∑V increases, ^RtD_V shows a dramatic decline and Nb concentration increases considerably. This is possibly documented by rutile in highly metasomatized and oxidized MARID-type (MARID: mica–amphibole–rutile–ilmenite–diopside) mantle xenoliths from the Kaapvaal craton, which also show a negative V–Nb covariation. In addition, their Nb/Ta covaries with V concentrations: For V concentrations <1,250 ppm, Nb/Ta ranges between 35 and 45, whereas for V > 1,250 ppm, Nb/Ta is considerably lower (5–15). This relationship is mainly controlled by a change in Nb concentrations, suggesting that the indirect dependence of ^RtD_Nb on fO₂, which is not mirrored in ^RtD_Ta, can exert considerable influence on rutile Nb–Ta fractionation.     

Recycled crust controls contrasting source compositions of Mesozoic and Cenozoic basalts in the North China Craton

We explore Fe/Mn and Nb/Ta ratios of basalts as potential tracers for differentiating melts of recycled mafic crustal lithologies from peridotitic melts. Trace elements and Fe/Mn ratios of the Mesozoic and Cenozoic basalts from East China were analyzed by ICP-MS. Low Nb/Ta ratios (15.4 ± 0.3 (2σ, n = 45)), high Nb and Ta contents (60.1 and 4.01 ppm) and high Fe/Mn ratios (64.7 ± 1.5 (2σ, n = 45)) characterize the <110 Ma basalts. Mesozoic basalts with ages >110 Ma are characterized by superchondritic Nb/Ta ratios (20.1 ± 0.3 (2σ, n = 25)), low Nb and Ta contents (10.8 and 0.54 ppm) and slightly lower Fe/Mn ratios (60.0 ± 1.1 (2σ, n = 25)). Both the Mesozoic and Cenozoic basalts have Fe/Mn ratios higher than basaltic melt formed by partial melting of peridotite at the same MgO and CaO levels. Although both the Mesozoic and Cenozoic basalts are characterized by highly fractionated REE patterns, the >110 Ma basalts have island arc-type trace element patterns (i.e., depletion in Nb and Ta), whereas OIB-type trace element patterns (e.g., no depletion in Nb and Ta) are characteristic of the <110 Ma basalts. Based on D_Fe/Mn values for olivine, clinopyroxene, orthopyroxene and garnet, high Fe/Mn ratios and negative correlations of Fe/Mn with Yb (Y) of the <110 Ma basalts suggest clinopyroxene/garnet-rich mantle sources. The lower Fe/Mn ratios and positive correlations of Fe/Mn with Y and Yb in the >110 Ma basalts suggest orthopyroxene/garnet-rich mantle sources. Combining these data with Sr-Nd isotopes, we present a conceptual model to explain the Nb/Ta ratios and PM-normalized trace element patterns of the >110 and <110 Ma basalts. Preferential melting of recycled ancient lower continental crust during Mesozoic lithospheric thinning resulted in (1) peridotite-melt/fluid reaction that formed the orthopyroxene/garnet-rich mantle sources for the >110 Ma basalts, and (2) peridotite + rutile-bearing eclogite mixing that formed the clinopyroxene/garnet-rich mantle sources for the <110 Ma basalts. The choice of models may indeed be arbitrary and non-unique, but the goal is to seek relatively simple forward models that explain the characteristics of the lavas, and the differences between the >110 and <110 Ma basalts, in a relatively consistent geodynamic framework.     

Water diffusion in dacitic melt

H₂O diffusion in dacitic melt was investigated at 0.48-0.95 GPa and 786-893 K in a piston-cylinder apparatus. The diffusion couple design was used, in which a nominally dry dacitic glass makes one half and is juxtaposed with a hydrous dacitic glass containing up to ∼8 wt.% total water (H₂O_t). H₂O concentration profiles were measured on quenched glasses with infrared microspectroscopy. The H₂O diffusivity in dacite increases rapidly with water content under experimental conditions, similar to previous measurements at the same temperature but at pressure <0.15 GPa. However, compared with the low-pressure data, H₂O diffusion at high pressure is systematically slower. H₂O diffusion profiles in dacite can be modeled by assuming molecular H₂O (H₂O_m) is the diffusing species. Total H₂O diffusivity D_H2Ot within 786-1798 K, 0-1 GPa, and 0-8 wt.% H₂O_t can be expressed as: where D_H2Ot is in m²/s, T is temperature in K, P is pressure in GPa, K = exp(1.49 − 2634/T) is the equilibrium constant of speciation reaction (H₂O_m+O?2OH) in the melt, X = C/18.015/[C/18.015 + (100 − C)/33.82], C is wt.% of H₂O_t, and 18.015 and 33.82 g/mol correspond to the molar masses of H₂O and anhydrous dacite on a single oxygen basis. Compared to H₂O diffusion in rhyolite, diffusivity in dacite is lower at intermediate temperatures but higher at superliquidus temperatures. This general H₂O diffusivity expression can be applied to a broad range of geological conditions, including both magma chamber processes and volcanic eruption dynamics from conduit to the surface.     

Trace element partitioning between ilmenite, armalcolite and anhydrous silicate melt: Implications for the formation of lunar high-Ti mare basalts

We performed a series of experiments at high pressures and temperatures to determine the partitioning of a wide range of trace elements between ilmenite (Ilm), armalcolite (Arm) and anhydrous lunar silicate melt, to constrain geochemical models of the formation of titanium-rich melts in the Moon. Experiments were performed in graphite-lined platinum capsules at pressures and temperatures ranging from 1.1 to 2.3 GPa and 1300-1400 °C using a synthetic Ti-enriched Apollo ‘black glass’ composition in the CaO-FeO-MgO-Al₂O₃-TiO₂-SiO₂ system. Ilmenite-melt and armalcolite-melt partition coefficients (D) show highly incompatible values for the rare earth elements (REE) with the light REE more incompatible compared to the heavy REE ( 0.0020 ± 0.0010 to 0.069 ± 0.010 for ilmenite; 0.0048 ± 0.0023 to 0.041 ± 0.008 for armalcolite). D values for the high field strength elements vary from highly incompatible for Th, U and to a lesser extent W (for ilmenite: 0.0013 ± 0.0008, 0.0035 ± 0.0015 and 0.039 ± 0.005, and for armalcolite 0.008 ± 0.003, 0.0048 ± 0.0022 and 0.062 ± 0.03), to mildly incompatible for Nb, Ta, Zr, and Hf (e.g. 0.28 ± 0.05 and : 0.76 ± 0.07). Both minerals fractionate the high field strength elements with D_Ta/D_Nb and D_Hf/D_Zr between 1.3 and 1.6 for ilmenite and 1.3 and 1.4 for armalcolite. Armalcolite is slightly more efficient at fractionating Hf from W during lunar magma ocean crystallisation, with D_Hf/D_W = 12-13 compared to 6.7-7.5 for ilmenite. The transition metals vary from mildly incompatible to compatible, with the highest compatibilities for Cr in ilmenite (D ∼ 7.5) and V in armalcolite (D ∼ 8.1). D values show no clear variation with pressure in the small range covered.Crystal lattice strain modelling of D values for di-, tri- and tetravalent trace elements shows that in ilmenite, divalent elements prefer to substitute for Fe while armalcolite data suggest REE replacing Mg. Tetravalent cations appear to preferentially substitute for Ti in both minerals, with the exception of Th and U that likely substitute for the larger Fe or Mg cations. Crystal lattice strain modelling is also used to identify and correct for very small (∼0.3 wt.%) melt contamination of trace element concentration determinations in crystals.Our results are used to model the Lu-Hf-Ti concentrations of lunar high-Ti mare basalts. The combination of their subchondritic Lu/Hf ratios and high TiO₂ contents requires preferential dissolution of ilmenite or armalcolite from late-stage, lunar magma ocean cumulates into low-Ti partial melts of deeper pyroxene-rich cumulates.     

Experimental study of partitioning of tantalum,niobium, manganese,and fluorine between aqueous fluoride fluid and granitic and alkaline melts

This study presents a new set of quantitative experimental data on the partitioning of Ta, Nb, Mn, and F between aqueous F-bearing fluid and water-saturated, Li- and F-rich haplogranite melts with varying alumina/alkali content at T = 650–850 °C and P = 100 MPa. The starting homogeneous glasses were preliminary obtained by melting of three gel mixtures of K₂O-Na₂O-Al₂O₃-SiO₂ composition with a variable Al₂O₃/(Na₂O+K₂O) ratio, ranging from 0.64 (alkaline) and 1.1 (near-normal) to 1.7 (alumina-rich). Ta, Nb, and Mn were originally present in glass only, whereas F was load in both the glass and the solution. The solutionto-glass weight ratio was 1.5–3.0. The compositions of quenched glass were measured by an electronic microprobe, and those of the aqueous solution, with the ICP-MS and ICP-AES methods. The F concentration in the quenched solution was calculated from the mass balance. Under experimental conditions the partition coefficients of Ta, Nb, and Mn between the fluid and the granitic melt (weight ratio ^fluid C _Ta/^melt C _Ta = ^fluid/melt D _Ta) are shown to be extremely low (0.001–0.008 for Ta, 0.001–0.022 for Nb, and 0.002–0.010 for Mn); thus, these metals partition preferentially into the melt. The coefficients ^fluid/melt D _Ta and ^fluid/melt D _Nb generally increase either with increasing alumina ratio A/NKM in the glass composition, or with rising temperature. The experiments also demonstrated that F preferentially concentrates in the melt; and the partition coefficients of F are below 1, being within the range of 0.1–0.7.

     

Bulk-rock Major and Trace Element Compositions of Abyssal Peridotites: Implications for Mantle Melting, Melt Extraction and Post-melting Processes Beneath Mid-Ocean Ridges

This paper presents the first comprehensive major and traceelement data for 130 abyssal peridotite samples from the Pacificand Indian ocean ridge–transform systems. The data revealimportant features about the petrogenesis of these rocks, mantlemelting and melt extraction processes beneath ocean ridges,and elemental behaviours. Although abyssal peridotites are serpentinized,and have also experienced seafloor weathering, magmatic signaturesremain well preserved in the bulk-rock compositions. The betterinverse correlation of MgO with progressively heavier rare earthelements (REE) reflects varying amounts of melt depletion. Thismelt depletion may result from recent sub-ridge mantle melting,but could also be inherited from previous melt extraction eventsfrom the fertile mantle source. Light REE (LREE) in bulk-rocksamples are more enriched, not more depleted, than in the constituentclinopyroxenes (cpx) of the same sample suites. If the cpx LREErecord sub-ridge mantle melting processes, then the bulk-rockLREE must reflect post-melting refertilization. The significantcorrelations of LREE (e.g. La, Ce, Pr, Nd) with immobile highfield strength elements (HFSE, e.g. Nb and Zr) suggest thatenrichments of both LREE and HFSE resulted from a common magmaticprocess. The refertilization takes place in the ‘cold’thermal boundary layer (TBL) beneath ridges through which theascending melts migrate and interact with the advanced residues.The refertilization apparently did not affect the cpx relicsanalyzed for trace elements. This observation suggests grain-boundaryporous melt migration in the TBL. The ascending melts may notbe thermally ‘reactive’, and thus may have affectedonly cpx rims, which, together with precipitated olivine, entrappedmelt, and the rest of the rock, were subsequently serpentinized.Very large variations in bulk-rock Zr/Hf and Nb/Ta ratios areobserved, which are unexpected. The correlation between thetwo ratios is consistent with observations on basalts that D_Zr/D_Hf< 1 and D_Nb/D_Ta < 1. Given the identical charges (5⁺ forNb and Ta; 4⁺ for Zr and Hf) and essentially the same ionicradii (R_Nb/R_Ta = 1·000 and R_Zr/R_Hf = 1·006–1·026),yet a factor of 2 mass differences (M_Zr/M_Hf = 0·511 andM_Nb/M_Ta = 0·513), it is hypothesized that mass-dependentD values, or diffusion or mass-transfer rates may be importantin causing elemental fractionations during porous melt migrationin the TBL. It is also possible that some ‘exotic’phases with highly fractionated Zr/Hf and Nb/Ta ratios may existin these rocks, thus having ‘nugget’ effects onthe bulk-rock analyses. All these hypotheses need testing byconstraining the storage and distribution of all the incompatibletrace elements in mantle peridotite. As serpentine containsup to 13 wt % H₂O, and is stable up to 7 GPa before it is transformedto dense hydrous magnesium silicate phases that are stable atpressures of 5–50 GPa, it is possible that the serpentinizedperidotites may survive, at least partly, subduction-zone dehydration,and transport large amounts of H₂O (also Ba, Rb, Cs, K, U, Sr,Pb, etc. with elevated U/Pb ratios) into the deep mantle. Thelatter may contribute to the HIMU component in the source regionsof some oceanic basalts. KEY WORDS: abyssal peridotites; serpentinization; seafloor weathering; bulk-rock major and trace element compositions; mantle melting; melt extraction; melt–residue interaction; porous flows; Nb/Ta and Zr/Hf fractionations; HIMU mantle sources     

Partitioning of Na between olivine and melt: An experimental study with application to the formation of meteoritic Na2O-rich chondrule glass and refractory forsterite grains

We report experimentally determined 1 atm olivine/melt D_Na partitioning data for low f_O2, a variety of melt compositions and a temperature range of 1325-1522 °C. We demonstrated that high-current electron microprobe analyses (EPMA, I = 500 nA, 600 s on the peak) allow quantitative determination of Na₂O in olivine down to ∼10 μg/g. The mean olivine/melt D_Na from 12 experimental runs is 0.0031 ± 0.0007 (1σ). This is the recommended value for low pressures and a wide range of natural compositions.This result is applied to the problem of the origin of alkalis in chondrules and the formation of chondritic refractory forsterite grains. The data on Semarkona (LL3.0) chondrules show that Na₂O is primordial and was present during olivine crystallization. For refractory forsterite grains from Murchison (CM2), we demonstrate that high CaO contents are not a result of equilibration with Na₂O-rich melts, but require high activities of CaO during their formation.     

The Al (Nb,Ta) Ti(in−2) substitution in titanite: the emergence of a new species?

Summary The highest (Nb, Ta) content ever encountered in titanite is reported from the Maríkov 11 pegmatite in northern Moravia, Czech Republic. This dike is a member of a pegmatite swarm of the beryl-columbite subtype, metamorphosed under conditions of the amphibolite facies. The pegmatite carries, i.a., rare tantalian rutile intergrown with titanian ixiolite, titanian columbite-tantalite, fersmite and microlite. Fissures generated in the Nb, Ta oxide minerals during deformation are filled with titanite, formed by reaction of the oxide minerals with metamorphic pore fluids. The titanite displays limited degrees of substitutions Na(Ta > Nb)(CaTi)_–1, (Ta > Nb)₄Ti_–4Si_–1 and AI(OH, F)(TiO)_–1, but an extensive (and occasionally the sole significant) substitution (Al > Fe³⁺)(Ta > Nb)Ti_–2, responsible for widespread oscillatory zoning. This substitution reduces the proportion of the titanite componentsensu stricto, CaTiSiO₄,O, to less than 50 mole % in many analyzed spots. The extreme composition corresponds to (Ca_0.994Na_0.011)(Ti_0.436Sn_0.007Al_0.280Fe³⁺ _0.006Ta_0.199Nb_0.079)Si_0.988O₄(O_0.974F_0.026). However, so far this substitution fails to generate compositions that would define a new species.

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Zusammenfassung Die AI(Nb, Ta)Ti_–2 Substitution im Titanit: Auftauchen einer neuen Mineralspecies? Die höchsten (Nb, Ta) Gehalte, die jemals für Titanit gefunden wurden, werden für den Maríkov II Pegmatit in Nordmähren, Tschechei, berichtet. Der Intrusivgang ist Teil eines Amphibolit-faziell überprägten Pegmatitschwarms vom Beryll-Columbit Subtypus Der Pegmatit führt u.a. seltene tantalbetonte Rutile verwachsen mit titanbetontem Ixiolith, titanbetontem Columbit-Tantalit, Fersmit and Mikrolith. Deformationsbedingte Frakturen in den (Nb, Ta) Oxiden sind mit Titanit, als Folge der Reaktion der metamorphen Porenlösungen mit den Oxidmineralen, verkittet. Titanit zeigt begrenzte Substitutionen Na(Ta > Nb)(CaTi)_–1,(Ta > Nb)₄Ti_–4Si_–1 and Al(OH, F)(TiO)_–1, aber extensive (und gelegentlich einzig bedeutsame) Substitution (Al >> Fe³⁺)(Ta > Nb)Ti_–2, die eine weitverbreitete, oszillierende Zonierung hervorruft. Diese Substitution verringert den Anteil der Titanit-Komponentesensu stricto, CaTiSiO,O, auf weniger als 50 Mol% in vielen Analysen. Die Extremzusammensetzung entspricht Ca_0.994Na_0.11) (T_10.436Sn_0.007Al_0.280Fe³⁺ _0.006Ta_0.199Nb_0.079)Si_0.988O₄(O_0.974F_0.026). Das AusmaB dieser Substitution ist unzureichend, um eine neue Mineralspecies zu definieren.

     

福建永定大坪花岗斑岩体的铌钽富集特征研究

福建大坪花岗斑岩体位于永定县城南部的大石凹—蓝地火山喷发盆地,具斑状结构,基质呈霏细结构、细-微粒结构。文章运用电子探针(EMPA)和激光剥蚀电感耦合等离子体质谱仪(LA-ICP-MS)等技术,对大坪岩体ZK10001钻孔中不同深度的岩石样品进行了矿物和岩石化学分析。分析结果表明,大坪岩体岩性为黑鳞云母碱长花岗斑岩,属于过铝质钙碱性花岗岩,具有较高的分异演化程度,Nb2O5和Ta2O5含量达到了花岗岩型稀有金属矿床的工业品位。铌钽矿物主要与黄玉、萤石的集合体呈稀疏浸染状、星点状产于基质间隙内,其次以星点状存在于石英和长石斑晶中。矿石矿物赋存特征与宜春钽铌矿床类似,可能具有一定的可选性和经济价值。大坪岩体的铌钽富集特征不同于斑岩型铜、钼矿床,与花岗岩型铌钽矿床也存在较大的差别,铌钽的富集过程经历了深部斑晶阶段和浅部基质阶段两阶段岩浆结晶分异作用,F等挥发分促进了铌钽在结晶残余岩浆中富集,在基质间隙间沉淀。大坪矿化岩体的发现暗示斑岩型铌钽矿床存在的可能性。     

Water speciation and diffusion in haploandesitic melts at 743-873 K and 100 MPa

Water is an important volatile component in andesitic eruptions and deep-seated andesitic magma chambers. We report an investigation of H₂O speciation and diffusion by dehydrating haploandesitic melts containing ?2.5 wt.% water at 743-873 K and 100 MPa in cold-seal pressure vessels. FTIR microspectroscopy was utilized to measure species [molecular H₂O (H₂O_m) and hydroxyl group (OH)] and total H₂O (H₂O_t) concentration profiles on the quenched glasses from the dehydration experiments. The equilibrium constant of the H₂O speciation reaction H₂O_m+O?2OH, K = (X_OH)²/(X_H2OmX_O) where X means mole fraction on a single oxygen basis, in this Fe-free andesite varies with temperature as ln K = 1.547-2453/T where T is in K. Comparison with previous speciation data on rhyolitic and dacitic melts indicates that, for a given water concentration, Fe-free andesitic melt contains more hydroxyl groups. Water diffusivity at the experimental conditions increases rapidly with H₂O concentration, contrary to previous H₂O diffusion data in an andesitic melt at 1608-1848 K. The diffusion profiles are consistent with the model that molecular H₂O is the diffusion species. Based on the above speciation model, H₂O_m and H₂O_t diffusivity (in m²/s) in haploandesite at 743-873 K, 100 MPa, and H₂O_t ? 2.5 wt.% can be formulated as

     

The partitioning behavior of As and Au in S-free and S-bearing magmatic assemblages

The partitioning of As and Au between rhyolite melt and low-salinity vapor (2 wt% NaCl eq.) in a melt-vapor-Au metal ± magnetite ± pyrrhotite assemblage has been quantified at 800 °C, 120 MPa and f_O2=NNO. The S-bearing runs have calculated values for the fugacities of H₂S, SO₂ and S₂ of logf_H2S=1.1, logf_SO2=-1.5, and logf_S2=-3.0. The ratio of H₂S to SO₂ is on the order of 400. The experiments constrain the effect of S on the partitioning behavior of As and Au at magmatic conditions. Calculated average Nernst-type partition coefficients (±1σ) for As between vapor and melt, , are 1.0 ± 0.1 and 2.5 ± 0.3 in the S-free and S-bearing assemblages, respectively. These results suggest that sulfur has a small, but statistically meaningful, effect on the mass transfer of As between silicate melt and low-salinity vapor at the experimental conditions. Efficiencies of removal, calculated following Candela and Holland (1986), suggest that the S-free and S-bearing low-salinity vapor can scavenge approximately 41% and 63% As from water-saturated rhyolite melt, respectively, during devolatilization assuming that As is partitioned into magnetite and pyrrhotite during second boiling. The S-free data are consistent with the presence of arsenous acid, As(OH)₃ in the vapor phase. However, the S-bearing data suggest the presence of both arsenous acid and a As-S complex in S-bearing magmatic vapor. Apparent equilibrium constants, , describing the partitioning of As between melt and vapor are −1.3 (0.1) and −1.1 (0.1) for the S-free and S-bearing runs, respectively. The increase in the value of with the addition of S suggests a role for S in complexing and scavenging As from the melt during degassing.The calculated vapor/melt partition coefficients (±1σ) for Au between vapor and melt, , in S-free and S-bearing assemblages are 15 ± 2.5 and 12 ± 0.3, respectively. Efficiencies of removal (Candela and Holland, 1986) for the S-free melt, calculated assuming that magnetite is the dominant Au-sequestering solid phase during crystallization (Simon et al., 2003), suggest that magmatic vapor may scavenge on the order of 72% Au from a water-saturated melt. Efficiencies of removal calculated for the S-bearing assemblage, assuming pyrrhotite and magnetite are the dominant Au-sequestering solid phases, indicate that vapor may scavenge on the order of 60% Au from the melt. These model calculations suggest that the loss of pyrrhotite and magnetite from a melt, owing to punctuated differentiation during ascent and emplacement, does not prohibit the ability of a rhyolite melt to generate a large-tonnage Au deposit. Apparent equilibrium constants describing the partitioning of Au between melt and vapor were calculated using the mean values for the S-free and S-bearing assemblages; only S-bearing data from runs longer than 400 h were used as shorter runs may not have reached equilibrium with respect only to vapor/melt partitioning of Au. The values for are −4.4 (0.1) and −4.2 (0.2) for the S-free and S-bearing runs, respectively. These data suggest that the presence of S does not affect the mass transfer of Au from degassing silicate melt to an exsolved, low-salinity vapor in a low-f_S2 assemblage (i.e., pyrrhotite-magnetite at NNO) at the experimental conditions reported here. Efficiencies of removal are calculated and used to model the mass transfer of Au from a crystallizing silicate melt to an exsolved, low-salinity vapor phase. The calculations suggest that the model, absolute tonnage of Au scavenged and transported by S-free and S-bearing vapors, from a crystallizing melt, would be comparable and that the time-integrated flux of low-salinity vapor could be responsible for a significant quantity of the Au in magmatic-hydrothermal ore deposits.     

Partitioning of F between H2O and CO2 fluids and topaz rhyolite melt

Fluid/melt distribution coefficients for F have been determined in experiments conducted with peraluminous topaz rhyolite melts and fluids consisting of H₂O and H₂O+CO₂ at pressures of 0.5 to 5 kbar, temperatures of 775°–1000°C, and concentrations of F in the melt ranging from 0.5 to 6.9 wt%. The major element, F, and Cl concentrations of the starting material and run product glasses were determined by electron microprobe, and the concentration of F in the fluid was calculated by mass balance. The H₂O concentrations of some run product glasses were determined by ion microprobe (SIMS). The solubility of melt in the fluid phase increases with increasing F in the system; the solubility of H₂O in the melt is independent of the F concentration of the system with up to 6.3 wt% F in the melt. No evidence of immiscible silica- and fluoriderich liquids was detected in the hydrous but water-undersaturated starting material glasses (8.5 wt% F in melt) or in the water-saturated run product glasses. F concentrates in topaz rhyolite melts relative to coexisting fluids at most conditions studied; however, D_F (wt% F in fluid/wt% F in melt) increases strongly with increasing F in the system. Maximum values of D_F in this study are significantly larger than those previously reported in the literature. Linear extrapolation of the data suggests that D_F is greater than one for water-saturated, peraluminous granitic melts containing 8 wt% F at 800° C and 2 kbar. D_F increases as temperature and as (H₂O/H₂O+CO₂) of the fluid increase. For topaz rhyolite melts containing 1 wt% F and with H₂O-rich fluids, D_F is independent of changes in pressure from 2 to 5 kbar at 800° C; for melts containing 1 wt% F and in equilibrium with CO₂-bearing fluids the concentrations of F in fluid increases with increasing pressure. F-and lithophile element-enriched granites may evolve to compositions containing extreme concentrations of F during the final stages of crystallization. If F in the melt exceeds 8 wt%, D_F is greater than one and the associated magmatic-hydrothermal fluid contains >4 molal F. Such F-enriched fluids may be important in the mass transport of ore constituents, i.e., F, Mo, W, Sn, Li, Be, Rb, Cs, U, Th, Nb, Ta, and B, from the magma.     

Determination of fluid/melt partition coefficients by LA-ICPMS analysis of co-existing fluid and silicate melt inclusions: Controls on element partitioning

Analyses of co-existing silicate melt and fluid inclusions, entrapped in quartz crystals in volatile saturated magmatic systems, allowed direct quantitative determination of fluid/melt partition coefficients. Investigations of various granitic systems (peralkaline to peraluminous in composition, log fO₂ = NNO−1.7 to NNO+4.5) exsolving fluids with various chlorinities (1-14 mol/kg) allowed us to assess the effect of these variables on the fluid/melt partition coefficients (D). Partition coefficients for Pb, Zn, Ag and Fe show a nearly linear increase with the chlorinity of these fluid (D_Pb ∼ 6 ∗ m_Cl, D_Zn ∼ 8 ∗ m_Cl, D_Ag ∼ 4 ∗ m_Cl, D_Fe ∼ 1.4 ∗ m_Cl, where m_Cl is the molinity of Cl). This suggests that these metals are dissolved primarily as Cl-complexes and neither oxygen fugacity nor the composition of the melt affects significantly their fluid/melt partitioning. By contrast, partition coefficients for Mo, B, As, Sb and Bi are highest in low salinity (1-2 mol/kg Cl) fluids with maximum values of D_Mo ∼ 20, D_B ∼ 15, D_As ∼ 13, D_Sb ∼ 8, D_Bi ∼ 15 indicating dissolution as non-chloride (e.g., hydroxy) complexes. Fluid/melt partition coefficients of copper are highly variable, but highest between vapor like fluids and silicate melt (D_Cu ? 2700), indicating an important role for ligands other than Cl. Partition coefficients for W generally increase with increasing chlorinity, but are exceptionally low in some of the studied brines which may indicate an effect of other parameters. Fluid/melt partition coefficients of Sn show a high variability but likely increase with the chlorinity of the fluid (D_Sn = 0.3-42, D_W = 0.8-60), and decrease with decreasing oxygen fugacity or melt peraluminosity.