Kiglapait geochemistry V: Strontium

The Kiglapait intrusion contains 330 ppm Sr and has $\text{Sr}\text{Ca}\text{= 5 × 10}{}^{\mathrm{?3}}$ and $\text{Rb}\text{Sr}\text{= 3 × 10}{}^{\mathrm{?3}}$, as determined by summation over the Layered Group of the intrusion. Wholerocks in the Lower Zone contain 403 F_L^0.141 ppm Sr, where F_L is the fraction of liquid remaining; Sr drops to 180 ppm at the peak of augite production (F_L = 0.11) and rises to a maximum of 430 ppm in the Upper Zone before decreasing to 172 ppm at the end of crystallization. Feldspars in the Lower Zone contain 532 F_L^0.090 ppm Sr, increasing to 680 ppm in the Upper Zone before decreasing to 310 ppm at the end. Clinopyroxenes contain 15 to 30 ppm Sr and have a mineral-melt distribution coefficient D = 0.06 except near the top of the intrusion where D = 0.10.The calculated feldspar-liquid distribution coefficient has an average value near 1.75 but shows four distinct trends when plotted against X_An of feldspar. The first two of these are strongly correlated with the modal augite content of the liquid, on average by the relation D = 1.4 + 0.02 Aug^L. The third (decreasing) trend is due to co-crystallization of apatite, and the fourth (increasing) trend can best be attributed to a triclinic-monoclinic symmetry change in the feldspar at An₂₆, 1030°C. The compound feldspar-liquid distribution coefficient K_D for $\text{Sr}\text{Ca}$ bears out these deductions in detail and yields ΔG_r for the Sr-Ca exchange ranging from nearly zero at the base of the Lower Zone to ?26 kJ/gramatom at the end of crystallization. The compound feldspar-liquid distribution coefficient K_D for $\text{Rb}\text{Sr}$ varies from 0.3 in the Lower Zone to 1.1 at the end of crystallization.The ratio $\text{Ca}{}^{\mathrm{F}}\text{Ca}{}^{\mathrm{L}}$ is about 1.45 for troctolitic liquids containing 5% augite, for which K_D (Sr-Ca) = 1.0 and D_Ca = D_Sr. For common basaltic liquids containing 20% augite, the Kiglapait data predict $\text{solSr}{}^{\mathrm{F}}\text{Sr}{}^{\mathrm{L}}\text{= 1.8}$, as commonly found elsewhere. The strong dependence of D_sr on augite content of the liquid illuminates the role of liquid composition and structure in determining the feldspar-liquid distribution coefficient. Conversely, a discontinuous change in the trend of D_Sr when apatite arrives shows that the effect is due to apatite crystallization itself, not to the continuous variation of the liquid as it becomes enriched in apatite component.     

Plagioclase—melt equilibria

The crystallization of plagioclase feldspar from magmatic liquid has been investigated experimentally under equilibrium conditions at 1 atm total pressure in the temperature range 1400-1095°C. Natural and synthetic melts of composition basalt to rhyolite were used, crystallizing plagioclase of composition An₈₉-An₃₂.The experimental results are analyzed initially in terms of elemental plagioclase/melt partition coefficients (D). D_Si is always less than unity and is invariant with temperature. D_A1 is always greater than unity and is relatively insensitive to temperature. D_Na is less than unity above 1200°C and is strongly dependent upon temperature. D_Ca is greater than unity below 1430°C and is strongly dependent upon temperature.Analysis of the temperature-dependence of equilibrium constants for plagioclase-melt formation and exchange reactions in which several mixing models for the melt are considered, leads to the conclusion that, with appropriate choice of melt-components, the melt-components mix quasi-ideally. At fixed temperature in the absence of H₂O, the equilibrium constant for the equilibrium of albite with the melt is insensitive to changes in melt-composition, and is insensitive to changes in pressure up to at least 10 kbars. As a consequence the composition of plagioclase crystallizing at known temperature and at low total pressure from a dry melt of known composition may be predicted []. However, the equilibrium constant is sensitive to changes in water pressure.The analysis further suggests that Na is intimately associated with tetrahedrally-coordinated Al in the melt, while Ca appears to be partitioned between at least two distinct melt-sites.     

Diffusion of ions in sea water and in deep-sea sediments

The tracer-diffusion coefficient of ions in water, D_j⁰, and in sea water, $\text{D}{}_{\mathrm{j}}{}^1$, differ by no more than zero to 8 per cent. When sea water diffuses into a dilute solution of water, in order to maintain the electro-neutrality, the average diffusion coefficients of major cations become greater but of major anions smaller than their respective $\text{D}{}_{\mathrm{j}}{}^1$ or D_j⁰ values. The tracer diffusion coefficients of ions in deep-sea sediments, D_j,sed., can be related to $\text{D}{}_{\mathrm{j}}{}^1$ by $\text{D}{}_{\mathrm{j,sed.}}\text{= D}{}_{\mathrm{j}}{}^1\text{·}\text{α}\text{θ}{}^2$, where θ is the tortuosity of the bulk sediment and a a constant close to one.     

Thermochemistry of the high structural state plagioclases

The enthalpies of solution of a suite of 19 high-structural state synthetic plagioclases were measured in a Pb₂B₂O₅ melt at 970 K. The samples were crystallized from analyzed glasses at 1200°C and 20 kbar pressure in a piston-cylinder apparatus. A number of runs were also made on Amelia albite and Amelia albite synthetically disordered at 1050–1080°C and one bar for one month and at 1200°C and 20 kbar for 10 hr. The component oxides of anorthite, CaO, Al₂O₃ and SiO₂, were remeasured.The ΔH of disorder of albite inferred in the present study from albite crystallized from glass is 3.23 kcal, which agrees with the 3.4 found by Holm and Kleppa (1968). It is not certain whether this value includes the ΔH of a reversible displacive transition to monoclinic symmetry, as suggested by Helgesonet al. (1978) for the Holm-Kleppa results. The enthalpy of solution value for albite accepted for the solid solution series is based on the heat-treated Amelia albite and is 2.86 kcal less than for untreated Amelia albite.The enthalpy of formation from the oxides at 970 K of synthetic anorthite is ?24.06 ± 0.31 kcal, significantly higher than the ?23.16 kcal found by Charluet al. (1978), and in good agreement with the value of ?23.89 ± 0.82 given by Robieet al. (1979), based on acid calorimetry.The excess enthalpy of mixing in high plagioclase can be represented by the expression, valid at 970 K: ΔH^ex(±0.16 kcal) = 6.7461 X_abX²_An + 2.0247 X_AnX²_Ab where X_Ab and X_An are, respectively, the mole fractions of NaAlSi₃O₈ and CaAl₂Si₂O₈. This ΔH^ex, together with the mixing entropy of Kerrick and Darken's (1975) Al-avoidance model, reproduces almost perfectly the free energy of mixing found by Orville (1972) in aqueous cation-exchange experiments at 700°C. It is likely that Al-avoidance is the significant stabilizing factor in the high plagioclase series, at least for X_An≥ 0.3. At high temperatures the plagioclases have nearly the free energies of ideal one-site solid solutions. The Al-avoidance model leads to the following Gibbs energy of mixing for the high plagioclase series: $\text{ΔG}{}^{\mathrm{mix}}\text{= ΔH}{}^{\mathrm{ex}}\text{+ RT X}{}_{\mathrm{Ab}}\text{ln[X}{}^2{}_{\mathrm{Ab}}\text{(2 ? X}{}_{\mathrm{Ab}}\text{)]+ X}{}_{\mathrm{An}}\text{ln}\text{[X}{}_{\mathrm{An}}\text{(1+X}{}_{\mathrm{An}}\text{)}{}^2\text{]}\text{4}$. The entropy and enthalpy of mixing should be very nearly independent of temperature because of the unlikelihood of excess heat capacity in the albite-anorthite join.     

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

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.     

Stability and phase equilibria of chloride and carbonate bearing scapolites at 750°C and 4000 bar

At 750°C and 4000 bar scapolite is stable relative to plagioclase + calcite over the range of plagioclase compositions An₅₃–An₈₃. The assemblage plagioclase + scapolite + calcite is stable relative to plagioclase + calcite over the ranges of plagioclase composition An₄₈-An₅₃ and An₈₃–An_91.5. When NaCl is present in the coexisting fluid the range of scapolite compositions stable relative to plagioclase increases. High mole fractions of NaCl in the fluid stabilize scapolite relative to plagioclases from An₂₅ to An₈₇ in the presence of excess calcite. Determination of the $\text{Cl}\text{(Cl + CO}{}_3\text{)}$ ratios of the synthetic scapolites shows that the range of stable scapolite compositions is significantly larger than heretofore proposed, and that even the chloride and carbonate bearing scapolites must be considered a four component solid solution. The K_D for the exchange of NaCl and CaCo₃ between coexisting scapolite, fluid and carbonate is given by the equation In $\text{K}{}_{\mathrm{D}}\text{= (?0.0028) [}\text{Al}\text{(Al + Si)}\text{]}{}^{\mathrm{?5.5580}}$. This equation implies that Cl-poor natural scapolites coexisted with fluids low in NaCl, and that regional occurrences of Cl-rich scapolites are likely to represent metamorphosed evaporite sequences.     

Density calculations for silicate liquids. I. Revised method for aluminosilicate compositions

Equations are developed for calculating the density of aluminosilicate liquids as a function of composition and temperature. The mean molar volume at reference temperature T_r, is given by $\text{V}{}_{\mathrm{r}}\text{= ∑X}{}_{\mathrm{i}}\text{V}\text{?}{}^{\mathrm{o}}{}_{\mathrm{i}}\text{+ X}{}_{\mathrm{A}}\text{V}\text{?}{}^{\mathrm{o}}{}_{\mathrm{A}}$, where the summation is taken over all oxide components except A1₂O₃, X stands for mole fraction, terms are constants derived independently from an analysis of volume-composition relations in alumina-free silicate liquids, and $\text{V}\text{?}{}^{\mathrm{o}}{}_{\mathrm{A}}$ is the composition-dependent apparent partial molar volume of Al₂O₃. The thermal expansion coefficient of aluminosilicate liquids is given by $\text{α = ∑X}{}_{\mathrm{i}}\text{}\text{?}\text{ga}{}_{\mathrm{i}}{}^{\mathrm{o}}\text{+ X}{}_{\mathrm{A}}\text{}\text{?}\text{ga}{}_{\mathrm{A}}{}^{\mathrm{o}}$, where $\text{}\text{?}\text{ga}{}_{\mathrm{i}}{}^{\mathrm{o}}$ terms are constants independent of temperature and composition, and $\text{}\text{?}\text{ga}{}^{\mathrm{o}}{}_{\mathrm{A}}$ is a composition-dependent term representing the effect of Al₂O₃ on the thermal expansion. Parameters necessary to calculate the volume of silicate liquids at any temperature T according to V(T) = V_rexp[α(T-T_r)], where T_r = 1400°C have been evaluated by least-square analysis of selected density measurements in aluminosilicate melts. Mean molar volumes of aluminosilicate liquids calculated according to the model equation conform to experimentally measured volumes with a root mean square difference of 0.28 $\text{cc}\text{mole}$ and an average absolute difference of 0.90% for 248 experimental observations. The compositional dependence of $\text{V}\text{?}{}^{\mathrm{o}}{}_{\mathrm{A}}$ is discussed in terms of several possible interpretations of the structural role of Al³⁺ in aluminosilicate melts.     

An experimental study of alkali metal distributions in feldspars and micas

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/cm² total pressure.Complete solid solution of RbMg₃AlSi₃O₁₀(OH)₂ in KMg₃AlSi₃O₁₀(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 AlSi₃O₈ in KAlSi₃O₈ has been found at all temperatures investigated.Distribution coefficients, expressed as $\text{K}{}_{\mathrm{d}}\text{= (}\text{Rb/K}\text{)}$ 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 $\text{K}{}_{\mathrm{D}}$ values and their approximate Rb end-member mole fraction ($\text{X}{}_{\mathrm{RM}}$) ranges of constancy are summarized as follows: (°C)$\text{T}$$\text{K}{}_{\mathrm{D}}{}^{\mathrm{Phlog/Vap.}}$$\text{X}{}_{\mathrm{RM}}$$\text{K}{}_{\mathrm{D}}{}^{\mathrm{Sandi/Vap.}}$$\text{X}{}_{\mathrm{rm}}$

     

9.

Distribution coefficients of Eu and Sr for plagioclase-liquid and clinopyroxene-liquid equilibria in oceanic ridge basalt: an experimental study     

Richard J. Williams 《Geochimica et cosmochimica acta》1974,38(9):1415-1433

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: log^PL_Sr = 7320/T ? 4.62logK^CPX_Sr = 18020/T ? 13.10. Similarly, the weight fraction distribution coefficients are given by the equations: logD^PL_Sr = 6570/T ? 4.30logD^CPX_Sr = 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.     

10.

Transfer and exchange equilibria in a portion of the pyroxene quadrilateral as deduced from natural and experimental data     

Ralph Kretz 《Geochimica et cosmochimica acta》1982,46(3):411-421

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:Fe²⁺ 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: $\text{> 1080°C: T =}\text{1000}\text{(0.468 + 0.246X}{}^{\mathrm{Cpx}}\text{? 0.123 ln (1–2 [Ca]))}$$\text{< 1080°C: T =}\text{1000}\text{(0.054 + 0.608X}{}^{\mathrm{Cpx}}\text{? 0.304 ln (1–2 [Ca]))}$, and the following equation for the temperature-dependence of the Mg-Fe distribution coefficient: $\text{T =}\text{1130}\text{(}\text{ln}\text{K}{}_{\mathrm{p}}\text{+ 0.505)}$, where T is absolute temperature, X is $\text{Fe}{}^{\mathrm{2+}}\text{(Mg + Fe}{}^{\mathrm{2+}}\text{))}$, [Ca] is $\text{Ca}\text{(Ca + Mg + Fe}{}^{\mathrm{2+}}\text{)}$ in Cpx, and K_D is the distribution coefficient, defined as $\text{X}{}^{\mathrm{Opx}}\text{/(1 ? X}{}^{\mathrm{Opx}}\text{) ÷ X}{}_{\mathrm{Cpx}}\text{/(1 ?}{}^{\mathrm{Cpx}}\text{)}$.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°.     

11.

On calculating activity coefficients and other excess functions from the intracrystalline exchange properties of a double-site phase     

John Geover 《Geochimica et cosmochimica acta》1974,38(10):1527-1548

For a phase at equilibrium in which two cation species are partitioned ideally between two sub-lattice sites, the excess functions of mixing (free energy, enthalpy and entropy) are directly related to the bulk composition of the phase and ΔG_E°(T, P), the standard-state intra- crystalline exchange free energy. If the phase is not at equilibrium internally, an additional ordering parameter is necessary to fix the excess free energy of mixing, G_mix^EX, unambiguously. Conversely, for any fixed G_mix^EX there exists an infinity of possible intracrystalline cation dis- tributions, only one of which is the equilibrium distribution for the specified temperature and pressure. As ideal intraphase cation ordering becomes more pronounced, G_mix^EX decreases. In response, the total free energy of mixing for the phase decreases progressively for non-end member compositions, approaching, at the limits of ordering, values appropriate for stabilizing compounds of intermediate composition.The model-dependent activity coefficient for component A in the phase, γ_A^T, can be calculated for any bulk composition, X_A^T, either from G_mix^EX directly or from more basic equations involving the interrelation of chemical potentials at equilibrium. A general form for γ_A^T is ln $\text{γ}{}_{\mathrm{A}}{}^{\mathrm{T}}\text{= 1n[}\text{2(X}{}_{\mathrm{A}}{}^{\mathrm{\alpha }}\text{X}{}_{\mathrm{A}}{}^{\mathrm{\beta }}\text{)}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{/}\text{(X}{}_{\mathrm{A}}{}^{\mathrm{\alpha }}\text{+X}{}_{\mathrm{A}}{}^{\mathrm{\beta }}\text{)}\text{]+Y}$, where Xj^κ denotes the mole fraction of species j in site κ. The first term on the right-hand side of this equation is the contribution to γ_A^T from ideal intracrystalline partitioning, and is common to the several theories lately presented to model intraphase cation partitioning. It can be shown rigorously that this term contributes to a negative deviation from ideality for the bulk phase. The second term is the contribution to the macroscopic activity coefficient from non-ideal intraphase partitioning, and is related to an enthalpy of mixing, H_mix^N in excess of that resulting from ideal inter-site cation ordering. While the expression represented by Y can take several functional forms, the additional enthalpy can be evaluated explicitly for specific non-ideal partitioning models from the relation $\text{H}{}_{\mathrm{mix}}{}^{\mathrm{N}}\text{= 2RT(1? X}{}_{\mathrm{A}}{}^{\mathrm{T}}\text{) ∝}\text{Y}\text{(1 ? X}{}_{\mathrm{A}}{}^{\mathrm{T}}\text{)}{}^2\text{dX}{}_{\mathrm{A}}{}^{\mathrm{T}}$.In those cases, G_mix^EX can also be determined exactly.     

12.

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

$\text{(}\text{K}{}^{\mathrm{P}}{}_{\mathrm{sp}}\text{K}{}^0{}_{\mathrm{sp}}\text{) +}\text{(?ΔVP + 0.5ΔKP}{}^2\text{)}\text{RT}$

where the volume (ΔV) and compressibility (ΔK) changes at atmospheric pressure (P = 0) are given by

$\text{ΔV =}\text{V}\text{?}\text{(M}{}^{\mathrm{+}}\text{, X}{}^{\mathrm{?}}\text{) ?}\text{V}\text{?}\text{[MX(s)]ΔK =}\text{K}\text{?}\text{(M}{}^{\mathrm{+}}\text{, X}{}^{\mathrm{?}}\text{) ?}\text{K}\text{?}\text{[MX(s)]}$

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.     

13.

Phase relations in the system NaCl-KCl-H2O II: Differential thermal analysis of the halite liquidus in the NaCl-H2O binary above 450°c     

W.D Gunter  I-Ming Chou  Sven Girsperger 《Geochimica et cosmochimica acta》1983,47(5):863-873

Thermal analysis of the halite liquidus in the system NaCl-H₂O has been conducted for NaCl mole fractions (X_NaCl) greater than 0.25 (i.e., > 50 wt. % NaCl) at pressures between 0.3 and 4.1 kb and temperatures greater than 450°C. The position of the liquidus was located by differential thermal analysis (DTA) of cooling scans only, as heating scans did not produce definitive DTA peaks. The dP/dT slope of the liquidus is positive and steep at high pressures, but at high X_NaCl, and pressures below 0.5 kb it appears to reverse slope and intersects the three-phase curve (liquid-halite-vapour) at a shallow angle. However, due to the complex nature of the DTA signal when P <- 0.5 kb, there is considerable doubt about exactly what event has been recorded in the experiments conducted at these low pressures.The solubility of halite can be expressed as a function of the mole-fractional-based activity of NaCl in the liquid phase (L) in temperature (T, °K) and pressure (P, bars) In $\text{α}{}_{\mathrm{NaCl(L.T.P)}}\text{=}\text{?19.884 ? 0.001275T ? 1388}\text{T + 3.2305 In (T) ? 0.07574PT}$ Our liquidus data (based on 10 compositions) above 500 bars for these brines were combined with this equation to generate activity coefficients of NaCl which were fit within their experimental uncertainties to the following one parameter Margules equation In $\text{γ}{}_{\mathrm{NaCl(L.T.P)}}\text{=}\text{(0.7268 ? 695.7}\text{T ? 0.1217PT)}\text{(1 ? X}{}_{\mathrm{NaCl}}\text{)}{}^2$. Concentrated solutions of NaCl show negative deviations from ideality which rapidly increase in magnitude with decreasing X_NaCl.     

14.

Strontium isotope geology of the South Mountain batholith,Nova Scotia     

D.B. Clarke  A.N. Halliday 《Geochimica et cosmochimica acta》1980,44(8):1045-1058

The South Mountain batholith of southwestern Nova Scotia is a large, peraluminous, granodiorite-granite complex which intrudes mainly greenschist facies metasediments of the Cambro-Ordovician Meguma Group. Using Rb-Sr isochrons constructed from whole rocks and mineral separates, the present study shows a variation in age and initial ratios of the intrusive phases of the batholith as follows: biotite granodiorite (371.8 ± 2.2 Ma, (${}^{87}\text{Sr}{}^{86}\text{Sr}\text{)}{}_{\mathrm{i}}$ ranges from 0.7076 ± 0.0003 to 0.7090 ± 0.0003, with the average = 0.7081); adamellite (364.3 ± 1.3 Ma, $\text{(}{}^{87}\text{Sr}{}^{86}\text{Sr}\text{)}{}_{\mathrm{i}}\text{= 0.70942 ± 35}$); porphyry (361.2 ± 1.4 Ma, $\text{(}{}^{87}\text{Sr}{}^{86}\text{Sr}\text{)}{}_{\mathrm{i}}\text{= 0.71021 ± 119}$); using λ⁸⁷Rb = 1.42 × 10^?11yr^?1.A suite of Meguma country rock samples showed a variation of ${}^{87}\text{Sr}{}^{86}\text{Sr}\text{= 0.7113?0.7177}$ at the time of intrusion of the batholith. A number of xenoliths of this material occurring in the marginal granodiorite had partially equilibrated isotopically with the granodiorite at a higher ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratio than elsewhere in the granodiorites. This evidence demonstrates that isotopic (and probably some accompanying bulk chemical) contamination by the Meguma rocks has been an important factor in determining the ultimate chemical composition and mineralogy of the South Mountain batholith.The $\text{(}{}^{87}\text{Sr}{}^{86}\text{Sr}\text{)}{}_{372}\text{= 0.7081}$ of the early granodiorites indicates that the parent magma of the South Mountain batholith was derived from a source unlike the Meguma Group. The precise nature of the source region cannot be determined by Rb-Sr work unless the degree of contamination with Megumalike material is known.     

15.

Geochemical modelling of basalts from DSDP Leg 65, East Pacific Rise,Gulf of California     

A.M. Kudo  S.E. Barker  K. Keil  Marvin H. Beeson 《Geochimica et cosmochimica acta》1982,46(12):2427-2434

Major and rare earth element (REE) data for basalts from Holes 483, 483B, and 485A of DSDP Leg 65, East Pacific Rise, mouth of the Gulf of California, support a simple fractional crystallization model for the genesis of rocks from this suite. The petrography and mineral chemistry (presented in detail elsewhere) provide no evidence for magma mixing, but rather a simple multistage cooling process. Based on its lowest TiO₂ content (0.88%), $\text{FeO}{}^1\text{MgO}$ ratio (0.95 with total Fe as FeO), and Mg# (100 $\text{Mg}\text{Mg + Fe}\text{″ = 70}$), sample 483-17-2-(78–83) has been selected as the most primitive primary magma of the samples analyzed. This is supported by the REE data which show this sample has the lowest total REE content, a $\text{La}\text{Sm}{}_{\mathrm{cn}}$ (chondrite-normalized) = 0.36, and $\text{Eu}\text{Sm}{}_{\mathrm{cn}}$ = 1.05. Because other samples analyzed have higher SiO₂, lower Mg#, and a negative Eu anomaly ($\text{Eu}\text{Sm}{}_{\mathrm{cn}}$ as low as 0.89), they are most likely derivative magmas. Wright-Doherty and trace element modelling support fractional crystallization of 14.1% plagioclase (An₈₈), 6.7% olivine (Fo₈₆), and 4.7% clinopyroxene (Wo₄₁En₄₉Fs₁₀) from 483-17-2-(78–83) to form the least differentiated sample with Mg# = 63. The $\text{La}\text{Sm}{}_{\mathrm{cn}}$ of this derivative magma is almost identical to the parent magma (0.35 to 0.36), but the other samples have higher $\text{La}\text{Sm}{}_{\mathrm{cn}}$ (0.45 to 0.51), more total REE, and lower Mg# (60 to 56). Both Wright-Doherty and trace element modelling indicate that the primary magma chosen cannot produce these more evolved samples. For the major elements, the TiO₂ and P₂O₅ are too low in the calculated versus the observed (1.38 to 1.90; 0.11 to 0.17, respectively, for example). Rayleigh fractionation calculates a lower $\text{La}\text{Sm}{}_{\mathrm{cn}}$ and requires about 60% crystal removal versus 40% for the Wright-Doherty. These more evolved samples must be derived from a parent magma different from the one selected here and, unfortunately, not sampled in this study. A magma formed by a smaller degree of partial melting with slightly more residual clinopyroxene left in the mantle than for sample 483-17-2-(78–83) is required.     

16.

Heat capacity measurements for cryolite (Na3AlF6) and reactions in the system NaFeAlSiOF     

《Geochimica et cosmochimica acta》1987,51(12):3087-3103

     

17.

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

     

18.

Distribution coefficients of major and trace elements; fractional crystallization in the alkali basalt series of Chaîne des Puys (Massif Central,France)   总被引：1，自引：0，他引：1  

Benoît Villemant  Henri Jaffrezic  Jean-Louis Joron  Michel Treuil 《Geochimica et cosmochimica acta》1981,45(11):1997-2016

Major and seventeen trace element distribution coefficients between main phenocrysts (olivine, clinopyroxene, amphibole, mica, feldspars and Fe-Ti oxides) and groundmass have been measured in the alkali basalt suite of Chaîne des Puys (Massif Central, France). The suite appears to be a well behaved crystal fractionation series. We pinpoint key elements whose behavior is closely related to the appearance or disappearance of specific crystal phases in the fractionation process. Ta, for instance, clearly indicates the role of hydrous silicates (amphiboles and micas). Distribution coefficients are shown to vary systematically along the differentiation trend. Significantly the hygromagmaphile tendency (Treuilet al., 1979) of U, Th, Ta and La is variable along the series.The mass balance equations,

$\text{D}{}^{\mathrm{i}}\text{=}\text{∑}\text{;}\text{x}{}_{\mathrm{j}}\text{D}{}_{\mathrm{j}}{}^{\mathrm{ii}}$

where Dⁱ and D_jⁱ are the bulk and mineral/liquid distribution coefficients respectively, and x_j the weight fractions of the fractionating phases, are solved by least square resolution of the overdetermined system, taking into account the analytical errors on data. The solution applied to the Chaîne des Puys suite leads to a coherent and quantitative model of the fractional crystallization process. The suite has apparently evolved in three stages. Each stage is characterized by constant bulk distribution coefficients and a specific mineral assemblage. Amphibole fractionation plays an important role in the early stages. Some intensive parameters (T, ? ?_O2, P_H2O) as well as f (weight fraction of residual liquid) are also estimated.     

19.

Investigations of an intrusive contact,northwest Nelson,New Zealand—II. Diffusion of radiogenic and excess ⁴⁰Ar in hornblende revealed by ${}^{40}\text{Ar}{}^{39}\text{Ar}$ age spectrum analysis     

T.Mark Harrison  Ian McDougall 《Geochimica et cosmochimica acta》1980,44(12):2005-2020

The Rameka Gabbro, emplaced 367 Ma ago, experienced a well documented reheating on intrusion of the Separation Point Batholith 114 Ma ago. ${}^{40}\text{Ar}{}^{39}\text{Ar}$ age spectrum analyses of hornblende from the Rameka Gabbro show diffusion gradients which provide information on the ⁴⁰Ar boundary concentration during reheating.Three samples of hornblende exhibit age spectra that conform to a model of ⁴⁰Ar loss by diffusion, implying a zero ⁴⁰Ar boundary concentration during heating. The calculated ⁴⁰Ar loss from these samples, together with a model of heat flow in the aureole, provide estimates of diffusion coefficients of ⁴⁰Ar in Mg-rich hornblende which correspond to an activation energy, E, of ~60 kcal-mol^?1 and a frequency factor. D₀, of ~ 10^?3 cm²-sec^?1. When combined with laboratory diffusion results, these data yield a well defined diffusion law (E = 63.3 ± 1.7 kcal-mol^?1, $\text{D}{}_0\text{= 0.022}{}^{\mathrm{+0.048}}{}_{\mathrm{?0.010}}\text{cm}{}^2\text{-}\text{sec}{}^{\mathrm{?1}}$).The age spectra of the eight other samples record steep gradients of excess ⁴⁰Ar over the first few percent of gas release. Although this effect causes high apparent conventional K-Ar ages, the plateau segments of many sampes still record the crystallization age of 367 ± 5 Ma. These measurements show that the excess ⁴⁰Ar phase developed locally in the intergranular regions of the gabbro, following intrusion of the batholith. on time scales that varied from 10⁴ to 10⁶years. The minimum average ${}^{40}\text{Ar}{}^{36}\text{Ar}$ ratio of this component was found to be 1300 ± 400. The partial pressure of Ar was at least 10^?2 bars in some places.A single ${}^{40}\text{Ar}{}^{39}\text{Ar}$ age spectrum analysis of plagioclase reveals a ‘saddle-shaped” release pattern with a minimum at 140 Ma.In conjunction with theoretical diffusion models and a diffusion law, ${}^{40}\text{Ar}{}^{39}\text{Ar}$ age spectrum analysis of hornblende that has experienced a post-crystallization heating can provide close estimates of the maximum temperature of the thermal event as well as both age of crystallization and reheating.     

20.

The use of the specific interaction model to estimate the partial molal volumes of electrolytes in seawater     

Frank J Millero 《Geochimica et cosmochimica acta》1977,41(2):215-223

The specific interaction model has been used to determine the partial molal volume of electrolytes in 0.725 m NaCl and 35‰ salinity seawater solutions at 25°C. The partial molal volumes of electrolytes (MX) were estimated at a given ionic strength (I) from

$\text{V}\text{(}\text{MX}\text{) =}\text{V}{}^0\text{(}\text{MX}\text{) +}\text{S}{}_{\mathrm{v}}\text{I}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{(1 + I}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{)}\text{+ v}{}_{\mathrm{M}}\text{∑}\text{X}\text{B}{}_{\mathrm{<mtext>MX</mtext>}}\text{[X] + v}{}_{\mathrm{X}}\text{∑}\text{M}\text{B}{}_{\mathrm{<mtext>MX</mtext>}}\text{[X]}$

, where S_V is the Debye-Hückel limiting law slope, v_i is the number of ions i formed when MX dissociated, [i] is the total molality of ion i and B_MX is a specific interaction parameter that varies slowly with ionic strength. The values of $\text{V}\text{(}\text{MX}\text{)}$ estimated by using this equation were found to agree very well with experimental values in NaCl and seawater providing there are not strong interactions between M and X. For electrolytes that form ion pairs (i.e. MX°) corrections must be made. Methods are discussed for making these corrections.     

(°C)T	$\text{K}{}_{\mathrm{D}}{}^{\mathrm{Phlog/Vap.}}$	$\text{X}{}_{\mathrm{RM}}$	$\text{K}{}_{\mathrm{D}}{}^{\mathrm{Sanid/Vap.}}$	$\text{X}{}_{\mathrm{RM}}$
500	$\text{0.64 ± 0.11}$	0–0.2	$\text{0.17 ± 0.04}$	0–0.07
700	$\text{1.11 ± 0.11}$	0–0.2	$\text{0.33 ± 0.04}$	0–0.1
800	$\text{1.28 ± 0.03}$	0–0.2	$\text{0.45 ± 0.06}$	0–0.1

Distribution coefficients of Eu and Sr for plagioclase-liquid and clinopyroxene-liquid equilibria in oceanic ridge basalt: an experimental study

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: log^PL_Sr = 7320/T ? 4.62logK^CPX_Sr = 18020/T ? 13.10. Similarly, the weight fraction distribution coefficients are given by the equations: logD^PL_Sr = 6570/T ? 4.30logD^CPX_Sr = 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.     

Transfer and exchange equilibria in a portion of the pyroxene quadrilateral as deduced from natural and experimental data

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:Fe²⁺ 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: $\text{> 1080°C: T =}\text{1000}\text{(0.468 + 0.246X}{}^{\mathrm{Cpx}}\text{? 0.123 ln (1–2 [Ca]))}$$\text{< 1080°C: T =}\text{1000}\text{(0.054 + 0.608X}{}^{\mathrm{Cpx}}\text{? 0.304 ln (1–2 [Ca]))}$, and the following equation for the temperature-dependence of the Mg-Fe distribution coefficient: $\text{T =}\text{1130}\text{(}\text{ln}\text{K}{}_{\mathrm{p}}\text{+ 0.505)}$, where T is absolute temperature, X is $\text{Fe}{}^{\mathrm{2+}}\text{(Mg + Fe}{}^{\mathrm{2+}}\text{))}$, [Ca] is $\text{Ca}\text{(Ca + Mg + Fe}{}^{\mathrm{2+}}\text{)}$ in Cpx, and K_D is the distribution coefficient, defined as $\text{X}{}^{\mathrm{Opx}}\text{/(1 ? X}{}^{\mathrm{Opx}}\text{) ÷ X}{}_{\mathrm{Cpx}}\text{/(1 ?}{}^{\mathrm{Cpx}}\text{)}$.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°.     

On calculating activity coefficients and other excess functions from the intracrystalline exchange properties of a double-site phase

For a phase at equilibrium in which two cation species are partitioned ideally between two sub-lattice sites, the excess functions of mixing (free energy, enthalpy and entropy) are directly related to the bulk composition of the phase and ΔG_E°(T, P), the standard-state intra- crystalline exchange free energy. If the phase is not at equilibrium internally, an additional ordering parameter is necessary to fix the excess free energy of mixing, G_mix^EX, unambiguously. Conversely, for any fixed G_mix^EX there exists an infinity of possible intracrystalline cation dis- tributions, only one of which is the equilibrium distribution for the specified temperature and pressure. As ideal intraphase cation ordering becomes more pronounced, G_mix^EX decreases. In response, the total free energy of mixing for the phase decreases progressively for non-end member compositions, approaching, at the limits of ordering, values appropriate for stabilizing compounds of intermediate composition.The model-dependent activity coefficient for component A in the phase, γ_A^T, can be calculated for any bulk composition, X_A^T, either from G_mix^EX directly or from more basic equations involving the interrelation of chemical potentials at equilibrium. A general form for γ_A^T is ln $\text{γ}{}_{\mathrm{A}}{}^{\mathrm{T}}\text{= 1n[}\text{2(X}{}_{\mathrm{A}}{}^{\mathrm{\alpha }}\text{X}{}_{\mathrm{A}}{}^{\mathrm{\beta }}\text{)}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{/}\text{(X}{}_{\mathrm{A}}{}^{\mathrm{\alpha }}\text{+X}{}_{\mathrm{A}}{}^{\mathrm{\beta }}\text{)}\text{]+Y}$, where Xj^κ denotes the mole fraction of species j in site κ. The first term on the right-hand side of this equation is the contribution to γ_A^T from ideal intracrystalline partitioning, and is common to the several theories lately presented to model intraphase cation partitioning. It can be shown rigorously that this term contributes to a negative deviation from ideality for the bulk phase. The second term is the contribution to the macroscopic activity coefficient from non-ideal intraphase partitioning, and is related to an enthalpy of mixing, H_mix^N in excess of that resulting from ideal inter-site cation ordering. While the expression represented by Y can take several functional forms, the additional enthalpy can be evaluated explicitly for specific non-ideal partitioning models from the relation $\text{H}{}_{\mathrm{mix}}{}^{\mathrm{N}}\text{= 2RT(1? X}{}_{\mathrm{A}}{}^{\mathrm{T}}\text{) ∝}\text{Y}\text{(1 ? X}{}_{\mathrm{A}}{}^{\mathrm{T}}\text{)}{}^2\text{dX}{}_{\mathrm{A}}{}^{\mathrm{T}}$.In those cases, G_mix^EX can also be determined exactly.     

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

The effect of presure on the solubility of minerals in water and seawater can be estimated from In

$\text{(}\text{K}{}^{\mathrm{P}}{}_{\mathrm{sp}}\text{K}{}^0{}_{\mathrm{sp}}\text{) +}\text{(?ΔVP + 0.5ΔKP}{}^2\text{)}\text{RT}$

where the volume (ΔV) and compressibility (ΔK) changes at atmospheric pressure (P = 0) are given by

$\text{ΔV =}\text{V}\text{?}\text{(M}{}^{\mathrm{+}}\text{, X}{}^{\mathrm{?}}\text{) ?}\text{V}\text{?}\text{[MX(s)]ΔK =}\text{K}\text{?}\text{(M}{}^{\mathrm{+}}\text{, X}{}^{\mathrm{?}}\text{) ?}\text{K}\text{?}\text{[MX(s)]}$

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.     

Phase relations in the system NaCl-KCl-H2O II: Differential thermal analysis of the halite liquidus in the NaCl-H2O binary above 450°c

Thermal analysis of the halite liquidus in the system NaCl-H₂O has been conducted for NaCl mole fractions (X_NaCl) greater than 0.25 (i.e., > 50 wt. % NaCl) at pressures between 0.3 and 4.1 kb and temperatures greater than 450°C. The position of the liquidus was located by differential thermal analysis (DTA) of cooling scans only, as heating scans did not produce definitive DTA peaks. The dP/dT slope of the liquidus is positive and steep at high pressures, but at high X_NaCl, and pressures below 0.5 kb it appears to reverse slope and intersects the three-phase curve (liquid-halite-vapour) at a shallow angle. However, due to the complex nature of the DTA signal when P <- 0.5 kb, there is considerable doubt about exactly what event has been recorded in the experiments conducted at these low pressures.The solubility of halite can be expressed as a function of the mole-fractional-based activity of NaCl in the liquid phase (L) in temperature (T, °K) and pressure (P, bars) In $\text{α}{}_{\mathrm{NaCl(L.T.P)}}\text{=}\text{?19.884 ? 0.001275T ? 1388}\text{T + 3.2305 In (T) ? 0.07574PT}$ Our liquidus data (based on 10 compositions) above 500 bars for these brines were combined with this equation to generate activity coefficients of NaCl which were fit within their experimental uncertainties to the following one parameter Margules equation In $\text{γ}{}_{\mathrm{NaCl(L.T.P)}}\text{=}\text{(0.7268 ? 695.7}\text{T ? 0.1217PT)}\text{(1 ? X}{}_{\mathrm{NaCl}}\text{)}{}^2$. Concentrated solutions of NaCl show negative deviations from ideality which rapidly increase in magnitude with decreasing X_NaCl.     

Strontium isotope geology of the South Mountain batholith,Nova Scotia

The South Mountain batholith of southwestern Nova Scotia is a large, peraluminous, granodiorite-granite complex which intrudes mainly greenschist facies metasediments of the Cambro-Ordovician Meguma Group. Using Rb-Sr isochrons constructed from whole rocks and mineral separates, the present study shows a variation in age and initial ratios of the intrusive phases of the batholith as follows: biotite granodiorite (371.8 ± 2.2 Ma, (${}^{87}\text{Sr}{}^{86}\text{Sr}\text{)}{}_{\mathrm{i}}$ ranges from 0.7076 ± 0.0003 to 0.7090 ± 0.0003, with the average = 0.7081); adamellite (364.3 ± 1.3 Ma, $\text{(}{}^{87}\text{Sr}{}^{86}\text{Sr}\text{)}{}_{\mathrm{i}}\text{= 0.70942 ± 35}$); porphyry (361.2 ± 1.4 Ma, $\text{(}{}^{87}\text{Sr}{}^{86}\text{Sr}\text{)}{}_{\mathrm{i}}\text{= 0.71021 ± 119}$); using λ⁸⁷Rb = 1.42 × 10^?11yr^?1.A suite of Meguma country rock samples showed a variation of ${}^{87}\text{Sr}{}^{86}\text{Sr}\text{= 0.7113?0.7177}$ at the time of intrusion of the batholith. A number of xenoliths of this material occurring in the marginal granodiorite had partially equilibrated isotopically with the granodiorite at a higher ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratio than elsewhere in the granodiorites. This evidence demonstrates that isotopic (and probably some accompanying bulk chemical) contamination by the Meguma rocks has been an important factor in determining the ultimate chemical composition and mineralogy of the South Mountain batholith.The $\text{(}{}^{87}\text{Sr}{}^{86}\text{Sr}\text{)}{}_{372}\text{= 0.7081}$ of the early granodiorites indicates that the parent magma of the South Mountain batholith was derived from a source unlike the Meguma Group. The precise nature of the source region cannot be determined by Rb-Sr work unless the degree of contamination with Megumalike material is known.     

Geochemical modelling of basalts from DSDP Leg 65, East Pacific Rise,Gulf of California

Major and rare earth element (REE) data for basalts from Holes 483, 483B, and 485A of DSDP Leg 65, East Pacific Rise, mouth of the Gulf of California, support a simple fractional crystallization model for the genesis of rocks from this suite. The petrography and mineral chemistry (presented in detail elsewhere) provide no evidence for magma mixing, but rather a simple multistage cooling process. Based on its lowest TiO₂ content (0.88%), $\text{FeO}{}^1\text{MgO}$ ratio (0.95 with total Fe as FeO), and Mg# (100 $\text{Mg}\text{Mg + Fe}\text{″ = 70}$), sample 483-17-2-(78–83) has been selected as the most primitive primary magma of the samples analyzed. This is supported by the REE data which show this sample has the lowest total REE content, a $\text{La}\text{Sm}{}_{\mathrm{cn}}$ (chondrite-normalized) = 0.36, and $\text{Eu}\text{Sm}{}_{\mathrm{cn}}$ = 1.05. Because other samples analyzed have higher SiO₂, lower Mg#, and a negative Eu anomaly ($\text{Eu}\text{Sm}{}_{\mathrm{cn}}$ as low as 0.89), they are most likely derivative magmas. Wright-Doherty and trace element modelling support fractional crystallization of 14.1% plagioclase (An₈₈), 6.7% olivine (Fo₈₆), and 4.7% clinopyroxene (Wo₄₁En₄₉Fs₁₀) from 483-17-2-(78–83) to form the least differentiated sample with Mg# = 63. The $\text{La}\text{Sm}{}_{\mathrm{cn}}$ of this derivative magma is almost identical to the parent magma (0.35 to 0.36), but the other samples have higher $\text{La}\text{Sm}{}_{\mathrm{cn}}$ (0.45 to 0.51), more total REE, and lower Mg# (60 to 56). Both Wright-Doherty and trace element modelling indicate that the primary magma chosen cannot produce these more evolved samples. For the major elements, the TiO₂ and P₂O₅ are too low in the calculated versus the observed (1.38 to 1.90; 0.11 to 0.17, respectively, for example). Rayleigh fractionation calculates a lower $\text{La}\text{Sm}{}_{\mathrm{cn}}$ and requires about 60% crystal removal versus 40% for the Wright-Doherty. These more evolved samples must be derived from a parent magma different from the one selected here and, unfortunately, not sampled in this study. A magma formed by a smaller degree of partial melting with slightly more residual clinopyroxene left in the mantle than for sample 483-17-2-(78–83) is required.     

Distribution coefficients of major and trace elements; fractional crystallization in the alkali basalt series of Chaîne des Puys (Massif Central,France)

Major and seventeen trace element distribution coefficients between main phenocrysts (olivine, clinopyroxene, amphibole, mica, feldspars and Fe-Ti oxides) and groundmass have been measured in the alkali basalt suite of Chaîne des Puys (Massif Central, France). The suite appears to be a well behaved crystal fractionation series. We pinpoint key elements whose behavior is closely related to the appearance or disappearance of specific crystal phases in the fractionation process. Ta, for instance, clearly indicates the role of hydrous silicates (amphiboles and micas). Distribution coefficients are shown to vary systematically along the differentiation trend. Significantly the hygromagmaphile tendency (Treuilet al., 1979) of U, Th, Ta and La is variable along the series.The mass balance equations,

$\text{D}{}^{\mathrm{i}}\text{=}\text{∑}\text{;}\text{x}{}_{\mathrm{j}}\text{D}{}_{\mathrm{j}}{}^{\mathrm{ii}}$

where Dⁱ and D_jⁱ are the bulk and mineral/liquid distribution coefficients respectively, and x_j the weight fractions of the fractionating phases, are solved by least square resolution of the overdetermined system, taking into account the analytical errors on data. The solution applied to the Chaîne des Puys suite leads to a coherent and quantitative model of the fractional crystallization process. The suite has apparently evolved in three stages. Each stage is characterized by constant bulk distribution coefficients and a specific mineral assemblage. Amphibole fractionation plays an important role in the early stages. Some intensive parameters (T, ? ?_O2, P_H2O) as well as f (weight fraction of residual liquid) are also estimated.     

Investigations of an intrusive contact,northwest Nelson,New Zealand—II. Diffusion of radiogenic and excess 40Ar in hornblende revealed by 40Ar39Ar age spectrum analysis

The Rameka Gabbro, emplaced 367 Ma ago, experienced a well documented reheating on intrusion of the Separation Point Batholith 114 Ma ago. ${}^{40}\text{Ar}{}^{39}\text{Ar}$ age spectrum analyses of hornblende from the Rameka Gabbro show diffusion gradients which provide information on the ⁴⁰Ar boundary concentration during reheating.Three samples of hornblende exhibit age spectra that conform to a model of ⁴⁰Ar loss by diffusion, implying a zero ⁴⁰Ar boundary concentration during heating. The calculated ⁴⁰Ar loss from these samples, together with a model of heat flow in the aureole, provide estimates of diffusion coefficients of ⁴⁰Ar in Mg-rich hornblende which correspond to an activation energy, E, of ~60 kcal-mol^?1 and a frequency factor. D₀, of ~ 10^?3 cm²-sec^?1. When combined with laboratory diffusion results, these data yield a well defined diffusion law (E = 63.3 ± 1.7 kcal-mol^?1, $\text{D}{}_0\text{= 0.022}{}^{\mathrm{+0.048}}{}_{\mathrm{?0.010}}\text{cm}{}^2\text{-}\text{sec}{}^{\mathrm{?1}}$).The age spectra of the eight other samples record steep gradients of excess ⁴⁰Ar over the first few percent of gas release. Although this effect causes high apparent conventional K-Ar ages, the plateau segments of many sampes still record the crystallization age of 367 ± 5 Ma. These measurements show that the excess ⁴⁰Ar phase developed locally in the intergranular regions of the gabbro, following intrusion of the batholith. on time scales that varied from 10⁴ to 10⁶years. The minimum average ${}^{40}\text{Ar}{}^{36}\text{Ar}$ ratio of this component was found to be 1300 ± 400. The partial pressure of Ar was at least 10^?2 bars in some places.A single ${}^{40}\text{Ar}{}^{39}\text{Ar}$ age spectrum analysis of plagioclase reveals a ‘saddle-shaped” release pattern with a minimum at 140 Ma.In conjunction with theoretical diffusion models and a diffusion law, ${}^{40}\text{Ar}{}^{39}\text{Ar}$ age spectrum analysis of hornblende that has experienced a post-crystallization heating can provide close estimates of the maximum temperature of the thermal event as well as both age of crystallization and reheating.     

The use of the specific interaction model to estimate the partial molal volumes of electrolytes in seawater

The specific interaction model has been used to determine the partial molal volume of electrolytes in 0.725 m NaCl and 35‰ salinity seawater solutions at 25°C. The partial molal volumes of electrolytes (MX) were estimated at a given ionic strength (I) from

$\text{V}\text{(}\text{MX}\text{) =}\text{V}{}^0\text{(}\text{MX}\text{) +}\text{S}{}_{\mathrm{v}}\text{I}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{(1 + I}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{)}\text{+ v}{}_{\mathrm{M}}\text{∑}\text{X}\text{B}{}_{\mathrm{<mtext>MX</mtext>}}\text{[X] + v}{}_{\mathrm{X}}\text{∑}\text{M}\text{B}{}_{\mathrm{<mtext>MX</mtext>}}\text{[X]}$

, where S_V is the Debye-Hückel limiting law slope, v_i is the number of ions i formed when MX dissociated, [i] is the total molality of ion i and B_MX is a specific interaction parameter that varies slowly with ionic strength. The values of $\text{V}\text{(}\text{MX}\text{)}$ estimated by using this equation were found to agree very well with experimental values in NaCl and seawater providing there are not strong interactions between M and X. For electrolytes that form ion pairs (i.e. MX°) corrections must be made. Methods are discussed for making these corrections.