An electrochemical study of Ni²⁺, Co²⁺, and Zn²⁺ ions in melts of composition CaMgSi₂O₆     

Krystyna W. Semkow  Ronald A. Rizzo  Larry A. Haskin  David J. Lindstrom 《Geochimica et cosmochimica acta》1982,46(10):1879-1889

Cyclic voltammetry has been done for Ni²⁺, Co²⁺, and Zn²⁺ in melts of diopside composition in the temperature range 1425 to 1575°C. Voltammetric curves for all three ions excellently match theoretical curves for uncomplicated, reversible charge transfer at the Pt electrode. This implies that the neutral metal atoms remain dissolved in the melt. The reference electrode is a form of oxygen electrode. Relative to that reference assigned a reduction potential of 0.00 volt, the values of standard reduction potential for the ions are $\text{E}{}^1\text{(}\text{Ni}{}^{\mathrm{2+}}\text{Ni}{}^0\text{,}\text{diopside}\text{, 1500°C) = ?0.32 ± .01}\text{V}$, $\text{E}{}^1\text{(}\text{Co}{}^{\mathrm{2+}}\text{Co}{}^0\text{,}\text{diopside}\text{, 1500°C) = ?0.45 ± .02}\text{V}$, and $\text{E}{}^1\text{(}\text{Zn}{}^{\mathrm{2+}}\text{Zn}{}^0\text{,}\text{diopside}\text{, 1500°C) = ?0.53 ± .01}\text{V}$. The electrode reactions are rapid, with first order rate constants of the order of 10^?2 cm/sec. Diffusion coefficients were found to be 2.6 × 10^?6 cm²/sec for Ni²⁺, 3.4 × 10^?6 cm²/sec for Co²⁺, and 3.8 × 10^?6 cm²/sec for Zn²⁺ at 1500°C. The value of $\text{E1}$ ($\text{Ni}{}^{\mathrm{2+}}\text{Ni}{}^0$, diopside) is a linear function of temperature over the range studied, with values of ?0.35 V at 1425°C and ?0.29 V at 1575°C. At constant temperature the value of $\text{E}{}^1\text{(}\text{Ni}{}^{\mathrm{2+}}\text{Ni}{}^0\text{, 1525°C}$) was not observed to vary with composition over the range CaO · MgO · 2SiO₂ to CaO·MgO·3SiO₂ or from 1.67 CaO·0.33MgO·2SiO₂ to 0.5 CaO·1.5MgO·2SiO₂. The value for the diffusion coefficient for Ni²⁺ decreased by an order of magnitude at 1525°C over the compositional range CaO · MgO · 1.25SiO₂ to CaO · MgO · 3SiO₂. This is consistent with a mechanism by which Ni²⁺ ions diffuse by moving from one octahedral coordination site to another in the melt, with the same Ni²⁺ species discharging at the cathode regardless of the SiO₂ concentration in the melt.  相似文献   

Complex formation in the ternary system Mg(II)-CO₂-H₂O     

Walter Riesen  Heinz Gamsjäger  Paul W. Schindler 《Geochimica et cosmochimica acta》1977,41(9):1193-1200

The carbonato and hydrogencarbonato complexes of Mg²⁺ were investigated at 25 and 50° in solutions of the constant ClO₄^? molality (3 M) consisting preponderantly of NaClO₄. The experimental data could be explained assuming the following equilibria: Mg²⁺ + CO_2B + H₂O ag MgHCO⁺₃ + H⁺, $\text{log}{}^1\text{β}{}_1\text{= ?7.64}{}_4\text{± 0.01}{}_7\text{(25°), ?7.46}{}_2\text{± 0.01}{}_1\text{(50°)}$, Mg²⁺ + 2 CO_2g + 2 H₂Oag Mg(HCO₃)⁰₂ ± 2 H⁺, $\text{log}{}^1\text{β}{}_2\text{= ?15.00 ± 0.14 (25°)}$, ?15.37 ± 0.39 (50°), Mg²⁺ + CO_2g + H₂Oag MgCO⁰₃ + 2 H⁺, $\text{log}{}^1\text{k}{}_1\text{= ?15.64 ± 0.06 (25°)}$,?15.23 ± 0.02 (50°), with the assumption γ_MgCO3⁰ = γ_Mg(HCO3)⁰2, ΔG⁰(I = 0) for the reaction MgCO⁰₃ + CO_2g + H₂O = Mg(HCO₃)⁰₂ was estimated to be ?3.9₁ ± 0.8₆ and 0.6 ± 2.4 kJ/mol at 25 and 50°C, respectively. The abundance of carbonate linked Mg(II) species in fresh water systems is discussed.  相似文献   

The system pargasite-H₂O-CO₂: a model for melting of a hydrous mineral with a mixed-volatile fluid—I. Experimental results to 8 kbar     

J.R Holloway 《Geochimica et cosmochimica acta》1973,37(3):651-666

The stability of the amphibole pargasite [NaCa₂Mg₄Al(Al₂Si₆))O₂₂(OH)₂] in the melting range has been determined at total pressures (P) of 1.2 to 8 kbar. The activity of H₂O was controlled independently of P by using mixtures of H₂O + CO₂ in the fluid phase. The mole fraction of H₂O in the fluid ($\text{X}{}_{\mathrm{H}}{}_2\text{O}{}^{\mathrm{1fl}}$) ranged from 1.0 to 0.2.At P < 4 kbar the stability temperature (T) of pargasite decreases with decreasing $\text{X}{}_{\mathrm{H}}{}_2\text{O}{}^{\mathrm{1fl}}$ at constant P. Above P ? 4 kbar stability T increases as $\text{X}{}_{\mathrm{H}}{}_2\text{O}{}^{\mathrm{1fl}}$ is decreased below one, passes through a T maximum and then decreases with a further decrease in $\text{X}{}_{\mathrm{H}}{}_2\text{O}{}^{\mathrm{1fl}}$. This behavior is due to a decrease in the H₂O content of the silicate liquid as $\text{X}{}_{\mathrm{H}}{}_2\text{O}{}^{\mathrm{1fl}}$ decreases. The magnitude of the T maximum increases from about 10°C (relative to the stability T for $\text{X}{}_{\mathrm{H}}{}_2\text{O}{}^{\mathrm{1fl}}\text{= 1}$) at P = 5 kbar to about 30°C at P = 8 kbar, and the position of the maximum shifts from $\text{X}{}_{\mathrm{H}}{}_2\text{O}{}^{\mathrm{1fl}}\text{? 0.6}$ at P = 5 kbar to $\text{X}{}_{\mathrm{H}}{}_2\text{O}{}^{\mathrm{1fl}}\text{? 0.4}$ at P = 8 kbar.The H₂O content of liquid coexisting with pargasite has been estimated as a function of at 5 and 8 kbar P, and can be used to estimate the H₂O content of magmas. Because pargasite is stable at low values of $\text{X}{}_{\mathrm{H}}{}_2\text{O}{}^{\mathrm{1fl}}$ at high P and T, hornblende can be an important phase in igneous processes even at relatively low H₂O fugacities.  相似文献   

The solubilities of calcite,aragonite and vaterite in CO₂-H₂O solutions between 0 and 90°C,and an evaluation of the aqueous model for the system CaCO₃-CO₂-H₂O     

L.Niel Plummer  Eurybiades Busenberg 《Geochimica et cosmochimica acta》1982,46(6):1011-1040

Calculations based on approximately 350 new measurements (Ca_T-PCO₂) of the solubilities of calcite, aragonite and vaterite in CO₂-H₂O solutions between 0 and 90°C indicate the following values for the log of the equilibrium constants K_C, K_A, and K_V respectively, for the reaction CaCO₃(s) = Ca²⁺ + CO^2?₃: $\text{Log K}{}_{\mathrm{C}}\text{= ?171.9065 ? 0.077993T +}\text{2839.319}\text{T}\text{+ 71.595 log T}$$\text{Log K}{}_{\mathrm{A}}\text{= ?171.9773 ? 0.077993T +}\text{2903.293}\text{T}\text{+71.595 log T}$$\text{Log K}{}_{\mathrm{V}}\text{= ?172.1295 ? 0.077993T +}\text{3074.688}\text{T}\text{+ 71.595 log T}$ where T is in ^oK. At 25°C the logarithms of the equilibrium constants are ?8.480 ± 0.020, ?8.336 ± 0.020 and ?7.913 ± 0.020 for calcite, aragonite and vaterite, respectively.The equilibrium constants are internally consistent with an aqueous model that includes the CaHCO⁺₃ and CaCO⁰₃ ion pairs, revised analytical expressions for CO₂-H₂O equilibria, and extended Debye-Hückel individual ion activity coefficients. Using this aqueous model, the equilibrium constant of aragonite shows no PCO₂-dependence if the CaHCO⁺₃ association constant is between 0 and 90°C, corresponding to the value logK_Cahco⁺3 = 1.11 ± 0.07 at 25°C. The CaCO⁰₃ association constant was measured potentiometrically to be between 5 and 80°C, yielding logK_CaCO⁰3 = 3.22 ± 0.14 at 25°C.The CO₂-H₂O equilibria have been critically evaluated and new empirical expressions for the temperature dependence of K_H, K₁ and K₂ are $\text{log K}{}_{\mathrm{H}}\text{= 108.3865 + 0.01985076T ?}\text{6919.53}\text{T}\text{? 40.45154 log T +}\text{669365.}\text{T}{}^2$, $\text{log K}{}_1\text{= ?356.3094 ? 0.06091964T +}\text{21834.37}\text{T}\text{+ 126.8339 log T —}\text{1684915.}\text{T}{}^2$ and logK₂ = ?107.8871 ? 0.03252849T + 5151.79/T + 38.92561 logT ? 563713.9/T² which may be used to at least 250°C. These expressions hold for 1 atm. total pressure between 0 and 100°C and follow the vapor pressure curve of water at higher temperatures.Extensive measurements of the pH of Ca-HCO₃ solutions at 25°C and 0.956 atm PCO₂ using different compositions of the reference electrode filling solution show that measured differences in pH are closely approximated by differences in liquid-junction potential as calculated by the Henderson equation. Liquid-junction corrected pH measurements agree with the calculated pH within 0.003-0.011 pH.Earlier arguments suggesting that the CaHCO⁺₃ ion pair should not be included in the CaCO₃-CO₂-H₂O aqueous model were based on less accurate calcite solubility data. The CaHCO⁺₃ ion pair must be included in the aqueous model to account for the observed PCO₂-dependence of aragonite solubility between 317 ppm CO₂ and 100% CO₂.Previous literature on the solubility of CaCO₃ polymorphs have been critically evaluated using the aqueous model and the results are compared.  相似文献   

Revised values for the Gibbs free energy of formation of [Al(OH)_{4 aq}⁻], diaspore,boehmite and bayerite at 298.15 K and 1 bar,the thermodynamic properties of kaolinite to 800 K and 1 bar,and the heats of solution of several gibbsite samples     

Bruce S. Hemingway  Richard A. Robie  James A. Kittrick 《Geochimica et cosmochimica acta》1978,42(10):1533-1543

Solution calorimetric measurements compared with solubility determinations from the literature for the same samples of gibbsite have provided a direct thermochemical cycle through which the Gibbs free energy of formation of [Al(OH)_{4 aq}^?] can be determined. The Gibbs free energy of formation of [Al(OH)_{4 aq}^?] at 298.15 K is ?1305 ± 1 kJ/mol. These heat-of-solution results show no significant difference in the thermodynamic properties of gibbsite particles in the range from 50 to 0.05 μm.The Gibbs free energies of formation at 298.15 K and 1 bar pressure of diaspore, boehmite and bayerite are ?9210 ± 5.0, ?918.4 ± 2.1 and ?1153 ± 2 kJ/mol based upon the Gibbs free energy of [A1(OH)_{4 aq}^?] calculated in this paper and the acceptance of ?1582.2 ± 1.3 and ?1154.9 ± 1.2 kJ/mol for the Gibbs free energy of formation of corundum and gibbsite, respectively.Values for the Gibbs free energy formation of [Al(OH)_{2 aq}⁺] and [AlO_{2 aq}^?] were also calculated as ?914.2 ± 2.1 and ?830.9 ± 2.1 kJ/mol, respectively. The use of [AlC_{2 aq}^?] as a chemical species is discouraged.A revised Gibbs free energy of formation for [H₄SiO_4aq⁰] was recalculated from calorimetric data yielding a value of ?1307.5 ± 1.7 kJ/mol which is in good agreement with the results obtained from several solubility studies.Smoothed values for the thermodynamic functions C_P⁰, ($\text{H}{}_{\mathrm{T}}{}^0\text{- H}{}_{298}{}^0\text{)}\text{T}$, $\text{(}\text{G}{}_{\mathrm{T}}{}^0\text{- H}{}_{298}{}^0\text{)}\text{T}$, S_T⁰ - S₀⁰, $\text{ΔH}{}_{\mathrm{?,298}}{}^0$ kaolinite are listed at integral temperatures between 298.15 and 800 K. The heat capacity of kaolinite at temperatures between 250 and 800 K may be calculated from the following equation: C_P⁰ = 1430.26 ? 0.78850 T + 3.0340 × 10^?4T² ?1.85158 × 10^?4T²$\text{1}\text{2}\text{+ 8.3341 × 10}{}^6\text{T}{}^{\mathrm{?2}}$.The thermodynamic properties of most of the geologically important Al-bearing phases have been referenced to the same reference state for Al, namely gibbsite.  相似文献   

Experimental hydrogen isotope studies—I. Systematics of hydrogen isotope fractionation in the systems epidote-H₂O,zoisite-H₂O and AlO(OH)-H₂O     

Colin M. Graham  Simon M.F. Sheppard  Timothy H.E. Heaton 《Geochimica et cosmochimica acta》1980,44(2):353-364

$\text{H}\text{D}$ Fractionation factors between epidote minerals and water, and between the AlO(OH) dimorphs boehmite and diaspore and water, have been determined between 150 and 650°C. Small water mineral ratios were used to minimise the effect of incongruent dissolution of epidote minerals. Waters were extracted and analysed directly by puncturing capsules under vacuum. Hydrogen diffusion effects were eliminated by using thick-walled capsules.$\text{H}\text{D}$ Exchange rates are very fast between epidote and water (and between boehmite and water), complete exchange taking only minutes above 450°C but several months at 250°C. Exchange between zoisite and water (and between diaspore and water) is very much slower, and an interpolation method was necessary to determine fractionation factors at 450 and below.For the temperature range 300–650°C, the $\text{H}\text{D}$ equilibrium fractionation factor (α^e) between epidote and water is independent of temperature and Fe content of the epidote, and is given by 1000 In α_epidote-H2O^e = ?35.9 ± 2.5, while below 300°C 1000 In , with a ‘cross-over’ estimated to occur at around 185°C. By contrast, zoisite-water fractionations fit the relationship 1000 In .All studied minerals have hydrogen bonding. Fractionations are consistent with the general relationship: the shorter the O-H -- O bridge, the more depleted is the mineral in D.On account of rapid exchange rates, natural epidotes probably acquired their H-isotope compositions at or below 200°C, where fractionations are near or above 0%.; this is in accord with the observation that natural epidotes tend to concentrate D relative to other coexisting hydrous minerals.  相似文献   

Mineral-solution equilibria—III. The system Na₂OAl₂O₃SiO₂H₂OHCl     

Robert K. Popp  John D. Frantz 《Geochimica et cosmochimica acta》1980,44(7):1029-1037

Chemical equilibrium between sodium-aluminum silicate minerals and chloride bearing fluid has been experimentally determined in the range 500–700°C at 1 kbar, using rapid-quench hydrothermal methods and two modifications of the Ag + AgCl acid buffer technique. The temperature dependence of the thermodynamic equilibrium constant (K) for the reaction $\text{NaAlSi}{}_3\text{O}{}_8\text{+ HCl}{}^{\mathrm{o}}\text{= NaCl}{}^{\mathrm{o}}\text{+}\text{1}\text{2Al}{}_2\text{SiO}{}_5\text{, +}\text{5}\text{2SiO}{}_2\text{+}\text{1}\text{2H}{}_2\text{O}$ Albite Andalusite Qtz. can be described by the following equation: log k = ?4.437 + 5205.6/T(K) The data from this study are consistent with experimental results reported by Montoya and Hemley (1975) for lower temperature equilibria defined by the assemblages albite + paragonite + quartz + fluid and paragonite + andalusite + quartz + fluid. Values of the equilibrium constants for the above reactions were used to estimate the difference in Gibbs free energy of formation between NaCl^o and HCl^o in the range 400–700°C and 1–2 kbar. Similar calculations using data from phase equilibrium studies reported in the literature were made to determine the difference in Gibbs free energy of formation between KCl^o and HCl^o. These data permit modelling of the chemical interaction between muscovite + kspar + paragonite + albite + quartz assemblages and chloride-bearing hydrothermal fluids.  相似文献   

Determination of the ⁸⁷Rb decay constant     

D.W. Davis  J. Gray  G.l. Gumming  H. Baadsgaard 《Geochimica et cosmochimica acta》1977,41(12):1745-1749

The decay constant ⁸⁷Rb has been redetermined by measuring the amount of radiogenic ⁸⁷Sr produced over a period of 19 years, in 20 g samples of purified RbClO₄, using isotope dilution techniques. The rubidium sample was spiked with ⁸⁴Sr and the nanogram quantities of strontium separated by coprecipitation with Ba(NO₃)₂. Analyses were carried out on a 25cm, 90° sector mass spectrometer equipped with a Spiraltron electron multiplier. Measurement of three independent ratios permitted continuous monitoring of the ion beam fractionation. The average of nine determinations gives a value for the decay constant of $\text{1.419(±0.012) × 10}{}^{\mathrm{?11}}\text{yr}{}^{\mathrm{?1}}\text{(2σ)}$. [$\text{τ}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{= 4.89(±0.04) × 10}{}^{10}\text{yr}$.]  相似文献   

Mineral-solution equilibria—I. An experimental study of complexing and thermodynamic properties of aqueous MgCl₂ in the system MgO-SiO₂-H₂O-HCl     

John D. Frantz  Robert K. Popp 《Geochimica et cosmochimica acta》1979,43(8):1223-1239

Speciation of aqueous magnesium in the system MgO-SiO₂-H₂O-HCl in supercritical aqueous fluids has been investigated using standard rapid-quench hydrothermal techniques and a modification of the Ag + AgCl buffer method (Frantz and Eugster, 1973. Am. J. Sci.267, 268–286). A concentric double-capsule charge was utilized. The outer gold capsule contained the assemblage talc + quartz + Ag + AgCl + H₂O-MgCl₂ fluid; the inner platinum capsule, Ag + AgCl + H₂O-HCl fluid. During the experiments, and thus $\text{?}{}_{\mathrm{HCl}}$ equilibrated between the two capsules. After quenching, measurement of the chloride concentration in the fluid in the inner capsule and total magnesium in the fluid in the outer capsule defines the concentrations of HCl and Mg that coexist with talc + quartz in the outer capsule. Changes in the measured molality of HCl as a function of the total magnesium concentration at constant P and T were used to identify the predominant species of magnesium in the hydrothermal fluid. Experimental results showed that at 2000 bar, MgCl°₂ is the predominant species above 550°C and Mg²⁺, below 400°C. Data at intermediate temperatures when combined with the dissociation constant for HCl were used to obtain the dissociation constant for MgCl°₂. The results of these experiments were combined with results from experiments using Ag + AgCl in conjunction with the oxygen buffer, hematite-magnetite, to obtain the equilibrium constant for the reaction $\text{1}\text{3}\text{Talc + 2HC1° H}{}_2\text{O MgCl°}{}_2\text{+}\text{4}\text{3}\text{Quartz +}\text{4}\text{3}\text{H}{}_2\text{O}$ from which the difference in Gibbs free energy of MgCl°₂ and HC1° was obtained as a function of temperature at 1000, 1500 and 2000 bar pressure, Solubility constants for brucite. forsterite, chrysotile, and talc were calculated.  相似文献   

Stability of ethylxanthate ion in neutral and weakly acidic media. Part 1: Influence of pH     

M. Maillot  J.-L. Cecile  R. Bloise 《International Journal of Mineral Processing》1984,13(3):193-210

Xanthates are used in the flotation of sulfide ores although their aqueous solutions are not stable under certain conditions. Their stability in acidic and weakly acidic aqueous solutions was therefore investigated, as these media are required for some processes.The peak absorbances of ethylxanthate ion and carbon disulfide were first determined in aqueous solution. The decomposition of ethylxanthate ion was analyzed by measuring variations in absorbance (at 301 nm) and pH with respect to time. A pH regulation system was then used while measuring variations in absorbance and productions of protons caused by xanthate decomposition.The results concerning xanthate half-lives show good agreement with the literature, but the kinetic results deviate substantially. The following relation was obtained for half-life: We established that ethylxanthate decomposition at pH 4 is a first order reaction with respect to ethylxanthate concentration, and postulating this order to the other pH values, the following kinetic relation was found: where v is the rate of decomposition (mol l^?1 min^?1), and [EtX^?]_∞ is the ethylxanthate concentration when the decomposition equilibria are reached (mol l^?1). The better concentration was found to obey the law:   相似文献   

Thermodynamics of brine-salt equilibria—I. The systems NaCl-KCl-MgCl₂-CaCl₂-H₂O and NaCl-MgSO₄-H₂O at 25°C     

James R. Wood 《Geochimica et cosmochimica acta》1975,39(8):1147-1163

A thermodynamic model for concentrated brines has been developed which is capable of predicting the solubilities of many of the common evaporite minerals in chloro-sulfate brines at 25°C and 1 atm. The model assumes that the behaviour of the mean stoichiometric ionic activity coefficient in mixtures of aqueous electrolytes can be described by the Scatchard deviation function and Harned's Rule. In solutions consisting of one salt and H₂O, the activity coefficient is described by the expression where $\text{a}\text{?}$ and B? salt specific parameters obtained from data regression. In a mixture of n electrolytes and H₂O, B? for the ith component is given by $\text{B}{}^{\mathrm{<mtext>i</mtext><mtext>?</mtext>}}{}_{\mathrm{i}}\text{=B}\text{i}\text{?}{}_{\mathrm{i}}\text{+σ α}{}_{\mathrm{ij}}\text{y}{}_{\mathrm{j}}$ where α_ij is a (constant) mixing parameter characterizing the interaction of the i and j components and y_j is the ionic strength fraction of the jth component. The activity of H₂O is obtained from a Gibbs-Duhem integration and does not require any additional parameters or assumptions. In this study, parameters have been obtained for the systems NaCl-KCl-MgCl₂-CaCl₂-H₂O and NaCl-MgSO₄-H₂O at 25°C and 1 atm. Computed solubility curves and solution compositions predicted for invariant points in these systems agree well with the experimental data. The model is flexible and easily extended to other systems and to higher temperatures.  相似文献   

Rates of reaction of pyrite and marcasite with ferric iron at pH 2     

C.L Wiersma  J.D Rimstidt 《Geochimica et cosmochimica acta》1984,48(1):85-92

The relative reactivities of pulverized samples (100–200 mesh) of 3 marcasite and 7 pyrite specimens from various sources were determined at 25°C and pH 2.0 in ferric chloride solutions with initial ferric iron concentrations of 10^?3 molal. The rate of the reaction: was determined by calculating the rate of reduction of aqueous ferric ion from measured oxidation-reduction potentials. The reaction follows the rate law: where m_Fe³⁺ is the molal concentration of uncomplexed ferric iron, k is the rate constant and $\text{A}\text{M}$ is the surface area of reacting solid to mass of solution ratio. The measured rate constants, k, range from 1.0 × 10^?4 to 2.7 × 10^?4 sec^?1 ± 5%, with lower-temperature/early diagenetic pyrite having the smallest rate constants, marcasite intermediate, and pyrite of higher-temperature hydrothermal and metamorphic origin having the greatest rate constants. Geologically, these small relative differences between the rate constants are not significant, so the fundamental reactivities of marcasite and pyrite are not appreciably different.The activation energy of the reaction for a hydrothermal pyrite in the temperature interval of 25 to 50°C is 92 kJ mol^?1. This relatively high activation energy indicates that a surface reaction controls the rate over this temperature range. The BET-measured specific surface area for lower-temperature/early diagenetic pyrite is an order of magnitude greater than that for pyrite of higher-temperature origin. Consequently, since the lower-temperature types have a much greater $\text{A}\text{M}$ ratio, they appear to be more reactive per unit mass than the higher temperature types.  相似文献   

Spallation production of ³He, ²¹Ne,and ³⁸Ar from target elements in the Bruderheim chondrite     

D.D Bogard  P.J Cressy 《Geochimica et cosmochimica acta》1973,37(3):527-546

The concentrations of noble gas isotopes of He, Ne and Ar have been measured in eight mineral separates of the Bruderheim chondrite. The cosmic-ray-produced nuclides ²¹Ne and ³⁸Ar were correlated by a computer least-squares fitting program with the elemental composition in each separate of potential targets for nuclear production yielding the following production equations: $\text{[}{}^{21}\text{Ne, 10}{}^{\mathrm{?8}}\text{cm}{}^3\text{/g] = k(0.45[Mg] + 0.085[Si] + 0.060[S] + 0.017[Ca] + 0.0044[Fe + Ni])}$; $\text{[}{}^{38}\text{Ar, 10}{}^{\mathrm{?8}}\text{cm}{}^3\text{/g] = k(2.6[K] + 0.37[Ca] + 0.08[Ti + Cr + Mn] + 0.021[Fe + Ni])}$ with elemental concentrations in weight per cent and k equal to the reciprocal of the cosmic-ray exposure age of Bruderheim. The P(S)/P(Cr + Mn + Fe + Ni) weight production ratio for ³He was determined to be 1.53; relative productions of ³He from O, Mg and Si and ²¹Ne from Al proved to be incalculable.  相似文献   

The ²¹Ne production rate in stony meteorites estimated from ¹⁰Be and other radionuclides     

R.K Moniot  T.H Kruse  C Tuniz  W Savin  G.S Hall  T Milazzo  D Pal  G.F Herzog 《Geochimica et cosmochimica acta》1983,47(11):1887-1895

The ¹⁰Be contents of 28 stony meteorites with known ²¹Ne contents range from 0.97 to 23 dpm/kg and give an average ²¹Ne production rate (P₂₁) of (0.28 ± 0.02) × 10⁸ cm³ STP/g-Myr for shielding conditions corresponding to ${}^{22}\text{Ne}{}^{21}\text{Ne}\text{= 1.114}$ in an H-chondrite. Our $\text{P}{}_{21}\text{(}{}^{10}\text{Be)}$ agrees with others' P₂₁ based on ²²Na, ⁸¹Kr and ⁵³Mn but not on ²⁶A1. Temporal variations in the cosmic ray flux do not explain the disagreement satisfactorily; major errors in the radionuclide half-lives are not indicated. The discrepancy seems rooted in the data selection and the difficulties of making accurate corrections for shielding, chemical composition and other sources of variability.  相似文献   

The effect of pressure on the solubility of minerals in water and seawater     

Frank J Millero 《Geochimica et cosmochimica acta》1982,46(1):11-22

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 ($\text{V}\text{?}$) and compressibilty ($\text{K}\text{?}$) in water and seawater have been tabulated for some ions from 0 to 50°C. The compressibility change is quite large (~10 × 10^?3 cm³ 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 K_sp versus P and molal volume data (Macdonald and North, 1974; North, 1974). Calculated values of $\text{K}{}^{\mathrm{P}}{}_{\mathrm{sp}}\text{K}{}^{\mathrm{o}}{}_{\mathrm{sp}}$ for the solubility of CaCO₃, SrSO₄ and CaF₂ 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   

Mineral-solution equilibria—IV. Solubilities and the thermodynamic properties of FeCl₂⁰ in the system Fe₂O₃-H₂-H₂O-HCl     

N.Z. Boctor  R.K. Popp  J.D. Frantz 《Geochimica et cosmochimica acta》1980,44(10):1509-1518

The solubility of hematite in chloride-bearing hydrothermal fluids was determined in the temperature range 400–600°C and at 1000 and 2000 bars using double-capsule, rapid-quench hydrothermal techniques and a modification of the Ag + AgCl buffer method (Frantz and Popp, 1979). The changes in the molalities of associated hydrogen chloride () as a function of the molality of total iron in the fluid at constant temperature and pressure were used to identify the predominant species of iron in the hydrothermal fluid. The molality of associated HCl varied from 0.01 to 0.15. Associated FeCl₂⁰ was found to be the most abundant species in equilibrium with hematite. Determination of Cl/Fe in the fluid in equilibrium with hematite yields values approximately equal to 2.0 suggesting that ferrous iron is the dominant oxidation state.The equilibrium constant for the reaction Fe₂O₃ + 4HCl⁰ + H₂ = 2FeCl₂⁰ + 3H₂O was calculated and used to estimate the difference in Gibbs free energy between FeCl₂⁰ and HCl⁰ in the temperature range 400–600°C at 1000 and 2000 bars pressure.  相似文献   

Oxygen and sulfur isotope equilibria in the BaSO4HSO4−H2O system from 110 to 350°C and applications     

Minoru Kusakabe  Brian W. Robinson 《Geochimica et cosmochimica acta》1977,41(8):1033-1040

Oxygen isotope exchange between BaSO₄ and H₂O from 110 to 350°C was studied using 1 m H₂SO₄-1 m NaCl and 1 m NaCl solutions to recrystallize the barite. The slow exchange rate (only 7% exchange after 1 yr at 110°C and 91% exchange after 22 days at 350°C in 1 m NaCl solution) prompted the use of the partial equilibrium technique. However, runs at 300 and 350°C were checked by complete exchange experiments. The temperature calibration curve for the isotope exchange is calculated giving most weight to the high temperature runs where the partial equilibrium technique can be tested. Oxygen isotope fractionation factors (α) in 1 m NaCl solution (110–350°C), assuming a value of 1.0407 for α_CO2H2O at 25°C, are: .These data, when corrected for ion hydration effects in solution (Truesdell, 1974), give the fractionation factors in pure water: .In the 1 m H₂SO₄-1 m NaCl runs, sulfur isotope fractionation between HSO^?₄ and BaSO₄ is less than the detection limit of 0.4%. A barite-sulfide geothermometer is obtained by combining HSO^?₄H₂S and sulfide-H₂S calibration data.Barite in the Derbyshire ore field, U.K., appears to have precipitated in isotopic equilibrium with water and sulfur in the ore fluid at temperatures less than 150°C. At the Tui Mine, New Zealand, the barite-water geothermometer indicates temperatures of late stage mineralization in the range 100–200°C. A temperature of 350 ± 20°C is obtained from the barite-pyrite geothermometer at the Yauricocha copper deposit, Peru, and oxygen isotope analyses of the barite are consistent with a magmatic origin for the ore fluids.  相似文献   

Theoretical prediction of phase relations among aqueous solutions and minerals: Salton Sea geothermal system     

Dennis K. Bird  Denis L. Norton 《Geochimica et cosmochimica acta》1981,45(9):1479-1494

  相似文献   

Helium accumulation in groundwater,I: An evaluation of sources and the continental flux of crustal ⁴He in the Great Artesian Basin,Australia     

T. Torgersen  W.B. Clarke 《Geochimica et cosmochimica acta》1985,49(5):1211-1218

The rate of accumulation of ⁴He in the groundwaters of the J-aquifer of the Great Artesian Basin, Australia has been determined using ¹⁴C and hydrologic ages. For groundwaters less than 50 Kyr in age, the ⁴He accumulation rate is 4.6 × 10^?12 HeAU (where ) in close agreement with in-situ production rate of ⁴He (3.95 × 10^?12 HeAU) based on U and Th concentrations of 1.7 and 6.1, respectively, of the sandstone. For groundwaters older than 100 Kyr, the rate of ⁴He accumulation is 2.91 × 10^?10 HeAU based on hydrologic ages; or 74 × the rate of in-situ production. The rate of ⁴He “production” due to weathering of the aquifer rock is calculated to be ~10^?16 HeAU, indicating that the weathering input of ⁴He is insignificant. If the groundwater of the GAB can be considered as a trap for the total crustal production of ⁴He, the rate of ⁴He accumulation under a steady-state flux is calculated to be 3.02 × 10^?10 HeAU, in agreement with the measured accumulation rate. It is concluded that over long times the ⁴He accumulation rate in groundwater aquifers may be controlled by the whole crust flux of ⁴He.  相似文献   

${}^3\text{He}{}^4\text{He}$ ratio,noble gas abundance and K-Ar dating of diamonds—An attempt to search for the records of early terrestrial history     

M. Ozima  S. Zashu  O. Nitoh 《Geochimica et cosmochimica acta》1983,47(12):2217-2224

The ${}^3\text{He}{}^4\text{He}$ ratios measured in 27 Southern Africa diamond stones, four from Premier Mine and the rest of unidentified origin, range from 4.2 × 10^?8 to 3.2 × 10^?4, with three stones above 1 × 10^?4. We conclude that the initial helium isotopic ratio (${}^3\text{He}{}^4\text{He)}{}_0$ in the earth was significantly higher than that of the planetary helium-A (${}^3\text{He}{}^4\text{He = 1.42 × 10}{}^{\mathrm{?4}}$), but close to the solar helium (${}^3\text{He}{}^4\text{He ? 4 × 10}{}^{\mathrm{?4}}$).The apparent K-Ar ages for the twelve diamonds of unidentified origin show enormously old age, indicating excess argon-40. ${}^3\text{He}{}^4\text{He}$ evolution in diamonds suggests that the diamonds with the high ${}^3\text{He}{}^4\text{He}$ ratio (>2 × 10^?4) may be as old as the earth.Noble gas elemental abundance in the diamonds relative to the air noble gas abundance shows monotonie decrease with a decreasing mass number.This paper discusses the implications of these observations on the early solar system and the origin of diamonds.  相似文献