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1.
Fission and alpha track radiography techniques have been used to measure partition coefficients (D) at trace (ppm) concentration levels for the actinide elements Th, U, and Pu between synthetic whitlockite and coexisting “haplobasaltic” silicate liquid at 1 bar pressure and 1250°C at oxygen fugacities from 10?8.5 and 10?0.7 bars. Pu is much more readily incorporated into crystalline phases than is U or Th under reducing conditions (fO2 = 10?8.5), because Pu is primarily trivalent, whereas U and Th are tetravalent. Definitive valence state assignments cannot be made, but our best estimates of corrected partition coefficients for Pu+3, Pu+4, Th+4, U+4, and U+6 are, for whitlockite 3.6/<?0.6/1.2/0.5/?0.002. The effect of changing pressure and liquidus temperature is relatively small, which probably reflects a weak temperature dependence for D (whitlockite) but possibly could be due to cancellation of opposing temperature and pressure effects. Comparison of experiments at trace U levels with those containing percent concentrations of UO2 indicate that Si is involved in the substitution of U in whitlockite with U + 2Si ? Ca + 2P being the most likely mechanism. Du is lower. 0.3 vs 0.5. at percent levels compared to 20 ppm. This is best explained by the effect of U on melt structure or by a decrease in the fraction of tetravalent U at high U concentrations.  相似文献   

2.
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3.
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4.
In this experimental study, we examine the mineral-melt partitioning of major and trace elements between clinopyroxene and CO2-rich kimberlitic melts at a pressure of 6 GPa and temperatures of 1410°C and 1430°C. The melts produced contain ∼ 28 wt% dissolved CO2, and are saturated with olivine and clinopyroxene. To assess the effects of temperature, crystal and melt compositions on trace element partitioning, experiments were performed in the model CaO-MgO-Al2O3-SiO2-CO2 system. Our results reveal that all the elements studied, except Al, Mg, Si, and Ga, are incompatible in clinopyroxene. Partition coefficients show a considerable range in magnitude, from ∼ 10−3 for DU and DBa to ∼ 2.5 for DSi. The two experimental runs show similar overall partitioning patterns with the D values being lower at 1430°C. Rare earth elements display a wide range of partition coefficients, DLa (0.012-0.026) being approximately one order of magnitude lower than DLu (0.18-0.23). Partition coefficients for the 2+ and 3+ cations entering the M2-site exhibit a near-parabolic dependence on radius of the incorporated cations as predicted from the lattice strain model. This underlines the contribution made by the crystal structure toward controlling the distribution of trace elements. Using data obtained in this study combined with that in the published literature, we also discuss the effects that other important parameters, namely, melt composition, pressure, and temperature, could have on partitioning.Our partition coefficients have been used to model the generation of the Group I (GI) kimberlites from South Africa. The numerical modeling shows that kimberlitic melts can be produced by ∼0.5% melting of a MORB-type depleted source that has been enriched by small-degree melts originating from a similar depleted source. This result suggests that the source of GI kimberlites may be located at the lithosphere-asthenosphere transition. Percolation of small degree melts from the asthenosphere would essentially create a metasomatic horizon near the bottom of the non-convecting sublithospheric mantle. Accumulation of such small degree melts together with the presence of volatiles and conductive heating would trigger melting of the ambient mantle and subsequently lead to eruption of kimberlitic melts. Additionally, our model shows that the GI source can be generated by metasomatism of a 2 Ga old MORB source ca. 1 Ga ago. Assuming that MORB-type mantle is the most depleted source of magmas on earth, then this is the oldest age at which the GI source could have existed. However, this age most likely reflects the average age of a series of metasomatic events than that of a single event.  相似文献   

5.
The solubility of U and Th in aqueous solutions at P-T-conditions relevant for subduction zones was studied by trapping uraninite or thorite saturated fluids as synthetic fluid inclusions in quartz and analyzing their composition by Laser Ablation-ICPMS. Uranium is virtually insoluble in aqueous fluids at Fe-FeO buffer conditions, whereas its solubility increases both with oxygen fugacity and with salinity to 960 ppm at 26.1 kbar, Re-ReO2 buffer conditions and 14.1 wt% NaCl in the fluid. At 26.1 kbar and 800°C, uranium solubility can be reproduced by the equation: log\textU = 2.681 + 0.1433logf\textO2 + 0.594\textCl, \log {\text{U}} = 2.681 + 0.1433\log f{\text{O}}_{2} + 0.594{\text{Cl,}} where fO2 is the oxygen fugacity, and Cl is the chlorine content of the fluid in molality. In contrast, Th solubility is generally low (<10 ppm) and independent of oxygen fugacity or fluid salinity. The solubility of U and Th in clinopyroxene in equilibrium with uraninite and thorite was found to be in the order of 10 ppm. Calculated fluid/cpx partition coefficients of Th are close to unity for all conditions. In contrast, Dfluid/cpx for uranium increases strongly both with oxygen fugacity and with salinity. We show that reducing or NaCl-free fluids cannot produce primitive arc magmas with U/Th ratio higher than MORB. However, the dissolution of several wt% of oxidized, saline fluids in arc melts can produce U/Th ratios several times higher than in MORB. We suggest that observed U/Th ratios in arc magmas provide tight constraints on both the salinity and the oxidation state of subduction zone fluids.  相似文献   

6.
Trace element partition coefficients between clinopyroxenes and associated glassy matrix (Cpx/L D) have been determined for 13 REE, HFSE4+,5+, U, Th, Sr, Pb, Sc and V from combined LA-ICP-MS/EMP analyses in selected trachytes and trachyphonolites from Campi Flegrei. Composition of clinopyroxene and glass is pretty homogeneous in the trachyphonolites, pointing to an overall attainment of the equilibrium conditions. In trachytes, conversely, phases show some compositional heterogeneity (due to the presence of clinopyroxene xenocrysts) that requested a more careful petrographic and geochemical inspection of the samples to assess the equilibrium clinopyroxene composition. In the trachyte clinopyroxenes, REE are compatible from Nd to Lu (Cpx/L D up to 2.9), like Y, Ti, Sc and V. The Cpx/L D for Eu is lower than those of the adjacent REE, highlighting Eu2+ contribution. High D values are also shown by U, Th, Pb, Zr, Hf, Nb and Ta relatively to basaltic and andesitic systems, whereas the D Sr is roughly similar to that found for less evolved magmas. Trachyphonolites are characterized by an overall decrease of the Cpx/L D for highly-charged cations (with the exception of V), and by a slight increase of D Sr. REE are still compatible from Nd to Lu (Cpx/L D up to 2.1), like Ti, Y, Sc and V. This variation is also predicted for REE and Y by models based on the elastic strain theory, being consistent with the slightly lower polymerization degree estimated for the trachyphonolites. However, the observed Cpx/L D (REE,Y) are matched by the modelled ones only considering very low T (≤825°C), which are believed unlikely. This mismatch cannot be attributed to effects induced by the water-rich composition of the trachyte–trachyphonolite suite, since they would lower the observed Cpx/L D (REE,Y). Moreover, the anomalous inflections of measured Cpx/L D for HREE suggests some crystal-chemical control, such as the entrance of these elements in a site distinct from M2. It is concluded that the large Cpx/L D determined for trachytes and trachyphonolites are likely induced by hitherto unconstrained changes of the Z3+ activities related to the composition of melt and/or solid. All these considerations strongly highlight the importance of a direct characterization of trace element partitioning in natural samples from magmatic systems poorly characterized by experimental studies. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

7.
The apparent equilibrium constant for the exchange of Fe and Ni between coexisting olivine and sulfide liquid (KD = (XNiS/XFeS)liquid/(XNiSi12O2/XFeSi12O2)olivine; Xi = mole fraction) has been measured at controlled oxygen and sulfur fugacities (fO2 = 10−8.1 to 10−10 and fS2 = 10−0.9 to 10−1.7) over the temperature range 1200 to 1385°C, with 5 to 37 wt% Ni and 7 to 18 wt% Cu in the sulfide liquid. At log fO2 of −8.7 ± 0.1, and log fS2 of −0.9 to −1.7, KD is relatively insensitive to sulfur fugacity, but comparison with previous results shows that KD increases at very low sulfur fugacities. KD values show an increase with the nickel content of the sulfide liquid, but this effect is more complex than found previously, and is greatest at log fO2 of −8.1, lessens with decreasing fO2, and KD becomes independent of melt Ni content at log fO2 ≤ −9.5. The origin of this variation in KD with fO2 and fS2 is most likely the result of nonideal mixing of Fe and Ni species in the sulfide liquid. Such behavior causes activity coefficients to change with either melt oxygen content or metal/sulfur ratio, effects that are well documented for metal-rich sulfide melts.Application of these experimental results to natural samples shows that the relatively large dispersion that exists in KD values from different olivine + sulfide-saturated rock suites can be interpreted as arising from variations in fO2, fS2, and the nickel content of the sulfide liquid. Estimates of fO2 based on KD and sulfide melt composition in natural samples yields a range from fayalite-magnetite-quartz (FMQ)-1 to FMQ-2 or lower, which is in good agreement with previous values determined for oceanic basalts that use glass ferric/ferrous ratios. Anomalously high KD values recorded in some suites, such as Disko Island, probably reflect low fS2 during sulfide saturation, which is consistent with indications of low fO2 for those samples. It is concluded that the variation in KD values from natural samples reflects olivine-sulfide melt equilibrium at conditions within the T-fO2-fS2 range of terrestrial mafic magmas.  相似文献   

8.
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9.
Ulf Hålenius  Klaus Langer 《Lithos》1980,13(3):291-294
Six natural chloritoid crystals with Fe2+ and Fe3+ contents ranging from 4.15 to 12.81 and from 0.411 to 0.849g-atoms/l, respectively, as determined by means of microprobe and Mössbauer techniques, served as reference material to develop non-destructive microscope-spectrophotometric methods for quantitative Fe2+ – Fe3+ determinations in chloritoids from unpolarized spectra of (001) platelets. Fe2+ concentrations in g-atom/l can be obtained from [ [Fe3+]=C1xD1/t where D1 = log10(I0/I at 28,000 cm-1 and t=crystal thickness in cm; C1 is a conttant that may be influenced somewhat by experimental conditions and is found to be 0.002289 with the experimental set-up used in this study. Fe2+ concentrations in g-atom/l can be obtained from [Fe2+]=C1xD1/D1-C3 with D2=log10(I0/I) at 16,300 cm?1 and constants C4 = 45.36 and C5 = 3.540. Due to the uncertainties in absorbance measurements, D1 and D2 and the thickness measurements, the accuracies are ±0.05 and ±0.15 g-atom/l for [Fe3+] and [Fe2+], respectively. The determinations may be carried out on chloritoid grains in normal thin sections with an areal resolution of ～10 μm.  相似文献   

10.
There is a positive correlation between the concentration of P2O5 in basic magmas and the concentration of the REE and also between their light: heavy ratio, represented by both Ce/Yb and Nd/Sm. This suggests that a phosphate mineral, such as apatite or whitlockite, both of which can contain high concentrations of REE, is present in the magma source regions. Thermodynamic calculations indicate that fluorapatite is stable over the whole P-T range of magma generation, but at the greatest depths it may co-exist with whitlockite in the presence of fluorphlogopite. Using published REE crystal-liquid distribution coefficients, it is evident that for P2O5-rich basic magmas with 700–1000 times chondritic abundances of LREE, garnet need not have contributed significantly to their composition. The most convincing match of hypothetical liquid with actual basic magma is for the derivation of mid-ocean ridge (MOR) basalts from plagioclase- or spinel-lherzolite containing 3 times chondritic REE by ∼5% partial melting. The more P2O5-rich, and hence REE-rich, basic magmas are apparently derived from crystalline sources which are progressively impoverished in garnet and clinopyroxene, or in other words, the greater the REE concentration of basic magma, the more refractory is the mineral assemblage of the source. There is some evidence for a compositional dependence of radiogenic neodymium and lead in basic magma, and one way that this can be reconciled with mantle source-region evolution is to postulate that fusion is not always accompanied by isotopic equilibrium.  相似文献   

11.
Trace element partitioning between apatite and silicate melts   总被引：7，自引：0，他引：7  
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 DHf > DZr, DTa ≈ DNb, and DBa > DRb > DCs. 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.  相似文献   

12.
The osmotic coefficients of FeCl3 at 25 °C from 0.15 to 1.7 m [Rumyantsev et al., Z. Phys. Chem., 218, 1089-1127, 2004] have been used to determine the Pitzer parameters (β(0), β(1) and C?) for FeCl3. Since the differences in the Pitzer coefficients of rare earths in NaCl and NaClO4 are small, the values of Fe(ClO4)3 have been estimated using the differences between La(ClO4)3 and LaCl3. The Pitzer coefficients for FeCl3 combined with enthalpy and heat capacity data for the rare earths can be used to estimate the activity coefficients of Fe3+ in NaCl over a wide range of temperatures (0 to 50 °C) and ionic strength (0 to 6 m).The activity coefficients of Fe3+ in NaCl and NaClO4 solutions have been used to determine the activity coefficients of Fe(OH)2+ in these solutions from the measured first hydrolysis constants of Fe3+ [Byrne et al., Mar. Chem., 97, 34-48, 2005]. The activity coefficients of , Fe(OH)3 and from 0 to 50 °C have also been determined from the solubility measurements of Fe(III) in NaCl solutions [Liu and Millero, Geochim. Cosmochim Acta, 63, 3487-3497, 1999]. These activity coefficients have been fitted to the Pitzer equations. These results can be used to estimate the speciation of Fe(III) with OH− in natural waters with high concentrations of NaCl from 0 to 50 °C.  相似文献   

13.
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14.
Oldhamite is a major Th and U bearing phase in the enstatite meteorites. Oldhamite from E-6 chondrites has mean Th and U abundances of 1550 ± 80 ppb Th and 410 ± 20 ppb U, with ThU = 3.8 ± .2. With the exception of ferroan alabandite which contains 25 ± 1 ppb U, no other Th or U enriched phases were located in the E-6 chondrites, and nearly all of the total rock Th and U can be accounted for by oldhamite. In Khairpur (E6), excess fossil fission tracks were observed in enstatite grains in contact with oldhamite which indicates the presence of 244Pu in oldhamite. Oldhamite from St. Mark's (E5) and Abee (E4) also shows actinide enrichments but at levels about half the E-6 results. Niningerite in Abee contains 45 ± 5 ppb U and due to its high reported modal abundance is an important U reservoir in Abee. The U content of oldhamite from the aubrite Peña Blanca Spring is 1920 ± 100 ppb. All ThU values measured in this study cluster tightly around a value of 4 which indicates a lack of ThU fractionation in both oldhamite and in the enstatite meteorites, themselves. This lack of fractionation, along with the presence of 244Pu in oldhamite and reported rare earth enrichments also in oldhamite, suggests that the enstatite chondrites may be well-suited for PuU chronology and for providing the initial PuU value in the early solar system.  相似文献   

15.
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   

16.
根据X射线衍射(XRD)分析发现: A Fe3(SO4)2(OH)6(A=K+、H3O+)系列铁钒的XRD数据十分相近,难以用XRD区别,需通过能谱(EDS)辅助分析,才能区分此类铁矾。另外,此类铁矾的003和107面网间距d随K+含量增大而增大,且呈一元三次方程的关系;而033和220面网间距d随K+含量增大而减小,呈一元二次方程的关系。对该现象从铁矾晶体结构方面进行解释:K+、H3O+离子位于较大空隙中,且沿着Z轴方向排列,当K+、H3O+离子之间相互替换时,会导致该铁矾晶体结构在Z轴方向有较明显的变化。  相似文献   

17.
We report rates of oxygen exchange with bulk solution for an aqueous complex, IVGeO4Al12(OH)24(OH2)128+(aq) (GeAl12), that is similar in structure to both the IVAlO4Al12(OH)24(OH2)127+(aq) (Al13) and IVGaO4Al12(OH)24(OH2)127+(aq) (GaAl12) molecules studied previously. All of these molecules have ε-Keggin-like structures, but in the GeAl12 molecule, occupancy of the central tetrahedral metal site by Ge(IV) results in a molecular charge of +8, rather than +7, as in the Al13 and GaAl12. Rates of exchange between oxygen sites in this molecule and bulk solution were measured over a temperature range of 274.5 to 289.5 K and 2.95 < pH < 4.58 using 17O-NMR.Apparent rate parameters for exchange of the bound water molecules (η-OH2) are kex298 = 200 (±100) s−1, ΔH‡ = 46 (±8) kJ · mol−1, and ΔS‡ = −46 (±24) J · mol−1 K−1 and are similar to those we measured previously for the GaAl12 and Al13 complexes. In contrast to the Al13 and GaAl12 molecules, we observe a small but significant pH dependence on rates of solvolysis that is not yet fully constrained and that indicates a contribution from the partly deprotonated GeAl12 species.The two topologically distinct μ2-OH sites in the GeAl12 molecule exchange at greatly differing rates. The more labile set of μ2-OH sites in the GeAl12 molecule exchange at a rate that is faster than can be measured by the 17O-NMR isotopic-equilibration technique. The second set of μ2-OH sites have rate parameters of kex298 = 6.6 (±0.2) · 10−4 s−1, ΔH‡ = 82 (±2) kJ · mol−1, and ΔS‡ = −29 (±7) J · mol−1 · K−1, corresponding to exchanges ≈40 and ≈1550 times, respectively, more rapid than the less labile μ2-OH sites in the Al13 and GaAl12 molecules. We find evidence of nearly first-order pH dependence on the rate of exchange of this μ2-OH site with bulk solution for the GeAl12 molecule, which contrasts with Al13 and GaAl12 molecules.  相似文献   

18.
Although, the kinetic reactivity of a mineral surface is determined, in part, by the rates of exchange of surface-bound oxygens and protons with bulk solution, there are no elementary rate data for minerals. However, such kinetic measurements can be made on dissolved polynuclear clusters, and here we report lifetimes for protons bound to three oxygen sites on the AlO4Al12(OH)24(H2O)127+ (Al13) molecule, which is a model for aluminum-hydroxide solids in water. Proton lifetimes were measured using 1H NMR at pH ∼ 5 in both aqueous and mixed solvents. The 1H NMR peak for protons on bound waters (η-H2O) lies near 8 ppm in a 2.5:1 mixture of H2O/acetone-d6 and broadens over the temperature range −20 to −5 °C. Extrapolated to 298 K, the lifetime of a proton on a η-H2O is τ298 ∼ 0.0002 s, which is surprisingly close to the lifetime of an oxygen in the η-H2O (∼0.0009 s), but in the same general range as lifetimes for protons on fully protonated monomer ions of trivalent metals (e.g., Al(H2O)63+). The lifetime is reduced somewhat by acid addition, indicating that there is a contribution from the partly deprotonated Al13 molecule in addition to the fully protonated Al13 at self-buffered pH conditions. Proton lifetimes on the two distinct sets of hydroxyls bridging two Al(III) (μ2-OH) differ substantially and are much shorter than the lifetime of an oxygen at these sites. The average lifetimes for hydroxyl protons were measured in a 2:1 mixture of H2O/dmso-d6 over the temperature range 3.7-95.2 °C. The lifetime of a hydrogen on one of the μ2-OH was also measured in D2O. The τ298 values are ∼0.013 and ∼0.2 s in the H2O/dmso-d6 solution and the τ298 value for the μ2-OH detectable in D2O is τ298 ∼ 0.013 s. The 1H NMR peak for the more reactive μ2-OH broadens slightly with acid addition, indicating a contribution from an exchange pathway that involves a proton or hydronium ion. These data indicate that surface protons on minerals will equilibrate with near-surface waters on the diffusional time scale.  相似文献   

19.
Helium, neon, argon, krypton and xenon data are presented from stepwise heating of samples of the mineral whitlockite from the chondritic meteorite St. Severin. The xenon is shown to be a uniform mixture derived from 244Pu fission and rare-earth element spallation. The krypton similarly contains spallation products and 86Kr from 244Pu fission. Plutonium-244 fission yields of 86Kr/129Xe/131Xe/132Xe/134Xe/136Xe = 1.9 ± 0.5/4.8 ± 5.5/24.6 ± 2.0/88.5 ±3.0/93.9 ± 0.8/  100 are obtained. The helium, neon and argon are dominated by spallation and radiogenic 4He and 40Ar. A pile neutron irradiation experiment does not yield a unique Pu/U ratio for this mineral but yields ratios varying from 0.045 down to 0.017. Both the high concentration of 244Pu fission xenon and the high ratio of Pu/U previously reported by Wasserburget al. (J. Oeophys. Res. 74, 4221–4232, 1969) are thus confirmed.  相似文献   

20.
The sodium solubility in silicate melts in the CaO-MgO-SiO2 (CMS) system at 1400 °C has been measured by using a closed thermochemical reactor designed to control alkali metal activity. In this reactor, Na(g) evaporation from a Na2O-xSiO2 melt imposes an alkali metal vapor pressure in equilibrium with the molten silicate samples. Because of equilibrium conditions in the reactor, the activity of sodium-metal oxide in the molten samples is the same as that of the source, i.e., aNa2O(sample) = aNa2O(source). This design also allows to determine the sodium oxide activity coefficient in the samples. Thirty-three different CMS compositions were studied. The results show that the amount of sodium entering from the gas phase (i.e., Na2O solubility) is strongly sensitive to silica content of the melt and, to a lesser extent, the relative amounts of CaO and MgO. Despite the large range of tested melt compositions (0 < CaO and MgO < 40; 40 < SiO2 < 100; in wt%), we found that Na2O solubility is conveniently modeled as a linear function of the optical basicity (Λ) calculated on a Na-free basis melt composition. In our experiments, γNa2O(sample) ranges from 7 × 10−7 to 5 × 10−6, indicating a strongly non-ideal behavior of Na2O solubility in the studied CMS melts (γNa2O(sample) ? 1). In addition to showing the effect of sodium on phase relationships in the CMS system, this Na2O solubility study brings valuable new constraints on how melt structure controls the solubility of Na in the CMS silicate melts. Our results suggest that Na2O addition causes depolymerization of the melt by preferential breaking of Si-O-Si bonds of the most polymerized tetrahedral sites, mainly Q4.  相似文献   

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