Partitioning of trace elements between rutile and silicate melts: Implications for subduction zones   总被引：9，自引：0，他引：9  

Stephan Klemme  Stefan Prowatke  Detlef Günther 《Geochimica et cosmochimica acta》2005,69(9):2361-2371

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.  相似文献   

Experimental determination of F and Cl partitioning between lherzolite and basaltic melt     

Célia Dalou  Kenneth T. Koga  Nobumichi Shimizu  Julien Boulon  Jean-Luc Devidal 《Contributions to Mineralogy and Petrology》2012,163(4):591-609

We experimentally determined F and Cl partition coefficients together with that of 19 trace elements (including REE, U-Th, HFSE and LILE) between basaltic melt and lherzolite minerals: olivine, orthopyroxene, clinopyroxene, plagioclase and garnet. Under conditions from 8 to 25 kbars and from 1,265 to 1,430°C, compatibilities of F and Cl are globally ordered as D ^Cpx/melt > D ^Opx/melt > D ^Grt/melt > D ^Ol/melt > D ^Plag/melt, and D _F ^mineral/melt is larger than D _Cl^mineral/melt. Four other major results were brought to light. (1) Chlorine partition coefficients positively correlate with the jadeite component in orthopyroxene, and increase of the CaTs component promotes Cl incorporation in clinopyroxene. (2) Variations of fluorine partition coefficients correlate strongly with melt viscosity. (3) F and Cl partition coefficients correlate with the Young’s modulus (E ₀) of pyroxene octahedral sites (M sites) and with Raman vibrational modes of pyroxenes. This demonstrates a fundamental interaction between the M site of pyroxenes and the incorporation of F and Cl. (4) We also determined the parameters of the lattice-strain model applied to 3+ cation trace elements for the two M sites in orthopyroxene and clinopyroxene: D ₀^M1, D ₀^M2, r ₀^M1, r ₀^M2, E ₀^M1 and E ₀^M2.  相似文献   

Partitioning behavior of chlorine and fluorine in the system apatite-silicate melt-fluid   总被引：3，自引：0，他引：3  

Edmond A. Mathez  James D. Webster 《Geochimica et cosmochimica acta》2005,69(5):1275-1286

The partitioning behavior of Cl among apatite, mafic silicate melt, and aqueous fluid and of F between apatite and melt have been determined in experiments conducted at 1066 to 1150 °C and 199-205 MPa. The value of D_Cl^apatite/melt (wt. fraction of Cl in apatite/Cl in melt) ≈0.8 for silicate melt containing less than ∼3.8 wt.% Cl. At higher melt Cl contents, small increases in melt Cl concentration are accompanied by large increases in apatite Cl concentration, forcing D_Cl^apatite/melt to increase as well. Melt containing less than 3.8% Cl coexists with water-rich vapor; that containing more Cl coexists with saline fluid, the salinity of which increases rapidly with small increases in melt Cl content, analogous to the dependency of apatite composition on melt Cl content. This behavior is due to the fact that the solubility of Cl in silicate melt depends strongly on the composition of the melt, particularly its Mg, Ca, Fe, and Si contents. Once the melt becomes “saturated” in Cl, additional Cl must be accommodated by coexisting fluid, apatite, or other phases rather than the melt itself. Because Cl solubility depends on composition, the Cl concentration at which D_Cl^apatite/melt and D_Cl^fluid/melt begin to increase also depends on composition. The experiments reveal that D_F^apatite/melt ≈3.4. In contrast to Cl, the concentration of F in silicate melt is only weakly dependent on composition (mainly on melt Ca contents), so D_F^apatite/melt is constant for a wide range of composition.The experimental data demonstrate that the fluids present in the waning stages of the solidification of the Stillwater and Bushveld complexes were highly saline. The Cl-rich apatite in these bodies crystallized from interstitial melt with high Cl/(F + OH) ratio. The latter was generated by the combined processes of fractional crystallization and dehydration by its reaction with the relatively large mass of initially anhydrous pyroxene through which it percolated.  相似文献   

变基性岩部分熔融过程中榍石的微量元素效应:以南迦巴瓦混合岩为例     

赵令浩  曾令森  高利娥  高家昊  王亚飞  张立飞 《岩石学报》2020,36(9):2714-2728

南迦巴瓦地区广泛出露的中下地壳变基性岩部分熔融形成的层状混合岩和淡色花岗岩,为研究部分熔融过程中榍石的地球化学行为对熔体的微量元素组成的影响提供了良好的机会。相对于源岩或熔融残留体,淡色体亏损Ti、V、REE、Y、Nb、Ta、U等元素,与混合岩中榍石的微量元素特征互补。混合岩、淡色体和榍石微量元素特征表明南迦巴瓦角闪岩部分熔融形成的淡色体的微量元素特征主要受控于榍石的地球化学行为。角闪岩脱水部分熔融过程中,由于长英质熔体的低Ti溶解度,榍石以未熔残留体形式存在于暗色体中,导致熔体亏损Ti、REE、Nb、Ta、V、U等元素和Sr/Y比值相对升高。关键元素在榍石和熔体之间的配分系数受熔体成分影响明显。角闪岩中变质榍石D_Nb/Ta<1,因此变质榍石残留导致熔体Nb/Ta相对于源岩升高;而高Si-Al花岗质熔体中榍石D_Nb/Ta>1,因此与高Si-Al熔体平衡的榍石的分离（转熔或结晶分异）将导致熔体Nb/Ta比值相对源岩降低。榍石在部分熔融过程中的微量元素效应为理解变基性岩部分熔融产生熔体的地球化学特征提供新的认识。  相似文献   

Trace element partitioning in the granulite facies     

Franziska Nehring  Stephen F. Foley  Pentti Hölttä 《Contributions to Mineralogy and Petrology》2010,159(4):493-519

Analyses of trace elements in the mineral phases of granulites provide important information about the trace element distribution in the lower crust. Since granulites are often considered residues of partial melting processes, trace element characteristics of their mineral phases may record mineral/melt equilibria thus giving an opportunity to understand the nature and composition of melts in the lower continental crust. This study provides an extensive set of mineral trace element data obtained by LA-ICP-MS analyses of mafic and intermediate granulites from Central Finland. Mass balance calculations using the analytical data indicate a pronounced contribution of the accessory minerals apatite for the REE and ilmenite for the HFSE. Coherent mineral/mineral ratios between samples point to a close approach to equilibrium except for minerals intergrown with garnet porphyroblasts. Mineral trace element data were used for the formulation of a set of D ^mineral/melt partition coefficients that is applicable for trace element modelling under lower crustal conditions. D ^mineral/melt were derived by the application of predictive models and using observed constant mineral/mineral ratios. The comparison of the calculated D ^mineral/melt with experimental data as well as the relationship between mineral trace element contents and a leucosome with a composition close to an equilibrium melt provides additional constraints on mineral/melt partitioning. The D values derived in this study are broadly similar to magmatic partition coefficients for intermediate melt compositions. They provide a first coherent set of D values for Sc, V, Cr and Ni between clinopyroxene, amphibole, garnet, orthopyroxene, ilmenite and melt. In addition, they emphasize the strong impact that ilmenite exerts on the distribution of Nb and Ta.  相似文献   

Partitioning of fluorine and chlorine between biotite and granitic melt: experimental calibration at 200 MPa H2O     

Jonathan P. Icenhower  D. London 《Contributions to Mineralogy and Petrology》1997,127(1-2):17-29

Experiments from 640 to 680?°C, 200 MPa H₂O at?f _O2?≈?NNO, employing a natural?F-rich?vitrophyric rhyolite from Spor Mountain, Utah, assessed the effect of variable Mg′ [100Mg/(Mg?+?Mn?+?Fe)] on the partitioning of fluorine and chlorine between biotite (Bt) and melt. Over this temperature interval, Bt (?±?fluorite, ?±?quartz) is the sole liquidus phase. Partition coefficients for fluorine between biotite and glass (D_F ^Bt/melt) show a strong dependence on the Mg′ of Bt.?D_F ^Bt/melt varies from???1.5 to 7.2 over the range of Mg′ from 21 to 76. A strong linear correlation between?D_F ^Bt/melt?and Mg′ has a slope of 9.4 and extrapolates through the origin (i.e., D_F ^Bt/melt?≈?0 at Mg′?=?0, an annite-siderophyllite solid solution in these experiments). D_Cl ^Bt/melt values (???1 to 6) in the same experiments vary inversely with Mg′. The Al-content of biotite does not vary with the aluminum saturation index (ASI?=?molar Al₂O₃/Σ alkali and alkaline earth oxides) of melt, but two exchange mechanisms involving Al appear to operate in these micas: (1) Al^vi?+?Al^iv?? Si^iv?+?Mg^iv, and Mg^iv?+?2Al^iv? 2Si^iv?+?□^iv. The effects of other components such as Li or other intensive parameters including f _O2 have yet to be evaluated?systematically. At comparable Mg′ of Bt, however, the Spor Mountain rhyolite yields higher D_F ^Bt/melt values than an Li-rich, strongly peraluminous melt previously investigated. The results indicate that the Mg′ of Bt exerts the principal control on halogen partitioning, with ASI and T as second-order variables. The experimental partition coefficients compare well with other experimental results but not with most volcanic rocks. Magmatic Bt from most rhyolites records higher D_F ^Bt/melt due to reequilibration with degassed (H₂O-depleted) magma and perhaps with F₂O_?1 exchange that may accompany oxidation ([Fe³⁺O] [Fe²⁺OH]_?1). This behavior is evident in magmatic biotite from a zoned peraluminous rhyolite complex near Morococala, Bolivia: Bt is sharply zoned with F-rich rims, but Bt(core)-melt inclusion pairs fall on our experimental curve for D_F ^Bt/melt. These experimental data can be used in part to assess the preservation of magmatic volatile contents in plutonic or volcanic silicic rocks. For plutonic rocks, the actual F-content of melt, not a relative activity ratio involving HF species, can be reasonably estimated if the mica has not undergone subsolidus reequilibration. This information is potentially useful for some shallow-level Ca-poor magmas that are thought to be rich in F (e.g., A- and S-type granites) but do not conserve F well as rocks.  相似文献   

Partition coefficients of Nb and Ta between rutile and anhydrous haplogranite melts   总被引：3，自引：1，他引：2  

Wen-Sheng Horng  Paul C. Hess 《Contributions to Mineralogy and Petrology》2000,138(2):176-185

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  相似文献   

The partitioning of sulfur between multicomponent aqueous fluids and felsic melts     

Bernd?Binder  Thomas?Wenzel  Hans?KepplerEmail author 《Contributions to Mineralogy and Petrology》2018,173(2):18

Sulfur partitioning between melt and fluid phase largely controls the environmental impact of volcanic eruptions. Fluid/melt partitioning data also provide the physical basis for interpreting changes in volcanic gas compositions that are used in eruption forecasts. To better constrain some variables that control the behavior of sulfur in felsic systems, in particular the interaction between different volatiles, we studied the partitioning of sulfur between aqueous fluids and haplogranitic melts at 200 MPa and 750–850 °C as a function of oxygen fugacity (Ni–NiO or Re–ReO₂ buffer), melt composition (Al/(Na?+?K) ratio), and fluid composition (NaCl and CO₂ content). The data confirm a first-order influence of oxygen fugacity on the partitioning of sulfur. Under “reducing conditions” (Ni–NiO buffer), D^fluid/melt is nearly one order of magnitude larger (323?±?14 for a metaluminous melt) than under “oxidizing conditions” (Re–ReO₂ buffer; 74?±?5 for a metaluminous melt). This effect is likely related to a major change in sulfur speciation in both melt and fluid. Raman spectra of the quenched fluids show the presence of H₂S and HS^? under reducing conditions and of SO₄^2? and HSO₄^? under oxidizing conditions, while SO₂ is undetectable. The latter observation suggests that already at the Re–ReO₂ buffer, sulfur in the fluid is almost completely in the S⁶⁺ state and, therefore, more oxidized than expected according to current models. CO₂ in the fluid (up to x_CO2?=?0.3) has no effect on the fluid/melt partitioning of sulfur, neither under oxidizing nor under reducing conditions. However, the effect of NaCl depends on redox state. While at oxidizing conditions, D^fluid/melt is independent of x_NaCl, the fluid/melt partition coefficient strongly decreases with NaCl content under reducing conditions, probably due to a change from H₂S to NaSH as dominant sulfur species in the fluid. A decrease of D^fluid/melt with alkali content in the melt is observed over the entire compositional range under reducing conditions, while it is prominent only between the peraluminous and metaluminous composition in oxidizing experiments. Overall, the experimental results suggest that for typical oxidized, silicic to intermediate subduction zone magmas, the degassing of sulfur is not influenced by the presence of other volatiles, while under reducing conditions, strong interactions with chlorine are observed. If the sulfur oxidation state is preserved during an explosive eruption, a large fraction of the sulfur released from oxidized magmas may be in the S⁶⁺ state and may remain undetected by conventional methods that only measure SO₂. Accordingly, the sulfur yield and the possible climatic impact of some eruptions may be severely underestimated.  相似文献   

Experimental studies of Ta2O5 and columbite–tantalite solubility in fluoride solutions from 300 to 550°C and 50 to 100 MPa     

George Pavlovich Zaraisky  Valentina Korzhinskaya  Nataliya Kotova 《Mineralogy and Petrology》2010,99(3-4):287-300

It is well established that the fractionation of Li–F granitic magmas at depth leads to the accumulation of flux elements such as F and Li, and metal cations such as Ta and Nb in residual melts. However, it remains to be determined whether magmatic fractionation is sufficient to concentrate Nb and Ta into economically significant quantities, and what role hydrothermal–metasomatic processes play in the formation of such ore deposits. In the literature, reliable data about the solubility of Ta and Nb in hydrothermal solutions is missing or incomplete. This study provides a quantitative experimental estimation of the possible contribution from hydrothermal processes in Ta enrichment in cupolas of albitized and greisenized Li–F granite. Experimental studies of Ta₂O₅ and columbite–tantalite (Mn,Fe)(Nb,Ta)₂O₆ solubility were carried out in fluoride solutions consisting of HF, NaF, KF, and LiF. At low fluoride concentrations (0.01 and 0.1 m), Ta₂O₅ solubility at 550°C and 100 MPa under Co–CoO oxidizing conditions is low (near 10^?5–10^?4 m) in all fluoride solutions (HF, NaF, KF, LiF). At high fluoride concentrations (1 and 2 m) the highest Ta₂O₅ concentrations (10^?1 m) were detected in HF solutions. In KF, NaF, and LiF solutions, the Ta₂O₅ solubility is also high (10^?3–10^?2 m). The dependence of columbite–tantalite (Nb₂O₅-59 wt. %, Ta₂O₅-18 wt. %) solubility as a function of solution composition, T, and P has also been investigated. Tantalum and Nb concentrations have the highest values in HF solutions at reduced conditions (up to 10^?3 to 10^?2 m Ta in 1 m HF). In 1 m NaF solutions, the concentrations of Nb and Ta are, respectively, 2.5 and 3 orders of magnitude less than those in the 1 m HF solutions. Solubility of Ta and Nb in KF solutions has intermediate values. It is established that in NaF and KF solutions the dependence of solubility on pressure is distinctly negative. The Nb and Ta contents increase with increasing concentrations of HF and KF in solution, however, they do not change with increasing NaF concentration. In NaHCO₃, Na₂CO₃, and HCl solutions columbite–tantalite solubility is low. Even in 1 m chloride solutions the content is within the limits of 10^?5 m for Nb and 10^?6 to 10^?8 m for Ta. We conclude that hydrothermal transport of Ta and Nb is possible only in concentrated fluoride solutions.  相似文献   

Solubility behavior of alkali aluminosilicate components in aqueous fluids and silicate melts at high pressure and temperature     

Bjorn O. Mysen  Lora Armstrong 《Geochimica et cosmochimica acta》2002,66(12):2287-2297

The solubility behavior of K₂O, Na₂O, Al₂O₃, and SiO₂ in silicate-saturated aqueous fluid and coexisting H₂O-saturated silicate melts in the systems K₂O-Al₂O₃-SiO₂-H₂O and Na₂O-Al₂O₃-SiO₂-H₂O has been examined in the 1- to 2-GPa pressure range at 1100°C. Glasses of Na- and K-tetrasilicate compositions with 0, 3, and 6 mol% Al₂O₃ were used as starting materials. In both systems, the oxides dissolve incongruently in aqueous fluid and silicate melt. When recalculated to an anhydrous basis, the aqueous fluids are enriched in alkalis and depleted in silica and alumina relative to their proportions in the starting materials. The extent of incongruency is more pronounced in the Na₂O-Al₂O₃-SiO₂-H₂O system than in the K₂O-Al₂O₃-SiO₂-H₂O system.The partition coefficients of the oxides, D_oxide^fluid/melt, are linear and positive functions of the oxide concentration in the fluid for each composition. There is a slight dependence of the partition coefficients on bulk composition. No effect of pressure could be discerned. For alkali metals, the fluid/melt partition coefficients range from 0.06 to 0.8. For Al₂O₃ this range is 0.01 to 0.2, and for SiO₂, it is 0.01 to 0.32. For all compositions, D_K2O^fluid/melt∼D_Na2O^fluid/melt>D_SiO2^fluid/melt>D_Al2O3^fluid/melt for the same oxide concentration in the fluid. D_K2O^fluid/melt, D_Na2O^fluid/melt, and D_SiO2^fluid/melt correlate negatively with the Al₂O₃ content of the systems. This correlation is consistent with a solubility model of alkalis that involve associated KOH°, NaOH°, silicate, and aluminate complexes.  相似文献   

Determination of zircon/melt trace element partition coefficients from SIMS analysis of melt inclusions in zircon   总被引：3，自引：0，他引：3  

J.B Thomas  R.J BodnarN Shimizu  A.K Sinha 《Geochimica et cosmochimica acta》2002,66(16):2887-2901

Partition coefficients (^zircon/meltD_M) for rare earth elements (REE) (La, Ce, Nd, Sm, Dy, Er and Yb) and other trace elements (Ba, Rb, B, Sr, Ti, Y and Nb) between zircon and melt have been calculated from secondary ion mass spectrometric (SIMS) analyses of zircon/melt inclusion pairs. The melt inclusion-mineral (MIM) technique shows that D_REE increase in compatibility with increasing atomic number, similar to results of previous studies. However, D_REE determined using the MIM technique are, in general, lower than previously reported values. Calculated D_REE indicate that light REE with atomic numbers less than Sm are incompatible in zircon and become more incompatible with decreasing atomic number. This behavior is in contrast to most previously published results which indicate D > 1 and define a flat partitioning pattern for elements from La through Sm. The partition coefficients for the heavy REE determined using the MIM technique are lower than previously published results by factors of ≈15 to 20 but follow a similar trend. These differences are thought to reflect the effects of mineral and/or glass contaminants in samples from earlier studies which employed bulk analysis techniques.D_REE determined using the MIM technique agree well with values predicted using the equations of Brice (1975), which are based on the size and elasticity of crystallographic sites. The presence of Ce⁴⁺ in the melt results in elevated D_Ce compared to neighboring REE due to the similar valence and size of Ce⁴⁺ and Zr⁴⁺. Predicted ^zircon/meltD values for Ce⁴⁺ and Ce³⁺ indicate that the Ce⁴⁺/Ce³⁺ ratios of the melt ranged from about 10⁻³ to 10⁻². Partition coefficients for other trace elements determined in this study increase in compatibility in the order Ba < Rb < B < Sr < Ti < Y < Nb, with Ba, Rb, B and Sr showing incompatible behavior (D_M < 1.0), and Ti, Y and Nb showing compatible behavior (D_M > 1.0).The effect of partition coefficients on melt evolution during petrogenetic modeling was examined using partition coefficients determined in this study and compared to trends obtained using published partition coefficients. The lower D_REE determined in this study result in smaller REE bulk distribution coefficients, for a given mineral assemblage, compared to those calculated using previously reported values. As an example, fractional crystallization of an assemblage composed of 35% hornblende, 64.5% plagioclase and 0.5% zircon produces a melt that becomes increasingly more enriched in Yb using the D_Yb from this study. Using D_Yb from Fujimaki (1986) results in a melt that becomes progressively depleted in Yb during crystallization.  相似文献   

Melt structural control on olivine/melt element partitioning of Ca and Mn     

Bjorn O. Mysen  Emily V. Dubinsky 《Geochimica et cosmochimica acta》2004,68(7):1617-1633

Relationships between mineral/silicate melt partition coefficients and melt structure have been examined by combining Ca and Mn olivine/melt partitioning data with available melt structure information. Compositions were chosen so that melts with olivine on their liquidii range in degree of polymerization, NBO/T, from ∼0.5 to ∼2.5 under near isothermal conditions (1350-1400°C). Olivine/melt Ca-Mn exchange coefficients, Ca(olivine)/CaO(melt)/MnO(olivine)/MnO(melt) (K_{D Ca-Mn}^olivine/melt), as a function of melt NBO/T have a parabolic shape with a minimum K_{D Ca-Mn}^olivine/melt-value at NBO/T near 1. Notably, published K_{D Fe2⁺-Mg}^olivine/melt versus NBO/T functions are also parabolic with a maximum in K_{D Fe2⁺-Mg}^olivine/melt near 1 (Kushiro and Mysen, 2002).The olivine/melt partitioning data are modeled in terms of structural units (Qⁿ-species) in the melt. The NBO/T-value corresponding to the minimum K_{D Ca-Mn}^olivine/melt is near that where the abundance ratio of Qⁿ-species, X_Q3/X_Q2, has its largest value. Therefore, the activity coefficient ratio in the melt, γ_Ca2⁺(melt)/γ_Mn2⁺(melt), attains a minimum where the abundance ratio of X_Q3/X_Q2 is at maximum. It is inferred from this relationship that Ca²⁺ in the melts is dominantly bonded to nonbridging oxygen (Ca-NBO) in Q³-species, whereas Mn²⁺ is bonded to nonbridging oxygen (Mn-NBO) in less polymerized Qⁿ-species such as Q².  相似文献   

High-precision high field strength element partitioning between garnet, amphibole and alkaline melt from Kakanui, New Zealand   总被引：2，自引：0，他引：2  

Eric C. Fulmer  Oliver Nebel  Wim van Westrenen 《Geochimica et cosmochimica acta》2010,74(9):2741-37

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.  相似文献   

Partitioning of Nb and Ta between rutile and felsic melt and the fractionation of Nb/Ta during partial melting of hydrous metabasalt   总被引：5，自引：0，他引：5  

Xiaolin Xiong  Hans Keppler  Huaiwei Ni  Yuan Li 《Geochimica et cosmochimica acta》2011,75(7):1673-1692

In order to fully assess the role of rutile in fractionation of Nb/Ta during partial melting of hydrous metabasalt, we have measured rutile - felsic melt partition coefficients (D values) for Nb and Ta with tonalitic to trondhjemitic compositions at 1.5-3.5 GPa, 900-1350 °C and ∼5.0-20 wt% H₂O. D_Nb, D_Ta and D_Nb/D_Ta range from 17 ± 1 to 246 ± 13, 34 ± 2 to 232 ± 25 and 0.51 ± 0.04 to 1.06 ± 0.13, respectively. For the compositions investigated, melt composition appears to have no observable effect on the partitioning; the effect of pressure is also slight; whereas temperature and H₂O have marked effects. D_Nb, D_Ta and D_Nb/D_Ta increase with decreasing temperature and H₂O content, showing a reversal of D_Nb/D_Ta from <1.0 to >1.0. Using the data that approached equilibrium and obeyed Henry’s law, expressions describing the dependences of D_Nb, D_Ta and D_Nb/D_Ta on temperature, pressure and melt H₂O content were obtained: