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1.
Plagioclase feldspar/magmatic liquid partition coefficients for Sr, Ba, Ca, Y, Eu2+, Eu3+ and other REE have been determined experimentally at 1 atm total pressure in the temperature range 1150–1400°C. Natural and synthetic melts representative of basaltic and andesitic bulk compositions were used, crystallizing plagioclase feldspar in the composition range An35–An85. Partition coefficients for Sr are greater than unity at all geologically reasonable temperatures, and for Ba are less than unity above approximately 1060°C. Both are strongly dependent upon temperature. Partition coefficients for the trivalent REE are relatively insensitive to temperature. At fixed temperature they decrease monotonically from La to Lu. The partition of Eu is a strong function of oxygen fugacity. Under extreme reducing conditions DEu approaches the value of DSr.  相似文献   

2.
Partition coefficients (zircon/meltDM) 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 DREE increase in compatibility with increasing atomic number, similar to results of previous studies. However, DREE determined using the MIM technique are, in general, lower than previously reported values. Calculated DREE 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.DREE 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 DCe 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 (DM < 1.0), and Ti, Y and Nb showing compatible behavior (DM > 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 DREE 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 DYb from this study. Using DYb from Fujimaki (1986) results in a melt that becomes progressively depleted in Yb during crystallization.  相似文献   

3.
The partitioning of La, Sm, Dy, Ho and Yb between garnet, calcic clinopyroxene, calcic amphibole and andesitic and basaltic liquids has been studied experimentally. Glasses containing one or more REE in concentrations of 500–2000 ppm were crystallized at pressures of 10–35 kbar, and temperatures of 900–1520°C. Water was added to stabilize amphibole and to allow study of partition coefficients over wide temperature ranges. Major element and REE contents of crystal rims and adjacent glass were determined by EPMA, with limits of detection for individual REE of 100–180 ppm. Measured partition coefficients, DREECryst-liq, are independent of REE concentration over the concentration ranges used.D-values show an inverse dependence on temperature, best illustrated for garnet. At a given temperature, they are almost always higher for equilibria involving andesitic liquid. Garnet shows by far the greatest range of D-values, with e.g. DLa < 0.05 and DYb ~ 44 for andesitic liquid at 940°C. DYb falls to ~ 12 at 1420°C. DSmGa-liq also correlates negatively with temperature and positively with the grossular content of garnet. Patterns of DreeCryst-Liq for calcic clinopyroxenes and amphiboles are sub-parallel, with D-values for amphibole generally higher. Both individual D-values and patterns for the crystalline phases studied are comparable with those determined for phenocryst-matrix pairs in natural dacites, andesites and basalts.D-values and patterns are interpreted in terms of the entry of REE3+ cations into mineral structures and liquids of contrasted major element compositions. The significance of the partition coefficients for models of the genesis of andesitic and Hy-normative basaltic magmas is assessed. Most magmas of these types in island arcs are unlikely to be produced by melting of garnet-bearing sources such as eclogite or garnet lherzolite.  相似文献   

4.
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 DTa > DNb, DHf > DZr and DU > DTh. 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, DNb/DTa and DHf/DZr are not significantly affected by melt composition. Because DU ? DTh, 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   

5.
Partition coefficients for the rare earth elements (REE) Ce, Sm and Tm between coexisting garnets and hydrous liquids have been determined at high pressure and temperatures (30 kbar and 1300 and 1500°C). Two synthetic systems were studied, Mg3Al2Si3O12-H2O and Ca3Al2Si3O12-H2O, in addition to a natural pyrope-bearing system.Deviations from Henry's Law behaviour occur at geologically relevant REE concentrations. At concentrations < 3 ppm Ce, < 12 ppm Sm, < 80 ppm Tm in pyrope and < 100 ppm Ce, < 250 ppm Sm, < 1000 ppm Tm in grossular (at 30 kbar and 1300°C), Dgarnet liquidREE increases as the REE concentration in the garnet decreases. At higher concentrations, DREE is constant. Dgrossular liquidREE also constant when the garnet contains less than about 2 ppm Sm or Tm. The REE concentration at which DREE becomes constant increases with increasing temperature, decreasing REE ionic radius and increasing Ca content of the garnet.Partitioning behaviour of Ce, Sm and Tm between a natural pyrope-rich garnet and hydrous liquid is analogous to that in the synthetic systems and substantiates the substitution model proposed by Harrison and Wood (1980).Values of DREEgarnet/liquid for which Henry's Law is obeyed are systematically higher for grossular than for pyrope (Dpyrope/liquid = 0.067(Ce), 0.108(Sm), 0.155(Tm) and Dgrossular/Liquid = 0.65(Ce), 0.75(Sm), 4.55(Tm).The implications of non-Henry's Law partitioning of REE for models of basalt petrogenesis involving garnet are far-ranging. Deviations from Henry's Law permit refinements to be made to calculated REE abundances once basic model parameters have been defined.  相似文献   

6.
The distribution of rare earth elements (REE) between clinopyroxene (cpx) and basaltic melt is important in deciphering the processes of mantle melting. REE and Y partition coefficients from a given cpx-melt partitioning experiment can be quantitatively described by the lattice strain model. We analyzed published REE and Y partitioning data between cpx and basaltic melts using the nonlinear regression method and parameterized key partitioning parameters in the lattice strain model (D 0, r 0 and E) as functions of pressure, temperature, and compositions of cpx and melt. D 0 is found to positively correlate with Al in tetrahedral site (Al T ) and Mg in the M2 site (MgM2) of cpx and negatively correlate with temperature and water content in the melt. r 0 is negatively correlated with Al in M1 site (AlM1) and MgM2 in cpx. And E is positively correlated with r 0. During adiabatic melting of spinel lherzolite, temperature, Al T , and MgM2 in cpx all decrease systematically as a function of pressure or degree of melting. The competing effects between temperature and cpx composition result in very small variations in REE partition coefficients along a mantle adiabat. A higher potential temperature (1,400°C) gives rise to REE partition coefficients slightly lower than those at a lower potential temperature (1,300°C) because the temperature effect overwhelms the compositional effect. A set of constant REE partition coefficients therefore may be used to accurately model REE fractionation during partial melting of spinel lherzolite along a mantle adiabat. As cpx has low Al and Mg abundances at high temperature during melting in the garnet stability field, REE are more incompatible in cpx. Heavy REE depletion in the melt may imply deep melting of a hydrous garnet lherzolite. Water-dependent cpx partition coefficients need to be considered for modeling low-degree hydrous melting.  相似文献   

7.
The distribution of sulfur between haplogranitic melt and aqueous fluid has been measured as a function of oxygen fugacity (Co-CoO-buffer to hematite-magnetite buffer), pressure (0.5-3 kbar), and temperature (750-850 °C). Sulfur always strongly partitions into the fluid. At a given oxygen fugacity, pressure and temperature, the distribution of sulfur between melt and fluid can be described by one constant partition coefficient over a wide range of sulfur concentrations. Oxygen fugacity is the most important parameter controlling sulfur partitioning. While the fluid/melt partition coefficient of sulfur is 468 ± 32 under Co-CoO buffer conditions at 2 kbar and 850 °C, it decreases to 47 ± 4 at an oxygen fugacity 0.5-1 log unit above Ni-NiO at the same pressure and temperature. A further increase in oxygen fugacity to the hematite-magnetite buffer has virtually no effect on the partition coefficient (Dfluid/melt = 49 ± 2). The dependence of Dfluid/melt on temperature and pressure was systematically explored at an oxygen fugacity 0.5-1 log units above Ni-NiO. At 850 °C, the effect of pressure on the partition coefficient is small (Dfluid/melt = 58 ± 3 at 0.5 kbar; 94 ± 9 at 1 kbar; 47 ± 4 at 2 kbar and 68 ± 5 at 3 kbar) and temperature also has only a minor effect on partitioning.The data show the “sulfur excess” observed in many explosive volcanic eruptions can easily be explained by the presence of a small fraction of hydrous fluid in the magma chamber before the eruption. The sulfur excess can be calculated as the product of the fluid/melt partition coefficient of sulfur and the mass ratio of fluid over melt in the erupted material. For a plausible fluid/melt partition coefficient of 47 under oxidizing conditions, a 10-fold sulfur excess corresponds to a 17.6 wt.% of fluid in the erupted material. Large sulfur excesses (10-fold or higher) are only to be expected if only a small fraction of the magma residing in the magma chamber is erupted.The behavior of sulfur, which seems to be largely independent of pressure and temperature under oxidizing conditions is very different from chlorine, where the fluid/melt partition coefficient strongly increases with pressure. Variations in the SO2/HCl ratio of volcanic gases, if they reflect primary processes in the magma chamber, therefore provide an indicator of pressure variations in a magma. In particular, major increases in the S/Cl ratio of an aqueous fluid coexisting with a felsic magma suggest a pressure reduction in the magma chamber and/or magma rising to the surface.  相似文献   

8.
The critical role of iron on crystal-silicate liquid relationships and melt differentiation is mainly controlled by the redox conditions prevailing in magmas, but the presently available database merely constrains the thermodynamic properties of iron-bearing components in strongly reduced and anhydrous molten silicate where iron is in the ferrous form. This paper provides new standard states for pure ferrous (FeOliq) and ferric (Fe2O3liq) molten iron oxides and extends the experimental database towards oxidizing and water-bearing domains. Iron-iridium, iron-platinum alloys, magnetite or hematite were equilibrated with synthetic silicic liquids at high temperature and high pressure under controlled oxygen fugacity (fO2) to determine activity-composition relationships for FeOliq and Fe2O3liq. Between 1000 and 1300°C, the fO2 ranges from that in air to 3-log units below that of the nickel-nickel oxide buffer (NNO). Experiments were performed on both anhydrous and hydrous melts containing up to 6-wt.% water. Incorporation of water under reducing conditions increases the activity coefficient of FeOliq but has an opposite effect on Fe2O3liq. As calcium is added to system, the effect of water becomes weaker and is inverted for Fe2O3liq. Under oxidizing conditions, water has a negligible effect on both activities of FeOliq and Fe2O3liq. In contrast, changes in redox conditions dominate the activity coefficients of both FeOliq and Fe2O3liq, which increase significantly with increasing fO2. The present results combined with the previous work provide a specific database on the energetics of iron in silicate melts that cover most of the condition prevailing in natural magmas.  相似文献   

9.
New experimental amphibole/melt partition coefficients from a variety of geologically relevant amphibole (pargasite, kaersutite, and K-richterite) and melt compositions obtained under conditions of interest to upper-mantle studies are combined with the results of X-ray single-crystal structure refinement. The ideal cation radii (r0), calculated using the lattice-site elastic-strain model of Blundy and Wood (1994) under the hypothesis of complete REE (rare earth elements) ordering at [8]M4, mostly differ significantly from those obtained from both the structure refinement and the ionic radius of [8]Ca2+. Heavier REE may also strongly deviate from the parabolic trends defined by the other REE. On the basis of the crystal-chemical knowledge of major-element site-preference in amphibole and the occurrence of two sites with different co-ordination within the M4 cavity (M4 for Ca and Na, M4′ for Fe2+ and Mg), we propose a new model for REE incorporation. LREE order at the [8]M4 site, whereas HREE prefer the M4′ site with lower co-ordination in amphiboles with a significant cummingtonite component, and may also enter the M2 octahedron, at least in richterite. This more complex model is consistent with the observed Amph/LD, and drops the usual assumption that REE behave as a homogeneous group and order at the M4 site. The availability of multiple crystal-chemical mechanisms for REE3+ incorporation explains why measured and estimated Amph/LDHREE may differ by up to one order of magnitude. When REE enter two different sites within the same cavity, a fit performed on the basis of a single curve may appear correct, but the values obtained for r0 are biased towards those of the dominant site, and the Young's modulus is underestimated. When REE are incorporated in multiple sites in different cavities, the observed pattern cannot be reduced to a single curve, and the partition coefficients of heavy REE would be strongly underestimated by a single-site fit. The simplistic assumption that REE occupy a single site within the amphibole structure can thus substantially bias predictive models based on the elastic-strain theory. Our combined approach allows linkage between fine-scale site preference and the macroscopic properties of minerals and provides more reliable predictive models for mineral/melt partitioning. After the possible site-assignments have been identified, the shape of the Onuma curves constructed from accurately determined Amph/LDREE now allows the active mechanisms for REE incorporation in amphiboles to be recognised even where site populations are not available. The REE preference for polyhedra with smaller size and lower co-ordination than those occupied by Ca invalidates the general idea that Ca acts as a “carrier” for REE. Received: 17 March 1999 / Accepted: 11 June 1999  相似文献   

10.
We have determined mineral-melt partition coefficients (D values) for 20 trace elements in garnet-pyroxenite run products, generated in 3 to 7 GPa, 1,425–1,750°C experiments on a high-Fe mantle melt (97SB68) from the Paraná-Etendeka continental-flood-basalt (CFB) province. D values for both garnet (∼Py63Al25Gr12) and clinopyroxene (∼Ca0.2Mg0.6Fe0.2Si2O6) show a large variation with temperature but are less dependent on pressure. At 3 GPa, D cpx/liq values for pyroxenes in garnet-pyroxenite run products are generally lower than those reported from Ca-rich pyroxenes generated in melting experiments on eclogites and basalts (∼Ca0.3–0.5Mg0.3–0.6Fe0.07–0.2Si2O6) but higher than those for Ca-poor pyroxenes from peridotites (∼Ca0.2Mg0.7Fe0.1Si2O6). D grt/liq values for light and heavy rare-earth elements are ≤0.07 and >0.8, respectively, and are similar to those for peridotitic garnets that have comparable grossular but higher pyrope contents (Py70–88All7–20Gr8–14). 97SB68 D LREEgrt/liq values are higher and D HREEgrt/liq values lower than those for eclogitic garnets which generally have higher grossular contents but lower pyrope contents (Py20–70Al10–50Gr10–55). D values agree with those predicted by lattice strain modelling and suggest that equilibrium was closely approached for all of our experimental runs. Correlations of D values with lattice-strain parameters and major-element contents suggest that the wollastonite component and pyrope:grossular ratio exert major controls on 97SB68 clinopyroxene and garnet partitioning, respectively. These are controlled by the prevailing pressure and temperature conditions for a given bulk-composition. The composition of co-existing melt was found to have a relatively minor effect on 97SB68 D values. The variations in D values displayed by different mantle lithologies are subtle and our study confirms previous investigations which have suggested that the modal proportions of garnet and clinopyroxene are by far the most influential factor in determining incompatible trace-element concentrations in mantle melts. The trace-element partition coefficients we have determined may be used to place high-pressure constraints on garnet-pyroxenite melting models.  相似文献   

11.
Trace element partitioning in plagioclase feldspar   总被引：4，自引：0，他引：4  
Compilation and interpretation of experimental and natural Nernst partition coefficient (plagioclase/meltD) data show that, with a few exceptions, increases in plagioclase/meltD correlate with decreasing anorthite-content of plagioclase. In contrast, increases of plagioclase/meltD for Ga, Sc, Cu, Zn, Zr, Hf and Ti, are better correlated against decreasing melt MgO or increasing melt SiO2 contents. plagioclase/meltD for Ti and the rare earth elements (REE) show little dependence on temperature, but increase as the melt water content increases. plagioclase/meltD for K and Sr are sensitive to pressure. Variations of D0 (the strain compensated partition coefficient), r0 (the size of the site into which REE substitute), and E (Young’s Modulus of this site) were parameterized against variations of melt SiO2, the An-content of plagioclase, and other combinations of variables, allowing plagioclase/meltDREE-Y to be calculated from a variety of input parameters. The interrelations of temperature, melt MgO and SiO2 content, and plagioclase anorthite-content for wet and dry systems were also parameterized to facilitate interpolation where such data are lacking. When combined, these semi-empirical parameterizations yield plagioclase/meltD results comparable to available experimental and natural data.  相似文献   

12.
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13.
The nature of the petrogenetic links between carbonatites and associated silicate rocks is still under discussion (i.e., [Gittins J., Harmer R.E., 2003. Myth and reality of the carbonatite–silicate rock “association”. Period di Mineral. 72, 19–26.]). In the Paleozoic Kola alkaline province (NW Russia), the carbonatites are spatially and temporally associated to ultramafic cumulates (clinopyroxenite, wehrlite and dunite) and alkaline silicate rocks of the ijolite–melteigite series [(Kogarko, 1987), (Kogarko et al., 1995), (Verhulst et al., 2000), (Dunworth and Bell, 2001) and (Woolley, 2003)]. In the small (≈ 20 km2) Vuoriyarvi massif, apatite is typically a liquidus phase during the magmatic evolution and so it can be used to test genetic relationships. Trace elements contents have been obtained for both whole rocks and apatite (by LA-ICP-MS). The apatites define a single continuous chemical evolution marked by an increase in REE and Na (belovite-type of substitution, i.e., 2Ca2+ = Na+ + REE3+). This evolution possibly reflects a fractional crystallisation process of a single batch of isotopically homogeneous, mantle-derived magma.The distribution of REE between apatite and their host carbonatite have been estimated from the apatite composition of a carbonatite vein, belonging to the Neskevara conical-ring-like vein system. This carbonatite vein is tentatively interpreted as a melt. So, the calculated distribution coefficients are close to partition coefficients. Rare earth elements are compatible in apatite (D > 1) with a higher compatibility for the middle REE (DSm : 6.1) than for the light (DLa : 4.1) and the heavy (DYb : 1) REE.  相似文献   

14.
Barium partitioning between alkali feldspar and a natural trachyte liquid, enriched with barium, has been determined as a function of pressure and temperature from 10 to 25 kb and 900°–1100° C. Both long duration experiments and a re-equilibration experiment suggest close approach to equilibrium. Partition coefficients (D Ba) decrease as both temperature and pressure increase (e.g., D Ba changes from 8.71 at 10 kb, 900° C to 1.48 at 25 kb, 1100° C). Water activity also controls the barium partitioning with a marked decrease in D Ba af/liq for addition of less than 0.8 wt% H2O, but with no apparent additional effect for higher water contents in the bulk composition (e.g., from 0.8–4.2 wt% H2O). The composition of alkali feldspar also has a significant effect on D Ba af/liq , but the data obtained do not allow derivation of a complete D-Or relationship. These new data suggest that Henry's Law is obeyed for most of the barium concentrations examined, and the limit of Henry's Law behaviour for barium in alkali feldspar is as high as 6 wt% BaO in alkali feldspar and 1.2 wt% BaO in the melt, similar to the results of Long (1978). The experimental results broadly overlap with natural data for D Ba, determined from coexisting alkali feldspar phenocrysts and glass (or groundmass).  相似文献   

15.
Based on 51 wholerock analyses by XRF and summation over the layered group, the Kiglapait Intrusion contains 4.7?1.6+1.2 ppm Y, which resides principally in augite and apatite. Using liquid compositions calculated by summation, the partition coefficient DAUG/LY is 0.95 ± 0.12 from 84 to 97 PCS (percent solidified) and 1.5 ± 0.4 above 97 PCS. For feldspar, the most likely value for D is 0.028 ± 0.02 (N = 6).REE analyses for 13 whole rocks were interpreted with the aid of yttrium models to yield trends for wholerocks and liquids vs PCS. Summations over the rocks of the layered group gave La = 2.5, Ce = 5.8, Nd = 3.9, Sm = 1.0, Eu = 0.8, Tb = 0.17, Yb = 0.37, and Lu = 0.06 ppm, with 2 s.d. errors near ± 30%. All these elements are highly incompatible until the arrival of augite, which affects chiefly the HREE, and apatite, which affects all (but more strongly, the LREE). The net result is that after apatite arrival at 94 PCS, the liquid compositions are nearly constant, hence DWR/LREE ≈ 1.0. These results are compatible with the mineralogy of the intrusion and the estimated partition coefficients for feldspar, olivine, augite, apatite, and Fe-Ti oxide minerals. For pre-apatite liquids, DFSP/LREE vary regularly with the normative di content of the liquid and change by an order of magnitude, hence the bulk liquid composition must be considered in any attempt to invert the compositions of feldspars to parent liquids.The Eu anomaly at first decreases in Kiglapait liquids due to plagioclase fractionation, but then increases due to removal of augite and apatite with negative Eu anomalies. The features dominantly responsible for Eu partitioning are liquid structure and, for monoclinic ternary feldspars, crystal structure. The former is best monitored by the augite or diopside content of the liquid and the latter, by the K content of the feldspar.The chondrite-normalized REE pattern for the intrusion has LaN = 7.4, LuN = 1.6, (Ce/Yb)N = 3.6, and Eu/Eu* = 2.4, indicating its feldspar-rich nature. The chilled margin of the nearby Hettasch Intrusion has a similar but more evolved pattern, corresponding roughly to the Kiglapait liquid at 70 PCS. As with other data, those for the REE suggest source differences for the two intrusions rather than a relationship due to fractionation.  相似文献   

16.
The effects of pressure and oxygen fugacity (fO2) on trace element partitioning between pargasitic amphibole and alkali-basaltic melts have been determined at pressures from 1.5 to 2.5 GPa and oxygen fugacities at 2 log units above and below the nickel–nickel oxide buffer. Amphibole crystallization experiments were performed in a piston cylinder apparatus and partition coefficients between amphibole and quenched melt of large-ion-lithophile elements (LILE: Rb, Sr, Ba), high-field-strength elements (HFSE: Zr, Nb, Ta, Hf, U, Th) and rare-earth elements (REE: La to Lu; +Y) were measured with a LASER ablation inductively coupled plasma – mass spectrometer. Increasing pressure from 1.5 to 2.5 GPa at similar temperatures and approximately constant fO2 increases D Rb but decreases D Zr and D Hf and D REE (D La, D Ce, D Pr). An empirical relationship was observed between D Zr and (Ti/Al)M2 in the amphibole, which can be described by:
Increasing the fO2 by ∼4 log units (∼NNO–2.0 to ∼NNO+2.2) at similar temperatures and constant pressure increases D Ba and D Nd but decreases D Ti. An increase in pressure or fO2 decreases the maximum partition coefficient (D o ), the Young's modulus (E) and the optimum ionic radius (r o ) of the A-, M2- and M4-lattice sites. The calculated r o values from the monovalent cations (Na, K, Rb) in the A site and the quadrivalent cations (Ti, Hf, Zr) in the M2 lattice sites suggests that amphiboles crystallized from alkaline basalt material have smaller 〈A-O〉 and 〈M2-O〉, mean bond-lengths than those formed from pargasitic materials at identical pressures and fO2's. The measured partition coefficients were used to calculate trace element concentrations in melts formed by partial melting of amphibole-bearing peridotite. This modeling demonstrates those changes in either the pressure or fO2 of melting can exert a significant effect on Rb/HFSE ratios in the melts and thus help explain the wide variations of these ratios sometimes observed in basaltic rock suites. Received: 7 August 1998 / Accepted: 7 June 2000  相似文献   

17.
Fractionation of selected REE between brine and vapour was experimentally determined using a large-volume rocking Ti-autoclave that allowed quasi-isobaric sampling of liquid-vapour pairs. Samples were extracted along the 350, 400 and 450 °C-isotherms of the H2O-NaCl system, and along the 400 °C isotherm of the CaCl2 system. Total salt concentrations were either 6.6 and 10 wt% NaCl or CaCl2, respectively, and total REE concentrations were about 2 ppm of each REE. Starting pH at room temperature was 1.8, added as HCl. In another series of experiments, REEs were added in amounts of 312 ppm. Here, the starting pH at room temperature was 0.5, added as HNO3:HCl=1:2. Liquid-vapour pairs (L-V) were analysed for REE by ICP-MS methods. L-V-partitioning of REE along a particular isotherm follows broadly the partitioning of the main salt components, NaCl or CaCl2. DREE=REEV/REEL decrease rapidly from the critical point with decreasing pressure (equivalent to increasing salinity of the liquid) as the solvus opens. This is independent of the total amount of the added REE. Log DREE values show approximately linear correlations with decreasing pressure from the critical point to salt-saturated conditions where the L-V curve meets the liquid + vapour + solid boundary. At given P and T, we found a systematic variation of DREE along the La-Lu suite. HREE are enriched in the vapour phase relative to LREE. Fractionation coefficients KD=(HREEV/HREEL)/(LREEV/LREEL) increase linearly with (P=Pcrit-P along a particular isotherm. At the 450 °C isotherm, KD (Lu/La) at the critical point (425 bar and 10 wt% NaCl) is 1; about 2.5 at 350 bar (33 wt% NaCl in the liquid); and about 5 if extrapolated to salt-saturation (250 bar and 52 wt% NaCl in the liquid). The REE fractionation behaviour is similar along the CaCl2-H2O solvus boundaries. Existing equations of state and thermodynamic databases of REE species cannot predict this behaviour at L-V-equilibrium conditions. That HREE are preferentially fractionated over LREE into the vapour phase has important petrogenetic consequences. In boiling hydrothermal systems, brines will be depleted in HREE relative to LREE. Isobaric cooling is ineffective for fractionation because the solvus closes and the system eventually shifts into the one-phase field. Fractionation is most effective in systems undergoing isothermal or adiabatic decompression. In an open system, where vapour may escape through cavities, fractionation is probably controlled by a Rayleigh fractionation process, resulting in larger overall fractionation effects. Similar fractionations probably occur during magma degassing at very shallow intrusion levels.  相似文献   

18.
The partitioning of samarium and thulium between garnets and melts in the systems Mg3Al2-Si3O12-H2O and Ca3Al2Si3O12-H2O has been studied as a function of REE concentration in the garnets at 30 kbar pressure. Synthesis experiments of variable time under constant P, T conditions indicate that garnet initially crystallizes rapidly to produce apparent values of D Sm (D Sm=concentration of Sm in garnet/concentration of Sm in liquid) which are too large in the case of pyrope and too small in the case of grossular. As the experiment proceeds, Sm diffuses out of or into the garnet and the equilibrium value of D Sm is approached. Approximate values of diffusion coefficients for Sm in pyrope garnet obtained by this method are 6 × 10–13 cm2 s–1 at 1,300 ° C and 2 × 10–12 cm2 s–1 at 1,500 ° C, and for grossular, 8.3 × 10–12 cm2 s–1 at 1,200 ° C and 4.6 × 10–11 cm2 s–1 at 1,300 ° C. The equilibrium values of D Sm have been reversed by experiments with Sm-free pyrope and Sm-bearing glass, and with Sm-bearing grossular and Sm-free glass.Between 12 ppm and 1,000 ppm Sm in pyrope at 1,300 ° C and between 80 ppm and >2 wt.% Tm in pyrope at 1,500 ° C, partition coefficients are constant and independent of REE concentration. Above 100 ppm of Sm in garnet at 1,500 ° C, partition coefficients are independent of Sm concentration. At lower concentrations, however, D Sm is dependent upon the Sm content of the garnet. The two regions may be interpreted in terms of charge-balanced substitution of Sm3Al5O12 in the garnet at high Sm concentrations and defect equilibria involving cation vacancies at low concentrations. At very low REE concentrations (< 1 ppm Tm in grossular at 1,300 ° C) DREE garnet/liquid again becomes constant with an apparent Henry's Law value greater than that at high concentrations. This may be interpreted in terms of a large abundance of cation vacancies relative to the number of REE ions.The importance of defects in the low concentration region has been confirmed by adding other REE (at 80 ppm level) to the system Mg3Al2Si3O12-H2O at low Sm concentrations. These change D Sm in the defect region, demonstrating their role in the production of vacancies.Experiments on a natural pyropic garnet indicate that defect equilibria are of importance to REE partitioning within the concentration ranges found in nature.  相似文献   

19.
Using fission and alpha track radiography techniques, we have measured partition coefficients (D) for the actinide elements Th, U and Pu between diopsidic clinopyroxene, whitlockite [β-Ca3 (PO4)2] and silicate liquid at 20kbar. Equilibrium partitioning at the crystal-liquid interface is assumed, and corrections for actinide zoning have been applied to the measured D values. Reproducibility for both actinide and minor element D values is carefully examined as a criterion for crystal-liquid interface equilibrium. The data are mostly compatible with interface equilibrium except for experiments at high cooling rates ( ? 30 deg/hr). Partition coefficients for Th/U/Pu of about 0.002/0.002/0.06 are measured for clinopyroxene and 1.2/0.5/3.4 for whitlockite. At an oxygen fugacity of 10?8.5, Pu is much more readily incorporated into the crystalline phases than is U or Th because of the importance of trivalent Pu. The DPu(cpx) is similar to D(cpx) of the light rare earths supporting the concept of Pu/(rare earth) dating.  相似文献   

20.
Diffusivities for calcium, iron, magnesium, manganese and aluminum have been measured for St. John's olivine undergoing cation exchange with synthetic basaltic melts. The variety of temperature, pressure and fO2 conditions under which the diffusivities were measured complement the equilibrium-partitioning study of calcium in olivine-bearing basalts by Jurewicz and Watson, 1988. Olivine was found to be anisotropic with respect to the diffusion of calcium, iron, magnesium and manganese. This anisotropy is a weak function of temperature, but strongly dependent upon oxygen fugacity.Because diffusion is independent of olivine composition over the small range of compositions used in this study, it could be shown that the absolute values of the diffusion coefficients were also functions of temperature and fO2. At near-atmospheric total pressure and an oxygen fugacity of 10–8atm, D Fe>D Mn>D Ca and D MgD Mn for a range of geologically reasonable temperatures. These relative diffusivities were shown to change with oxygen fugacity. The power-law dependence of diffusion on oxygen partial-pressure was determined for each cation and the results are consistent with the range of values given by Stocker (1978) and by other workers.For Ca and Fe, the effect of hydrostatic pressure on diffusion appears to be weak, at least for transport parallel to the c crystallographic direction. Unfortunately, no true activation volumes (or other pressure-related parameters) could be computed because the oxygen fugacity was not held constant over changes in pressure, and because accurate post-experiment reconstruction of sample orientation was not possible. Al was found to enter high-pressure olivines at concentrations of up to 0.14 weight percent, thus allowing aluminum diffusion to be characterized. The diffusivity of aluminum is, within error, the same as iron at 20 kb at 1430° C at the ambient fO2 of our piston-cylinder cells. This correspondence suggests that diffusion of Al may depend on transport of either Fe or of Fe +3 defects. While the results of these experiments are generally consistent with results published elsewhere, there are important inconsistencies. Tracer diffusion and interdiffusion in pure, ordered, olivine endmembers (e.g., tephroite and forsterite) showed significantly higher activation energies. This discrepancy could reflect the role of Fe+3 defects in diffusion; however, it may also suggest that order-disorder phenomena may be significant factors influencing diffusion in analog systems.The results of this study are applied to four petrologic problems: (1) calculation of rates of equilibration for olivine xenocrysts; (2) calculation of closure temperatures for the CaO/MgO olivine/basalt geothermometer (Jurewicz and Watson 1988); (3) delineation of an intrinsic-/O2 geobarometer; and (4) investigation of the dependence of olivine dissolution upon crystallographic orientation. In addition, it is demonstrated that diffusion-exchange experiments are useful for studying the dominant point-defect mechanisms for cation diffusion.Currently, a visiting scientist with Air Force Wright Aeronautical Laboratories Materials Laboratory (MLLM), Wright-Patterson AFB, OH 45433  相似文献   

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