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1.
A systematic analysis of micas contained in effusive, pyroclastic and hypabyssal rocks of the Alban Hills Volcanic District (AHVD) (Central Italy) was made in order to characterise minerals of pyroclastic units for tephrostratigraphy and to obtain as much information as possible on the activity of volatiles in this magmatic system. The phlogopite shows a large range of F contents (between 0.50 and 7.50 wt%) that make it possible to discriminate different AHVD lithologies; in particular, micas of lava groundmass are characterised by extremely high F (up to 7.50 wt%) and Ba (up to 9.70 wt%) contents, seldom or never found in other magmatic ultrapotassic rocks. Moreover, the micas of pyroclastics, ultramafic cumulates and holocrystalline inclusions made up of leucite, clinopyroxene and phlogopite (hereafter italites) show Mg/(Mg+Fe) values between 0.65 and 0.90 that are not correlated with F contents. The variations in F contents observed in the AHVD micas do not appear to be due to a “temperature” effect or pressure changes, but they may be due to variations in the H2O and CO2 activities in the magma chamber. They make it possible to differentiate three crystallisation environments in the AHVD magmatic system. The first one had elevated CO2 activity and formed the italites near the carbonate contact; these rocks represent, at least those enriched in clinopyroxene without skarn-minerals, the hypabyssal crystallisation of the AHVD magmas at the periphery of magma chamber. The second one, characterised by a higher water activity, is represented by the micas of the ultramafic cumulates and pyroclastic scorias, and is located in the inner part of magma chamber. The third environment, the groundmass of the lavas, it is not related with the previous ones and is characterised by the absence of water and by a high F activity. In general, our results suggest that the compositional variations observed in the micas (Al, Si, Ti, Ba) reflect different H2O activities (inversely correlated with F activity) in the magma chamber.  相似文献   

2.
The oxidation state of iron can significantly influence the physical and chemical properties of lower mantle minerals. To improve methods for estimation of Fe3+/∑Fe, synthetic assemblages of (Mg,Fe)(Si,Al)O3 perovskite and (Mg,Fe)O ferropericlase were synthesised from oxide starting mixtures in Re or Fe capsules at 26 GPa and 1650-1850 °C using a multianvil press. (Mg,Fe)(Si,Al)O3 majorite was also present in some of the run products. Both electron energy loss spectra (EELS) and Mössbauer spectra were measured for each run product, and a robust fitting method was developed for Mössbauer spectra using EELS results as a standard that enabled Fe3+/∑Fe of (Mg,Fe)(Si,Al)O3 perovskite to be determined from Mössbauer spectra of multiphase assemblages. There is a close to linear variation between Fe3+/∑Fe and Al concentration in (Mg,Fe)(Si,Al)O3 perovskite, independent of oxygen fugacity. The concentration of Fe3+ in (Mg,Fe)O increases with increasing iron concentration along curves of constant oxygen fugacity, where higher oxygen fugacity stabilises greater Fe3+ concentrations. Fe2+/Mg partition coefficients calculated from chemical composition data corrected for measured Fe3+/∑Fe showed values nearly identical within experimental error for all samples, and independent of Al concentration and oxygen fugacity. Simple empirical relations were derived to calculate Fe3+/∑Fe in (Mg,Fe)(Si,Al)O3 perovskite and (Mg,Fe)O ferropericlase samples for which no Mössbauer or EELS data were available, and tested by applying them to calculation of Fe2+/Mg partition coefficients from literature data for (Mg,Fe)(Si,Al)O3 perovskite-(Mg,Fe)O assemblages where only total iron concentrations had been measured. Results showed Fe2+/Mg partition coefficients that were equal to existing values within experimental error, hence confirming the validity of the empirical relations.  相似文献   

3.
Self-diffusion of oxygen in a natural phlogopite mica (annite 4%) has been measured under hydrothermal conditions at 2000 bars pressure and from 500 to 800°C using water enriched in18O. Diffusional transport is dominantly parallel to the c crystallographic axis. A linear Arrhenius plot was obtained with a pre-exponential term = (1.03 ± 0.38) × 10?9cm2sec?1 a and an activation energy of 29 ± 2kcal/g-atom O. The difference in transport rate between oxygens in the OH groups and those in tetrahedral sites is small to non-existent unless the OH oxygens diffuse much more slowly than the other oxygens, which we consider unlikely. A typical phlogopite crystal, 0.2 mm thick by 1 mm across will lose radiogenic argon faster than it will exchange oxygen at temperatures above 435°C, but the reverse holds at lower temperatures if the diffusion mechanism can be extrapolated to temperatures below 500°C. Such a crystal will lose only 5% of its argon if held at 380°C for 1 m.y., but could exchange 27% of its oxygen in that time. The rate at which phlogopite will undergo deformation by diffusional creep does not appear to be controlled by oxygen diffusion.  相似文献   

4.
The elastic moduli of a synthetic single crystal of pyrope (Mg3Al2Si3O12) have been determined using a technique based on Brillouin scattering. These results are used in an evaluation of the effect of composition on the elastic properties of silicate garnet solid solution series (Mg, Fe, Mn, Ca)3 (Al, Fe, Cr)2 Si3O12. In the pyralspites (Mg FeMn aluminum garnets), for which a large amount of data is available, this analysis indicates that the bulk modulus K is independent of the Fe2+/Mg2+ ratio, which is similar to the behavior observed in olivines and pyroxenes. However, the shear modulus μ of the garnets increases by 10% from the Mg to the Fe end member, in contrast to the decrease of μ with Fe content which is observed in olivines and pyroxenes. This contrasting behavior is most probably related to the oxygen coordination of the cation site occupied by Mg2+ and Fe2+ in these different minerals.  相似文献   

5.
Inclusions of ferropericlase and former (Mg,Fe)(Si,Al)O3 perovskite in diamonds from Kankan, Guinea believed to originate in the lower mantle were studied using Mössbauer spectroscopy to determine Fe3+/ΣFe. Fe3+ concentration in the (Mg,Fe)(Si,Al)O3 inclusion is consistent with empirical relations relating Fe3+/ΣFe to Al concentration, supporting the inference that it crystallised in the perovskite structure at lower mantle conditions. In ferropericlase there is a nearly linear variation of trivalent cation abundance with monovalent cation abundance, suggesting a substitution of the form Na0.5M0.53+O (M=Fe3+, Cr3+, Al3+). Excess positive charge is likely balanced by cation vacancies, where their abundance is observed to increase with increasing iron concentration, consistent with high-pressure experiments. The abundance of cation vacancies is related to oxygen fugacity, where ferropericlase inclusions from Kankan and São Luiz (Brazil) are inferred to have formed at conditions more oxidising than Fe-(Mg,Fe)O equilibrium, but more reducing than Re-ReO2 equilibrium. Fe2+/Mg partition coefficients between (Mg,Fe)(Si,Al)O3 and ferropericlase were calculated for inclusions co-existing in the same diamond using Mössbauer data and empirical relations based on high-pressure experimental work. Most values are consistent with high-pressure experiments, suggesting that these inclusions equilibrated at lower mantle conditions. The measured ferropericlase Fe3+ concentrations are consistent with diamond formation in a region of redox gradients, possibly arising from the subduction of oxidised material into reduced lower mantle. Reduction of carbonate to form ferropericlase and diamond is consistent with a slight shift of Kankan δ13C values to isotopically heavy compositions compared to the worldwide dataset, and could supply the oxygen necessary to satisfy the high Fe3+ concentration in (Mg,Fe)(Si,Al)O3 perovskite, as well as account for the high proportion of ferropericlase in the lower mantle paragenesis. The heterogeneity of lower mantle diamond sources indicates that the composition of lower mantle diamonds do not necessarily reflect those of the bulk mantle.  相似文献   

6.
Ten samples were recovered by the submersible “Cyana” submersible from two groups of hydrothermal vents located 2600 m deep along the East Pacific Rise at 13°N. The maximum measured temperature was 317°C and minimum pH 3.8. A systematic determination of major and trace elements has been carried out and mixing lines between a high-temperature component (HTC) and seawater are observed. The water chemistry of the HTC slightly differs for several elements at the two sites. This HTC is deprived of SO4 and Mg and is greatly enriched in most other species. Maximum concentrations are (in units per kg):Cl = 0.72mol; Br = 1.1mmol; Na = 0.55mol; K = 29mmol; Rb = 14 μmol; Ca = 52mmol; Sr = 170 μmol; Mn = 750 μmol; Fe = 1mmol; Al = 15 μmol; Si = 21mmol. For many elements, the magnitude of the anomaly relative to seawater does not compare with the results obtained from the Galapagos or East Pacific Rise 21°N. The enrichment of cations relative to seawater is likely related to the huge Cl excess through charge balance. TheBr/Cl ratio is close to that for seawater. However, it is not clear whether the Cl excess is due to gas release or basalt hydration (formation of amphibole chlorite or epidote).P-T dependence of SiO2 solubility suggests that water-rock interaction last occurred at a depth in excess of 1 km below the sea floor. A mixing line of87Sr/86Sr vs. Mg/Sr demonstrates that the HTCs have a nearly identical87Sr/86Sr ratio of 0.7041 for both sites. A water/rock ratio of about 5 is inferred, which differs from the 1.5 value obtained at 21°N.  相似文献   

7.
Major and trace elements have been determined in monzonoritic rocks (hypersthene-monzodiorite or jotunite) from two intrusions belonging to the South Rogaland anorthositic complex (Norway). The rare-earth abundance pattern reveals no Eu anomaly, or only a very small one. This fact together with field observations suggest that these rocks represent the parental magma of the anorthositic suite. High Ti and P abundances, low Si content, high Fe/Mg and K2O/SiO2 ratios are characteristics of the major element geochemistry. Absolute amounts of some trace elements abundances vary distinctly between the two intrusions. K/Rb ratios as high as 1700 are observed. Partial fusion of upper mantle kaersutite is proposed as a possible mechanism of magma generation. Partition coefficients between plagioclase phenocrysts and liquid are determined.  相似文献   

8.
Dissolved and particulate Mn and Fe in the nearshore waters were determined at 27 stations along the west coast of Taiwan during 19-23 November 2004. The latitudinal distributions of Mn and Fe were very similar; however, the concentration in the dissolved phase was lower, whereas that in the particulate phase was higher in the northern regime. The higher percentage of Fe than Mn that was associated with particles resulted in a two-order of magnitude higher particle-water partition coefficient for Fe, Kd(Fe), than that for Mn, Kd(Mn). The removal fluxes of Mn and Fe could be estimated by multiplying the particulate 234Th removal flux with the Mn/234Th and Fe/234Th ratios in suspended particles, which ranged from 0.1 to 3.8 mmol m−2 d−1 for Mn, and from 3.4 to 194.5 mmol m−2 d−1 for Fe. Residence times ranged from 1 to 20 days for Mn and Fe were estimated in the nearshore.  相似文献   

9.
An attempt to indicate the sources and pathways of selected chemical substances in precipitation over central Bohemia was accomplished with help of bulk samples, collected in a forested rural landscape approx. 30 km SE from Prague, capital of the Czech Republic. Samples have been collected monthly throughout the 1990s. They were analyzed to determine the concentration of selected major cations and anions (Na+, K+, Ca2+, Mg2+, NH4 +, SO4 2-, NO3 -, Cl-), as well as several minor and trace elements (Al, As, Be, Cd, Cu, Fe, Mn, Pb, Sr, Zn, F-).Set of the bulk samples shows strong mutual correlation of the main acidifiers - compounds of N, S (and F). Good correlation occurs also at the typical lithogenic elements Al, K, Na, Ca, Mg, Sr, and the typical elements originating from the flue gases of the combustion chambers burning low quality brown coal - As, (Be), Cd, Cu, Pb, and Zn. The only strong correlation of Cl with Na (and Mg) indicates that majority of these elements originates from the oceanic spray. The content of pollutants in precipitation depends on the air masses types and on the rout of their approach to the sampling site. The typing of synoptic situations was employed for the determination of the air masses types and routs and of the corresponding fronts and precipitation fields.  相似文献   

10.
Alteration of the oceanic crust during hydrothermal circulation of seawater produces fluxes of K, Rb and Cs between these reservoirs which are significant compared to the river input of these elements. The ocean crust U flux, on the other hand, is probably not significant. The upper crust, altered at low temperature, is a sink for all of these elements (as shown by direct analysis of upper crustal materials). The lower crust is a source for K, Rb, and Cs, based on the observation that high-temperature fluids exiting the crust as “host springs” are enhanced over seawater in K, Rb and Cs concentration. While the sign of the hot spring fluxes may be correct, the absolute magnitudes cannot be, as the calculated yearly hot spring flux of Rb and Cs significantly exceeds the total Rb and Cs inventory of newly formed unaltered crust. By modelling the crust as a melt/cumulate combination, we show that the crust as a whole is a sink for K, Rb, Cs, and probably U, with yearly fluxes of1.1 × 1013, 2.6 ×1010, 6.0 × 108 and 1.0 × 109g, respectively (com to yearly river dissolved fluxes of7.4 × 1013, 3.5 × 1010, 6.4 × 108and1.0 × 1010g, respectively). The alteratio oceanic crust appears capable of quantitatively balancing the river inputs of Rb and Cs. For K, an additional sink comprising~ 85% of the river input is necessary. Because this missing K sink cannot be arbitrarily manipulated without destroying the Rb and Cs balances, a sink with K/Rb higher than the continental crust is required, and may possible be found in the sediments of the continental shelves.  相似文献   

11.
Multivariate analysis methods have been applied to studying variations in the concentrations of Ag, Al, As, B, Ba, Br, Ca, Cd, Co, Cr, Cs, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, P, Pb, Rb, S, Sb, Si, Sn, Sr, Th, Tl, U, V, Zn, Cl?, NO 3 ? , SO 4 2? as components of precipitation at 11 rural stations under project “Ecogeochemistry of Barents Region”. Hierarchic factor analysis revealed the structure and space-time distribution of seven first-order factors and two second-order factors. The combinations of ingredients that determine the composition of first-order factors characterize the sources of precipitation composition, which have been found to be specific and volatile products of fuel oil and coal combustion, marine and earth aerosols, and biogenic processes. Second-order factors showed two independent sets of components, which are typical of the chemistry of precipitation at the examined stations in winter and summer. Step-by-step discriminant and cluster analysis made it possible to classify the observational stations by precipitation chemistry and demonstrate the extent of difference between them.  相似文献   

12.
Volume measurements for magnesiowüstite (Mg0.6Fe0.4)O, were carried out up to pressures of 10.1 GPa in the temperature range 300–1273 K, using energy-dispersive synchrotron X-ray diffraction. These data allow reliable determination of the temperature dependence of the bulk modulus and good constraint on the thermal expansitivity at ambient pressure which was previously not known for magnesiowüstite. From these data, thermal and elastic parameters were derived from various approaches based on the Birch–Murnaghan equation of state (EOS) and on the relevant thermodynamic relations. The results from three different equations of state are remarkably consistent. With (∂KT/∂P)T fixed at 4, we obtained K0=158(2) GPa, (∂KT/∂T)P=−0.029(3) GPa K−1, (∂KT/∂T)V=−3.9(±2.3)×10−3 GPa K−1, and αT=3.45(18)×10−5+1.14(28)×10−8T. The K0, (∂KT/∂T)P, and (∂KT/∂T)V values are in agreement with those of Fei et al. (1992) and are similar to previously determined values for MgO. The zero pressure thermal expansitivity of (Mg0.6Fe0.4)O is found to be similar to that for MgO (Suzuki, 1975). These results indicate that, for the compositional range x=0–0.4 in (Mg1−xFex)O, the thermal and elastic properties of magnesiowüstite exhibit a dependence on the iron content that is negligibly small, within uncertainties of the experiments. They are consequently insensitive to the Fe–Mg partitioning between (Mg, Fe)SiO3 perovskite and magnesiowüstite when applied to compositional models of the lower mantle. With the assumption that (Mg0.6Fe0.4)O is a Debye-like solid, a modified equation of heat capacity at constant pressure is proposed and thermodynamic properties of geophysically importance are calculated and tabulated at high temperatures.  相似文献   

13.
《Marine pollution bulletin》2009,58(6-12):807-815
Concentrations of 19 trace elements (V, Cr, Mn, Fe, Co, Cu, Zn, Se, Rb, Sr, Mo, Ag, Cd, Sb, Cs, Ba, Tl, Hg, and Pb) were determined in the liver of the striped dolphins (Stenella coeruleoalba) collected around Japan during 1977–1982 to examine the sex difference, age dependence, and interrelationships among trace elements. Tissue distribution of trace elements was also investigated in one adult and one fetus specimens. Generally, concentrations of Se, Sr, Ag, Cd, Cs, Ba, Hg, and Pb were higher in the tissues of adult than those of fetus, whereas the opposite trend was observed for Cr and Tl. There were no significant sex differences in the trace element levels in the liver. Significant positive correlations between age (0–26.5 years) and hepatic concentrations were found for Ag, Se, Hg, V, Fe, Pb, and Sr, suggesting their age-dependent accumulation in the liver. In contrast, hepatic concentrations of Mn and Zn decreased with age. Significant positive relationships were observed between Se, and Hg, Ag, V, Fe, and Sr in the liver.  相似文献   

14.
Production rates of22Na (T1/2 = 2.6years) from aluminium by the action of cosmic rays are measured at the Mont Blanc (altitude 4600 m), the Aiguille du Midi (3840 m), and the Col du Lautaret (2070 m). They are2.3 ± 0.5,1.8 ± 0.3,and0.77 ± 0.18 atoms min?1 kg?1, respectively, in good agreement with the calculated production rates, 2.4, 1.7 and 0.6 atoms min?1 kg?1, respectively, at the three stations.Production rates of24Na (T1/2 = 15hours) from aluminium and magnesium are also measured at the Aiguille du Midi; the observed rates of3.4 ± 0.4and6.0 ± 1.7 atoms min?1 kg?1, respectively, agree well with the theoretically expected rates of 3.7 and 5.6 atoms min?1 kg?1.The production rates of3H,7Be,10Be,14C,22Na,26Al,36Cl,37Ar,39Ar,53Mn,54Mn, and55Fe in terrestrial rocks by the action of cosmic rays are calculated in order to show the possibility of applying the measurements of these cosmogenic radionuclides to the earth science.  相似文献   

15.
K-Ar ages have been determined for sulfide minerals for the first time. The occurrence of adequate amounts of potassium-bearing sulfides with ideal compositions K3Fe10S14 (~10 wt.% K) and KFe2S3 (~16 wt.% K) in samples from a mafic alkalic diatreme at Coyote Peak, California, prompted an attempt to date these materials. K3Fe10S14, a massive mineral with conchoidal fracture, gives an age of 29.4 ± 0.5m.y.(40Ar/39Ar), indistinguishable from the 28.3 ± 0.4m.y.(40Ar/39Ar) and 30.2 ± 1.0m.y.8 (conventional K-Ar) ages obtained for associated phlogopite (8.7 wt.% K). KFe2S3, a bladed, fibrous sulfide, gives a younger age, 26.5 ± 0.5m.y.(40Ar/39Ar), presumably owing to Ar loss.  相似文献   

16.
The most abundant mineral on Earth has a perovskite crystal structure and a chemistry that is dominated by MgSiO3 with the next most abundant cations probably being aluminum and ferric iron. The dearth of experimental elasticity data for this chemically complex mineral limits our ability to calculate model seismic velocities for the lower mantle. We have calculated the single crystal elastic moduli (cij) for (Mg, Fe3 +)(Si, Al)O3 perovskite using density functional theory in order to investigate the effect of chemical variations and spin state transitions of the Fe3+ ions. Considering the favored coupled substitution of Mg2+-Si4 + by Fe3+-Al3+, we find that the effect of ferric iron on seismic properties is comparable with the same amount of ferrous iron. Ferric iron lowers the elastic moduli relative to the Al charge-coupled substitution. Substitution of Fe3+ for Al3+, giving rise to an Fe/Mg ratio of 6%, causes 1.8% lower longitudinal velocity and 2.5% lower shear velocity at ambient pressure and 1.1% lower longitudinal velocity and 1.8% lower shear velocity at 142 GPa. The spin state of the iron for this composition has a relatively small effect (< 0.5% variation) on both bulk modulus and shear modulus.  相似文献   

17.
Data for the diffusion of cations in pyroxenes are relevant to a variety of sub-solidus processes including order-disorder and exsolution. Similar data must also be available if the reliability of geobarometers and geothermometers involving pyroxenes is to be assessed. Two types of diffusion experiment have been performed to determine cation diffusion rates in pyroxenes: (1) interdiffusion between single crystals of diopside and polycrystalline sinters enriched in Al and Fe, and (2) interdiffusion between single crystals of diopside and a glass of the same composition which was isotopically enriched in26Mg and43Ca. Following high-temperature annealing for periods up to several hundred hours, analysis of the diffusion couples, using an electron microprobe and an ion microprobe respectively, failed to show any measurable diffusion profiles. From these “null result” experiments the diffusion coefficients (D) for Al and Fe in diopside are estimated to be less than4×10?14cm2s?1 at 1200°C, and values ofD for Ca and Mg in diopside are estimated to be less than7 × 10?14cm2s?1 at 1250°C. These rates are significantly slower than published tracer-type diffusion data for Ca and Al.A review of studies of order-disorder, microstructural coarsening, and diffusion in pyroxenes suggest that activation energies for cation exchange are typically in excess of 60 kcal mol?1. Transport rates will be assisted, and activation energies lowered by sample non-stoichiometry, inhomogeneities, high dislocation densities and the presence of water.The collective data for Al, Mg and Ca diffusion in diopside indicate diffusion coefficients? 10?15cm2s?1 at 1200°C. A comparison with data for diffusion in garnet, olivine and spinel suggests that pyroxenes may have the highest blocking temperatures.  相似文献   

18.
We determined concentrations of 23 trace elements (TEs), and stable carbon and nitrogen isotope (δ13C and δ15N) signatures in barramundi (Lates calcarifer) specimens collected along the coast of Vietnam in the Northern (NCZ), Central (CCZ) and Southern (SCZ) zones in the period 2007–2010. A combination of δ13C and δ15N signatures provided insight into ontogenetic shifts in barramundi foraging choices. There were clear zone-dependent differences in Mn, As, Sr and Tl concentrations; levels of Tl were highest in the NCZ, As in the CCZ, and Mn and Sr in the SCZ. Lowest concentrations of Rb occurred in the NCZ, Bi was lowest in the CCZ, and Cd and Cs were lowest in the SCZ. δ15N values significantly increased with increasing Zn, Se, Sn and Cs. Concentrations of TEs in barramundi from Vietnam were below worldwide guidelines for human consumption.  相似文献   

19.
40Ar/39Ar analyses have been made on phlogopite-bearing peridotite nodules from Bultfontein and phlogopite nodules from Du Toitspan, Kimberley area, South Africa. Neither definite plateau nor isochron age could be obtained due to the occurrence of an excess40Ar in phlogopite. However, the extrusion age of a phlogopite nodule from Du Toitspan has been estimated to be about 86 m.y. from the combination of the youngest40Ar/39Ar age in the intermediate temperature fraction with Rb/Sr age data reported for this area.Excess40Ar correlates with K-derived39Ar in some phlogopites suggesting that it is trapped in K- or K-similar sites and has been incorporated during phlogopite formation.The occurrence of large amounts of excess40Ar in phlogopite suggests that it was not formed at a shallow depth.  相似文献   

20.
87Sr/86Sr and143Nd/144Nd ratios, REE and selected minor and trace elements are presented and compared for present-day volcanic rocks in the Scotia Sea.Tholeiitic basalts from the South Sandwich Islands show widely ranging contents of some lithophile elements, e.g. K2O (0.09–0.55%) and Rb (1.55–14.2 ppm), but fairly constant Na2O and Sr. Total REE contents range from about 4–20 times chondritic abundances with significant light-REE depletion and both positive and negative Eu anomalies. The variations in minor and trace element abundances are consistent with low-pressure fractional crystallization of plagioclase and clinopyroxene but only minor amounts of olivine. The87Sr/86Sr and143Nd/144Nd ratios of the parental magmas are thought be 0.7038–0.7039 and 0.51301–0.51314 respectively, and indicate derivation of at least some87Sr from subducted ocean crust.The back-arc tholeiites in the Scotia Sea have lower87Sr/86Sr ratios (0.7028–0.7033), similar143Nd/144Nd ratios (0.51305) and are variably light-REE-enriched(CeN/YbN= 1.0–1.6). Total REE contents are comparable to those of the South Sandwich Islands tholeiites.  相似文献   

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