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1.
Diopside-melt and forsterite-melt rare earth (REE) and Ni partition coefficients have been determined as a function of bulk compositions of the melt. Available Raman spectroscopic data have been used to determine the structures of the melts coexisting with diopside and forsterite. The compositional dependence of the partition coefficients is then related to the structural changes of the melt.The melts in all experiments have a ratio of nonbridging oxygens to tetrahedral cations ( ) between 1 and 0. The quenched melts consist of structural units that have, on the average, 2 (chain), 1 (sheet) and 0 (three-dimensional network) nonbridging oxygens per tetrahedral cation. The proportions of these structural units in the melts, as well as the overall , change as a function of the bulk composition of the melt.It has been found that Ce, Sm, Tm and Ni crystal-liquid partition coefficients ( ) decrease linearly with increasing . The values of the individual REE crystal-liquid trace element partition coefficients have different functional relations to , so that the degree of light REE enrichment of the melts would depend on their .The solution mechanisms of minor oxides such as CO 2, H 2O, TiO 2, P 2O 5 and Fe 2O 3 in silicate melts are known. These data have been recast as changes of of the melts with regard to the type of oxide and its concentration in the melt. From such data the dependence of crystal-liquid partition coefficients on concentration and type of minor oxide in melt solution has been calculated. 相似文献
2.
New analyses of K, Rb, Sr and Ba contents and the ratios of eight amphiboles, one phlogopite, two diopsides and one host alkalic basalt for an amphibole are reported: The samples are mostly inclusions in alkalic basalts and occur in association with peridotite inclusions. Two of the samples are from alpine-type peridotite bodies — one from the Etang de Lhers massif in the French Pyrenees and the other from the Finero massif in the Ivrea zone in northern Italy. The kaersutites come from the following localities: Hoover Dam, Arizona; Deadman Lake, California; Massif Central, France; Queensland; Spring Mountain, New South Wales.The data indicate that kaersutitic amphiboles are genetically unrelated to their host basalts. The isotopic and trace element data of these amphiboles further strengthens the suggestion of BASU and MURTHY (1977) that kaersutites play a significant role in ocean ridge basalt genesis. In addition, pargasitic amphibole with higher ratios, if present, may be important in the source regions of alkalic basalts.The bulk amphibole lherzolite from Lherz has the ratio and ratio appropriate for source material of ridge tholeiites. If the diopside and the amphibole in this rock had isotopically equilibrated under upper mantle conditions, the data show the time of last equilibration to be approximately 735 m.y., in contrast to the young emplacement age of the ultramafic massif.The coexisting phlogopite and diopside in the spinel lherzolite inclusion from Kilbourne Hole, New Mexico, show, surprisingly, isotopic equilibration under upper mantle conditions despite their drastically different ratios. The data show that the phlogopite must have formed very recently in the upper mantle. This phlogopite also has a high ratio (1133), contrary to the commonly held view that mantle phlogopites have low ratios. The coexisting diopside shows high K content (778 ppm) and a lower ratio than the phlogopite. This phlogopite lherzolite has trace elemental and isotopic characteristics that may be adequate for the origin of alkalic basalts upon partial melting. 相似文献
3.
K and Rb distributions between aqueous alkali chloride vapour phase (0.7 molar) and coexisting phlogopites and sanidines have been investigated in the range 500 to 800°C at 2000 kg/cm 2 total pressure.Complete solid solution of RbMg 3AlSi 3O 10(OH) 2 in KMg 3AlSi 3O 10(OH) 2 exists at and above 700°C. At 500°C a possible miscibility gap between approximately 0.2 and 0.6 mole fraction of the Rb end-member is indicated.Only limited solid solution of Rb AlSi 3O 8 in KAlSi 3O 8 has been found at all temperatures investigated.Distribution coefficients, expressed as in solid/(Rb/K) in vapour, are appreciably temperature-dependent but at each temperature are independent of composition for low Rb end-member mole fractions in the solids. The determined values and their approximate Rb end-member mole fraction ( ) ranges of constancy are summarized as follows: (°C) | (°C)T | | | | | | 500 | | 0–0.2 | | 0–0.07 | | 700 | | 0–0.2 | | 0–0.1 | | 800 | | 0–0.2 | | 0–0.1 | 相似文献
4.
The Archean Yellowknife Supergroup (Slave Structural Province. Canada) is composed of a thick sequence of supracrustal rocks, which differs from most Archean greenstone belts in that it contains a large proportion ( ~ 80%) of sedimentary rocks. Felsic volcanics of the Banting Formation are characterized by HREE depletion without Eu-anomalies, indicating an origin by small degrees of partial melting of a mafic source, with minor garnet in the residua. Granitic rocks include synkinematic granites [HREE-depleted; low ( ) I], post-kinematic granites [negative Eu-anomalies, high ( ) I] and granitic gneisses with REE patterns similar to the post-kinematic granites. Sedimentary rocks (turbidites) of the Burwash and Walsh Formations have similar chemical compositions and were derived from 20% mafic-intermediate volcanics, 55% felsic volcanics and 25% granitic rocks. Jackson Lake Formation lithic wackes can be divided into two groups with Group A derived from 50% mafic-intermediate volcanics and 50% felsic volcanics and Group B, characterized by HREE depletion, derived almost exclusively from felsic volcanics.REE patterns of Yellowknife sedimentary rocks are similar to other Archean sedimentary REE patterns, although they have higher . These patterns differ significantly from typical post-Archean sedimentary REE patterns, supporting the idea that Archean exposed crust had a different composition than the present day exposed crust. 相似文献
5.
The C3O chondrites Kainsaz, Lancé and Ornans were studied by an acid dissolution technique, to characterize the noble-gas components in 3 mineral fractions: HF, HCl-solubles (99% of the meteorite), chromite and carbon (0.3–0.9%), and ‘phase Q’, a poorly characterized trace mineral (0.05–0.4%) containing most of the Ar, Kr, Xe. For all fractions, gas contents decline in the order Kainsaz > Lancé > Ornans; this trend parallels volatile contents but not heterogeneity of olivine composition or degree of metamorphism and seems to reflect progressively higher condensation temperatures from the solar nebula. Solubles contain nearly unfractionated Xe, and show ratios up to 850. Hence the high ratios (200–400) of bulk C3O chondrites must be due to an HF-soluble mineral (possibly magnetite). Phase Q contains ordinary planetary gases and a Ne component of Chromite and carbon contain Ne of and ‘CCF’ xenon (a peculiar component of possibly fissiogenic origin, enriched in the heavy isotopes but accompanied by a component enriched in the light isotopes).In all primitive chondrites, both the amount and the chemical separability of CCFXe parallel the abundance of promordial noble gases and other volatiles, such as C, N, Tl, Bi and In. The close correlation of CCFXe with various properties of undoubtedly local origin (volatile content, petrologic type, presence of ferrichromite and carbon, etc.) is more consistent with a local than with an extrasolar origin of this component. A volatile superheavy element seems to be the most plausible source, but the evidence is not conclusive. 相似文献
7.
Seventy-two basalts from 58 dredge stations located along the Mid-Atlantic Ridge from 29°N to 59°N have been analyzed for and for K, Rb, Cc, Sr and Ba. The Sr-isotope profile along the ridge has three distinct maxima, one coinciding with the Azores platform (0.70345), one at 45°N (0.70340) and the third at 35°N, in the vicinity of the Oceanographer Fracture Zone. Basalts from ridge segments between 29°N and 33°N, and 49°N and 59°N have ratios typical of ‘normal’ mid-ocean ridge basalts (0.70230–0.70280). Profiles of K, Rb, Cs, Sr, Bz, Rb/Sr and Ba/Sr are similar to the profile, but Rb/K, Cs/K and Ba/K show broad maxima between 35°N and 45°N.These variations result from chemical and isotopic heterogeneity in the mantle, and are interpreted as caused by a mantle plume beneath the Azores which mixes with the LIL-element-depleted asthenosphere. Additional plumes may exist beneath 45°N and 35°N.Compared to the LIL-element-depleted asthenosphere, the Azores mantle plume is 10 to 30 times enriched in LIL elements with very small (? 0.1) bulk crystal/melt partition coefficients (Rb, Cs, Ba, La). Mildly incompatible elements (0.1 < D < 1) (Sr, Sm, Yb) are only 0.8–3 times enriched. These, observations suggest that LIL element differences between these two mantle reservoirs resulted from processes involving solid-liquid equilibria and not vapor-solid or vapor-liquid equilibria. Isotope systematics indicate that neither mantle reservoir remained a closed system since the formation of the Earth, but it is not possible to determine the time at which heterogeneity first developed. 相似文献
8.
A suite of rocks from the Point Sal ophiolite, California, were analyzed for rare earth elements (REE), Sc, Co, Na 2O, Cr, Zn and FeO. The lavas all have either flat or slightly light REE (LREE) depleted profiles relative to chondrites. The lavas contain smectite or greenschist facies mineralogy and some have radiogenically enriched ratios. This is interpreted as evidence of basaltseawater interaction (Hopson et al., 1975; Davis and Lass, 1975). The smectite and zeolite bearing lavas that have been exposed to seawater for prolonged periods have anomalous Ce abundances. At higher grades of metamorphism, the lavas show no marked changes in light REE. The plutonic igneous rocks vary from early cumulus dunite to late stage, noncumulus diorite. All the plutonic rocks are light REE depleted with total REE abundance varying by a factor of 100 × between the dunites and diorites. Analyses of clinopyroxene and hornblende separates indicate that these two minerals strongly influence the REE characteristics of the early cumulates and late stage fractionates, respectively.In general, REE contents are: hornblende > clinopyroxene > plagioclase > orthopyroxene > olivine. Estimates of the REE compositions of parental lavas were obtained by calculating the REE contents of liquids in equilibrium with early cumulate clinopyroxenes. This reveals that the parent to the stratiform sequence was more depleted in light REE than the parent to the lava pile. 相似文献
9.
The distribution coefficients of Eu and Sr for plagioclase-liquid and clinopyroxene-liquid pairs as a function of temperature and oxygen fugacity were experimentally investigated using an oceanic ridge basalt enriched with Eu and Sr as the starting material. Experiments were conducted between 1190° and 1140°C over a range of oxygen fugacities between 10 ?8 and 10 ?14 atm.The molar distribution coefficients are given by the equations: logPLSr = 7320/ T ? 4.62 logKCPXSr = 18020/ T ? 13.10. Similarly, the weight fraction distribution coefficients are given by the equations: logDPLSr = 6570/ T ? 4.30 logDCPXSr = 18434/ T ? 13.62.Although the mole fraction distribution coefficients have a smaller dependence on bulk composition than do the weight fraction distribution coefficients, they are not independent of bulk composition, thereby restricting the application of these experimental results to rocks similar to oceanic ridge basalts in bulk composition.Because the Sr distribution coefficients are independent of oxygen fugacity, they may be used as geothermometers. If the temperature can be determined independently — for example, with the Sr distribution coefficients, the Eu distribution coefficients may be used as oxygen geobarometers. Throughout the range of oxygen fugacities ascribed to terrestrial and lunar basalts, plagioclase concentrates Eu but clinopyroxene rejects Eu. 相似文献
10.
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, D REECryst-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. D Yb falls to ~ 12 at 1420°C. D SmGa-liq also correlates negatively with temperature and positively with the grossular content of garnet. Patterns of D reeCryst-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 REE 3+ 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
11.
Two very different sets of ratios have been reported for early solar system materials. One group of samples yields high (0.015–0.016) ratios (Podosek, 1970a, 1972; Drozd et al., 1977) and calculations based on another group of analyses yield low ratios (~0.004) (Marti et al., 1977). Recently measured partition coefficients for Pu and Sm are used to evaluate the data of Marti et al. and ratios from other sources are also considered. A low ratio (~0.005) is favored, and some implications of this low ratio to galactic nucleosynthesis and meteorite age dating are briefly discussed. 相似文献
12.
The solubility of rutile has been determined in a series of compositions in the K 2O-Al 2O 3-SiO 2 system ( + Al 2O 3) = 0.38–0.90), and the CaO-Al 2O 3-SiO 2 system ( ). Isothermal results in the KAS system at 1325°C, 1400°C, and 1475°C show rutile solubility to be a strong function of the ratio. For example, at 1475°C the amount of TiO 2 required for rutile saturation varies from 9.5 wt% ( ) to 11.5 wt% ( ) to 41.2 wt% ( ). In the CAS system at 1475°C, rutile solubility is not a strong function of . The amount of TiO 2 required for saturation varies from 14 wt% ( ) to 16.2 wt% ( ).The solubility changes in KAS melts are interpreted to be due to the formation of strong complexes between Ti and K + in excess of that needed to charge balance Al 3+. The suggested stoichiometry of this complex is K 2Ti 2O 5 or K 2Ti 3O 7. In CAS melts, the data suggest that Ca 2+ in excess of A1 3+ is not as effective at complexing with Ti as is K +. The greater solubility of rutile in CAS melts when is less than 0.54 compared to KAS melts of equal ratio results primarily from competition between Ti and Al for complexing cations (Ca vs. K).TiK β x-ray emission spectra of KAS glasses ( ) with 7 mole% added TiO 2, rutile, and Ba 2TiO 4, demonstrate that the average Ti-O bond length in these glasses is equal to that of rutile rather than Ba 2TiO 4, implying that Ti in these compositions is 6-fold rather than 4-fold coordinated. Re-examination of published spectroscopic data in light of these results and the solubility data, suggests that the 6-fold coordination polyhedron of Ti is highly distorted, with at least one Ti-O bond grossly undersatisfied in terms of Pauling's rules. 相似文献
13.
Differences in the chemical composition of metamorphic and igneous pyroxene minerals may be attributed to a transfer reaction, which determines the Ca content of the minerals, and an exchange reaction, which determines the relative Mg:Fe 2+ ratios. Natural data for associated Ca pyroxene (Cpx) and orthopyroxene (Opx) or pigeonite are combined with experimental data for Fe-free pyroxenes, to produce the following equations for the Cpx slope of the solvus surface: , and the following equation for the temperature-dependence of the Mg-Fe distribution coefficient: , where T is absolute temperature, X is , [Ca] is in Cpx, and KD is the distribution coefficient, defined as .The transfer and exchange equations form useful temperature indicators, and when applied to 9 sets of well-studied rocks, yield pairs of temperatures that are in good agreement. For example, temperatures obtained for the Bushveld Complex are 1020°C (solvus equation) and 980°C (exchange equation), based on 7 specimens. The uncertainty in these numbers, due to precision and accuracy errors, is estimated to be ±60°. 相似文献
14.
The concentrations of 238Pu, 239 + 240Pu, 241Am and 137Cs were determined in rain samples collected at Monaco in the course of 1978–1979. Based on these data, the annual deliveries of these radionuclides to the Mediterranean by rain are computed to be 0.18 ± 0.01 pCim?2 for 238Pu, 8.1 ± 0.1 pCim?2 for 239 + 240Pu, 0.58 ± 0.02 pCim?2 for 241Am and 351 ± 4 pCim?2 for 137Cs.Comparing the delivery data with the mixed layer inventories of 239 + 240Pu and 241Am in the Mediterranean, the upper limits of the mean residence time of these radionuclides in the mixed layer were estimated to be 12.3 yr for 239 + 240pu and 2.9 yr for 241Am. These values are consistent with the conclusion deduced from the vertical distribution pattern of these transuranic elements in the Mediterranean.Based on delivery values, the annual activity ratios for , and are found to be 0,022, 0.072 and 0.023 respectively. The and activity ratios vary within relatively narrow ranges with time, while a much wider variation was observed for the activity ratio. The cause of the wider variation of the ratio may be related to the difference in the mean age of fallout brought down in different seasons. 相似文献
15.
Natural malachite is a well defined solid demonstrating reproducible solubility behavior over a wide range of pH. The following equilibrium constants associated with the malachite dissolution equilibrium at 25°C, 1 atm were determined: (infinite dilution) (0.72 ionic strength) (36.9‰ salinity seawater). The temperature dependence of a “mixed” equilibrium constant, Ksp+, of the form: has been measured at I = 0.72, yielding the relationship: within a 5–25°C temperature range. The effect of pressure on the solubility of malachite in water and seawater was estimated from partial molar volume and compressibility data. For 25 °C at infinite dilution and in seawater .Comparison of stoichiometric and apparent malachite equilibrium constants has been used to estimate the extent of copper(II) ion interaction at the ionic strength of seawater. In dilute carbonate medium (total alkalinity, TA = 2.4 meq/kg H2O, pH 8.3), 2.9% of total dissolved copper exists as the free copper(II) ion and in seawater ( S = 36.9%., TA = 2.3 meq/kg H2O, pH = 8.1), is 3.1%.Total dissolved copper levels of approximately 450–750 nMol/Kg are necessary to attain malachite saturation conditions in the open ocean. Observations of malachite particles suspended in seawater must be explained by precipitation or solid phase substitution reactions from localized environments rather than by direct precipitation from bulk seawater. 相似文献
16.
The effect of presure on the solubility of minerals in water and seawater can be estimated from In where the volume ( ΔV) and compressibility ( ΔK) changes at atmospheric pressure ( P = 0) are given by Values of the partial molal volume ( ) and compressibilty ( ) in water and seawater have been tabulated for some ions from 0 to 50°C. The compressibility change is quite large (~10 × 10 ?3 cm 3 bar ?1 mol ?1) for the solubility of most minerals. This large compressibility change accounts for the large differences observed between values of ΔV obtained from linear plots of In Ksp versus P and molal volume data (Macdonald and North, 1974; North, 1974). Calculated values of for the solubility of CaCO 3, SrSO 4 and CaF 2 in water were found to be in good agreement with direct measurements (Macdonald and North, 1974). Similar calculations for the solubility of minerals in seawater are also in good agreement with direct measurements (Ingle, 1975) providing that the surface of the solid phase is not appreciably altered. 相似文献
17.
Analyses have been made of REE contents of a well-characterized suite of deep-sea (> 4000 m.) principally todorokite-bearing ferromanganese nodules and associated sediments from the Pacific Ocean. REE in nodules and their sediments are closely related: nodules with the largest positive Ce anomalies are found on sediments with the smallest negative Ce anomalies; in contrast, nodules with the highest contents of other rare earths (3 + REE) are found on sediments with the lowest 3 + REE contents and vice versa. ratios in the nodules (～0.51244) point to an original seawater source but an identical ratio for sediments in combination with the REE patterns suggests that diagenetic reactions may transfer elements into the nodules. Analysis of biogenic phases shows that the direct contribution of plankton and carbonate and siliceous skeletal materials to REE contents of nodules and sediments is negligible. Inter-element relationships and leaching tests suggest that REE contents are controlled by a P-rich phase with a REE pattern similar to that for biogenous apatite and an Fe-rich phase with a pattern the mirror image of that for sea water. It is proposed that 3 + REE concentrations are controlled by the surface chemistry of these phases during diagenetic reactions which vary with sediment accumulation rate. Processes which favour the enrichment of transition metals in equatorial Pacific nodules favour the depletion of 3 + REE in nodules and enrichment of 3 + REE in associated sediments. In contrast, Ce appears to be added both to nodules and sediments directly from seawater and is not involved in diagenetic reactions. 相似文献
18.
The stability constants, , for borate complexes with the ions of Cu, Pb, Cd and Zn are determined in this work by DPASV in 0.7 M KNO 3 at metal concentrations of 10 ?7 M. The acidity constants of the Cu 2+ ion are determined by DPASV in the same conditions. The following values for log ( ) have been obtained: CuB: 3.48, CuB 2: 6.13, PbB: 2.20, PbB 2: 4.41, ZnB: 0.9, ZnB 2: 3.32, CdB: 1.42, and CdB 2: 2.7, while the values for the acidity constants of Cu are and . At the low concentration of boron in 35%. S sea-water complexes with borate represent only about 0.2% Cu, 0.03% Pb, 0.02% Zn and 0.003% Cd. 相似文献
19.
Pb isotope ratios have been measured in 12 volcanic rocks from the South Sandwich Islands. The ranges are . In and correlation diagrams, the South Sandwich data plot distinctly above the fields for ocean ridge basalts, and yield trends showing apparent mixing with a sedimentary end member similar to South Atlantic pelagic sediments as reported by Chow and Patterson (1962) and this study. Armstrong and Cooper (1971) have likewise shown that volcanics from the Lesser Antilles show mixing trends with North Atlantic sediments in Pb isotope correlation diagrams. The North Atlantic sediments have distinctly higher and ratios compared to the South Atlantic sediments. The parallel relationships between sediments and volcanic island arc rocks of the North and South Atlantic provide strong evidence for a component of Pb from subducted sediments in the lavas of the west Atlantic basin. In contrast to these data, lavas from the Mariana Arc in the western Pacific show little or no component of Pb from pelagic sediments. The reason for the different behaviors in the two settings is speculative. 相似文献
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