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Studies of Quaternary saline lakes-III. Mineral, chemical, and isotopic evidence of salt solution and crystallization processes in Owens Lake, California, 1969-1971

As a consequence of the 1969–1970 flooding of normally dry Owens Lake, a 2.4-m-deep lake formed and 20% of the 2-m-thick salt bed dissolved in it. Its desiccation began August 1969, and salts started crystallizing September 1970, ending August 1971. Mineralogic, brine-composition, and stable-isotope data plus field observations showed that while the evolving brine composition established the general crystallization timetable and range of primary and secondary mineral assemblages, it was the daily, monthly, and seasonal temperature changes that controlled the details of timing and mineralogy during this depositional process. Deuterium analyses of lake brine, interstitial brine, and hydrated saline phases helped confirm the sequence of mineral crystallizations and transformations, and they documented the sources and temperatures of waters involved in the reactions. Salts first crystallized as floating rafts on the lake surface. Natron and mirabilite, salts whose solubilities decrease greatly with lowering temperatures, crystallized late at night in winter, when surface-water temperatures reached their minima; trona, nahcolite, burkeite, and halite, salts with solubilities less sensitive to temperature, crystallized during the afternoon in summer, when surface salinities reached their maxima. However, different temperatures were generally associated with crystallization (at the surface) and accumulation (on the lake floor) because short-term temperature changes were transmitted to surface and bottom waters at different rates. Consequently, even when solubilities were exceeded at the surface, salts were preserved or not as a function of bottom-water temperatures. Halite, a nearly temperature-insensitive salt, was always preserved. Monitoring the lake-brine chemistry and mineralogy of the accumulating salts shows: (1) An estimated 0.9 × 10 6 tons of CO 2 was released to the atmosphere or consumed by the lake's biomass prior to most salt crystallization. (2) After deposition, some salts reacted in situ to form other minerals in less than one month, and all salts (except halite) decomposed or recrystallized at least once in response to seasons. (3) Warming in early 1971 caused solution of all the mirabilite and some of the natron deposited a few months earlier, a deepening of the lake (though the lake-surface lowered), and an increase in dissolved solids. (4) Phase and solubility-index data suggest that at the close of desiccation, Na 2 CO 3 ·7H 2 O, never reported as a mineral, could have been the next phase to crystallize.

Geochimica et Cosmochimica Acta

Changes in the H O Ar isotope composition of clays during retrograde alteration

K-Ar ages of illite alteration associated with Middle Proterozoic Athabasca unconformity-type U deposits in Saskatchewan range from 414 to 1493 Ma. The K-Ar ages correlate with water contents and δD values such that illites with young K-Ar ages have δD values as low as −169 and water contents as high as 7.7 wt.% whereas illites with older ages have δD values near −70 and water contents near 4 wt.%. Water extracted at 400°C from illites with low δD values and high water contents has low δD and δ 18 O values similar to those of modern meteoric water suggesting that some of the illites associated with the original deposition of the ore underwent varying degrees of retrograde alteration. The alteration is initiated by hydration of sites in the interlayer region of the illite which results in the partial resetting of the K-Ar ages and introduction of excess structural water in the form of interlamellar water. The interlamellar water is enriched in 18 O by about 7 per mil relative to the water that physically surrounded the clay particle. Further alteration decreases the δD value and increases the δ 18 O value of the illite by isotopic exchange between the mineral and the interlamellar water. Although the chemical compositions and XRD patterns of the altered illites indicate that no detectable smectite component is present in the samples, the isotopic results suggest that the altered illites may be an early precursor in the formation of mixed-layer illite/smectite by retrograde alteration of pure illite. The wide variation of δD values of chlorite and kaolinite from these U deposits is analogous to that of the illite suggesting that retrograde alteration of clays by meteoric water can be substantial. The general association of altered clays with areas containing the highest concentrations of U is probably related to localized permeability within the ore zone.

Geochimica et Cosmochimica Acta

Heat capacity measurements for cryolite (Na3AlF6) and reactions in the system NaFeAlSiOF

The heat capacity of cryolite (Na 3 AlF 6 ) has been measured from 7 to 1000 K by low-temperature adiabatic and high-temperature differential scanning calorimetry. Low-temperature data were obtained on material from the same hand specimen in the calorimetric laboratories of the University of Michigan and U.S. Geological Survey. The results obtained are in good agreement, and yield average values for the entropy of cryolite of: S 0 298 = 238.5 J / mol K "> S 0 298 = 238.5J/mol K S 0 T − S 0 298 = 145.114 ln T+ 193.009∗10 −3 T− 10.366∗ 10 5 T 2 − 872.89 J / mol K (273−836.5 K ) "> S 0 T −S 0 298 = 145.114lnT+ 193.009∗10 −3 T−10.366∗ 10 5 T 2 − 872.89J/mol K(273−836.5K) Δ S Trans = 9.9 J / mol K "> ΔS Trans = 9.9J/mol K S 0 T − S 0 298 =198.414 ln T+73.203∗ 10 −3 T−63.814∗ 10 5 T 2 −1113.11 J / mol K (836.5−1153 K ) "> S 0 T −S 0 298 =198.414 ln T+73.203∗ 10 −3 T−63.814∗10 5 T 2 −1113.11J/mol K(836.5−1153K) with the transition temperature between α- and β-cryolite taken at 836.5 K. These data have been combined with data in the literature to calculate phase equilibria for the system Na Fe Al Si O F. The resultant phase diagrams allow constraints to be placed on the f O 2 , f F 2 , a SiO 2 and T conditions of formation for assemblages in alkalic rocks. A sample application suggests that log f O 2 is approximately −19.2, log f F 2 is −31.9 to −33.2, and a SiO 2 is −1.06 at assumed P T "> PT conditions of 1000 K, 1 bar for the villiaumite-bearing Ilimaussaq intrusion in southwestern Greenland.

Geochimica et Cosmochimica Acta

Phase relations in the system NaCl-KCl-H 2 O. III: Solubilities of halite in vapor-saturated liquids above 445°C and redetermination of phase equilibrium properties in the system NaCl-H 2 O to 1000°C and 1500 bars

Halite solubilities along the three-phase curve in the binary system NaCl-H 2 O determined by DTA experiment can be represented by the equation Wt.% NaCl (±0.2) = 19.39 − 0.0364 t + 3.553 × 10 −4 T 2 − 2.298 × 10 −7 T 3 , where 447≦ T ≦ 800° C . Even though these halite solubilities are up to ~7 wt.% higher than those reported in literature, extrapolated values at temperatures below 447°C merge with the literature values. It is considered that the equation adequately describes halite solubilities between 382 and 800°C. The newly established solubility data are believed to be more reliable because they are compatible with data obtained by using synthetic fluid inclusions and with the observed DTA signals and also because they were measured in a relatively corrosion-free system. In an earlier publication (GUNTER et al ., 1983), we were puzzled greatly by multiple and rather unreproducible DTA peaks appearing during isobaric cooling (heating experiments were nondefinitive) at pressures below about 500 bars. These DTA signals apparently suggested that the “halite liquidus” swung sharply upward in temperature as pressure decreased from about 500 bars to that of the halite-saturated boiling curve. Further analysis of the data and helpful discussions with several individuals have revealed that the behavior is a consequence of the initial (precooling) separation of the fluid into NaCl-poor gas and NaCl-rich liquid that failed to homogenize in the short time encompassed by the DTA experiments. The present analysis is based on extrapolations of the slopes from pressures above 500 bars. Through use of these new halite solubility data and the data from synthetic fluid inclusions [formed by healing fractures in inclusion-free Brazilian quartz in the presence of two coexisting, immiscible NaCl-H 2 O fluids at various temperatures and pressures (Bodnar et al ., 1985)], phase equilibria in the system NaCl-H 2 O have been redetermined to 1000°C and 1500 bars.

Geochimica et Cosmochimica Acta

Kinetic theory of oxygen isotopic exchange between minerals and water

Kinetic and mass conservation equations are used to describe oxygen isotopic exchange between minerals and water in "closed" and open hydrothermal systems. In cases where n coexisting mineral phases having different reaction rates are present, the exchange process is described by a system of n + 1 simultaneous differential equations consisting of n pseudo first-order rate equations and a conservation of mass equation. The simultaneous solutions to these equations generate curved exchange trajectories on ??-?? plots. Families of such trajectories generated under conditions allowing for different fluid mole fractions, different fluid isotopic compositions, or different fluid flow rates are connected by positive-sloped isochronous lines. These isochrons reproduce the effects observed in hydrothermally exchanged mineral pairs including 1) steep positive slopes, 2) common reversals in the measured fractionation factors (??), and 3) measured fractionations that are highly variable over short distances where no thermal gradient can be geologically demonstrated. ?? 1987.

Geochimica et Cosmochimica Acta

Biogeochemical cycling in an organic-rich coastal marine basin. 7. Sulfur mass balance, oxygen uptake and sulfide retention

Sulfur and oxygen fluxes were quantified in the seasonally varying anoxic marine sedimentary system of Cape Lookout Bight, N.C., U.S.A. Over the three year study period, 1981–1983, the mean annual sulfate reduction rate was determined to be 18.2 ± 1.6 moles · m −2 · y −1 . This value, added to the estimate of the detrital sulfur input of 1.2 ± 4.4 gave a total sulfur input of 19.4 ± 4.7 moles · m −2 · y −1 . The sulfide flux to the sediment-water interface, measured in anaerobic benthic chambers was 4.6 ± 0.5 moles · m −2 · y −1 , and represented 37% of the annual oxygen uptake rate of 25.2 ± 2.8 moles · m −2 · y −1 . The sulfide burial rate, determined to be 15.5 ± 3.1 moles · m −2 · y −1 , was within 5% of the value predicted by summing the fluxes at the sediment-water interface. The C S "> CS weight ratio of sediment below the depth of diagenetic reaction was determined to be 2.75. The sulfide retention rate in these rapidly accumulating sediments (10 cm/yr) was 77 ± 19%. Comparison of this result with previous studies shows that rapid sediment accumulation and the lack of bioturbation control this unusually high degree of sulfide retention.

Geochimica et Cosmochimica Acta

Biogeochemical cycling in an organic-rich coastal marine basin. 8. A sulfur isotopic budget balanced by differential diffusion across the sediment-water interface

The sulfur isotopic composition of the sulfur fluxes occurring in the anoxic marine sediments of Cape Lookout Bight, N.C., U.S.A., was determined, and the result of isotopic mass balance was obtained via the differential diffusion model. Seasonal pore water sulfate δ 34 S measurements yielded a calculated sulfate input of 0.6%.. Sulfate transported into the sediments via diffusion appeared to be enriched in the lighter isotope because its concentration gradient was steeper, due to the increase in the measured isotopic composition of sulfate with depth. Similarly, the back diffusion of dissolved sulfide towards the sediment-water interface appeared enriched in the heavier isotope. The isotopic composition of this flux was calculated from measurements of the δ 34 S of dissolved sulfide and was determined to be 15.9%.. The isotopic composition of buried sulfide was determined to be −5.2%. and the detrital sulfur input was estimated to be −6.2%.. An isotope mass balance equation based upon the fluxes at the sediment-water interface successfully predicted the isotopic composition of the buried sulfur flux within 0.5%., thus confirming that isotopes diffuse in response to their individual concentration gradients.

Geochimica et Cosmochimica Acta

Evidence for Late-Paleozoic brine migration in Cambrian carbonate rocks of the central and southern Appalachians: Implications for Mississippi Valley-type sulfide mineralization

Many Lower Paleozoic limestones and dolostones in the Valley and Ridge province of the central and southern Appalachians contain 10 to 25 weight percent authigenic potassium feldspar. This was considered to be a product of early diagenesis, however, 40 Ar 39 Ar "> 40 Ar 39 Ar analyses of overgrowths on detrital K-feldspar in Cambrian carbonate rocks from Pennsylvania, Maryland, Virginia, and Tennessee yield Late Carboniferous-Early Permian ages (278–322 Ma). Simple mass balance calculations suggest that the feldspar could not have formed isochemically, but required the flux of multiple pore volumes of fluid through the rocks, reflecting regional fluid migration events during the Late-Paleozoic Alleghanian orogeny. Microthermometric measurements of fluid inclusions in overgrowths on detrital K-feldspar and quartz grains from unmineralized rocks throughout the study area indicate homogenization temperatures from 100° to 200°C and freezing point depressions of −14° to −18.5°C (18–21 wt.% NaCl equiv). The apparent similarity of these fluids to fluid inclusions in ore and gangue minerals of nearby Mississippi Valley-type (MVT) deposits suggests that the regional occurrences of authigenic K-feldspar and MVT mineralization may be genetically related. This hypothesis is supported by the discovery of authigenic K-feldspar intergrown with sphalerite in several mines of the Mascot-Jefferson City District, E. Tennessee. Regional potassic alteration in unmineralized carbonate rocks and localized occurrences of MVT mineralization are both explainable by a gravity-driven flow model, in which deep brines migrate towards the basin margin under a hydraulic gradient established during the Alleghanian orogeny. The authigenic K-feldspar may reflect the loss of K during disequilibrium cooling of the ascending brines. MVT deposits are probably localized manifestations of the same migrating fluids, occurring where the necessary physical and chemical traps are present.

Geochimica et Cosmochimica Acta

The decarbonation and heat capacity of ZnCO3

The decarbonation curve for ZnCO 3 has been determined in the pressure range 3–20 kbar by using a combination of cold-seal vessels and piston-cylinder apparatus with NaCl assemblies. Heat capacities for both synthetic and natural ZnCO 3 samples were measured by differential scanning calorimetry at temperatures ranging from 340 to 497 K. The results of these experiments indicate that the enthalpy of formation for smithsonite, ΔH f (1,298.15), is approximately −817. kJ/mol. which is about 4 kJ more negative than most tabulated values.

Geochimica et Cosmochimica Acta

Volatilization, transport and sublimation of metallic and non-metallic elements in high temperature gases at Merapi Volcano, Indonesia

Condensates, silica tube sublimates and incrustations were sampled from 500–800°C fumaroles and lava samples were collected at Merapi Volcano, Indonesia in Jan.–Feb., 1984. With respect to the magma, Merapi gases are enriched by factors greater than 10 5 in Se, Re, Bi and Cd; 10 4 –10 5 in Au, Br, In, Pb and W; 10 3 –10 4 in Mo, Cl, Cs, S, Sn and Ag; 10 2 –10 3 in As, Zn, F and Rb; and 1–10 2 in Cu, K, Na, Sb, Ni, Ga, V, Fe, Mn and Li. The fumaroles are transporting more than 10 6 grams/day ( g d "> gd ) of S, Cl and F; 10 4 –10 6 g/d of Al, Br, Zn, Fe, K and Mg; 10 3 –10 4 g d "> gd of Pb, As, Mo, Mn, V, W and Sr; and less than 10 3 g d "> gd of Ni, Cu, Cr, Ga, Sb, Bi, Cd, Li, Co and U. With decreasing temperature (800-500°C) there were five sublimate zones found in silica tubes: 1) cristobalite and magnetite (first deposition of Si, Fe and Al); 2) K-Ca sulfate, acmite, halite, sylvite and pyrite (maximum deposition of Cl, Na, K, Si, S, Fe, Mo, Br, Al, Rb, Cs, Mn, W, P, Ca, Re, Ag, Au and Co); 3) aphthitalite (K-Na sulfate), sphalerite, galena and Cs-K. sulfate (maximum deposition of Zn, Bi, Cd, Se and In; higher deposition of Pb and Sn); 4) Pb-K chloride and Na-K-Fe sulfate (maximum deposition of Pb, Sn and Cu); and 5) Zn, Cu and K-Pb sulfates (maximum deposition of Pb, Sn, Ti, As and Sb). The incrustations surrounding the fumaroles are also chemically zoned. Bi, Cd, Pb, W, Mo, Zn, Cu, K, Na, V, Fe and Mn are concentrated most in or very close to the vent as expected with cooling, atmospheric contamination and dispersion. The highly volatile elements Br, Cl, As and Sb are transported primarily away from high temperature vents. Ba, Si, P, Al, Ca and Cr are derived from wall rock reactions. Incomplete degassing of shallow magma at 915°C is the origin of most of the elements in the Merapi volcanic gas, although it is partly contaminated by particles or wall rock reactions. The metals are transported predominantly as chloride species. As the gas cools in the fumarolic environment, it becomes saturated with sublimate phases that fractionate from the gas in the order of their equilibrium saturation temperatures. Devolatilization of a cooling batholith could transport enough acids and metals to a hydrothermal system to play a significant role in forming an ore deposit. However, sublimation from a high temperature, high velocity carrier gas is not efficient enough to form a large ore deposit. Re, Se, Cd and Bi could be used as supporting evidence for magmatic fluid transport in an ore deposit.

Geochimica et Cosmochimica Acta

Effects of weathering on biological marker and aromatic hydrocarbon composition of organic matter in Phosphoria shale outcrop

GC-MS analyses were performed on core samples collected from a shale outcrop of the Permian Phosphoria Formation in Utah, U.S.A., to study effects of weathering on selected biological marker and aromatic (phenanthrene) hydrocarbon compounds. Among the biological markers, the most important weathering effects are a decrease in the 20S 20R "> 20S20R diastereomer ratio of the C 29 steranes and loss of low molecular weight triaromatic steroids. A decrease in the C 19 through C 22 tricylcic terpanes occurs relative to the total C 19 -C 26 tricyclic fraction. Pronounced loss of methyl-substituted phenanthrenes occurs relative to phenanthrene. No major effect on the overall distribution of pentacyclic terpanes is evident.

Geochimica et Cosmochimica Acta

Molecular weight of aquatic fulvic acids by vapor pressure osmometry

The molecular weights of aquatic fulvic acids extracted from five rivers were determined by vapor pressure osmometry with water and tetrahydrofuran as solvents. The values obtained ranged from 500 to 950 dallons, indicating that the molecular weights of aquatic fulvic acids are not as great as has been suggested in some other molecular weight studies. The samples were shown to be relatively monodisperse from radii of gyration measurements determined by small angle x-ray scattering. THF affords greater precision and accuracy than H 2 O in VPO measurements, and was found to be a suitable solvent for the determination of molecular weight of aquatic fulvic acid because it obviates the dissociation problem. An inverse correlation was observed with these samples between the concentration of Ca ++ and Mg ++ in the river water and the radii of gyration and molecular weights of the corresponding fulvic acid samples.

Geochimica et Cosmochimica Acta

Heat capacities of synthetic hedenbergite, ferrobustamite and CaFeSi2O6 glass

Heat capacities have been measured for synthetic hedenbergite (9–647 K), ferrobustamite (5–746 K) and CaFeSi 2 O 6 glass (6–380 K) by low-temperature adiabatic and differential scanning calorimetry. The heat capacity of each of these structural forms of CaFeSiO 6 exhibits anomalous behavior at low temperatures. The X-peak in the hedenbergite heat-capacity curve at 34.5 K is due to antiferromagnetic ordering of the Fe 2+ ions. Ferrobustamite has a bump in its heat-capacity curve at temperatures less than 20 K, which could be due to weak cooperative magnetic ordering or to a Schottky anomaly. Surprisingly, a broad peak with a maximum at 68 K is present in the heat-capacity curve of the glass. If this maximum, which occurs at a higher temperature than in hedenbergite is caused by magnetic ordering, it could indicate that the range of distortions of the iron sites in the glass is quite small and that coupling between iron atoms is stronger in the glass than in the edge-shared octahedral chains of hedenbergite. The standard entropy change, S o 298.15 − S o 0 , is 174.2 ± 0.3, 180.5 ± 0.3 and 185.7 ± 0.4 J/mol·K for hedenbergite, ferrobustamite and CaFeSi 2 O 6 glass, respectively. Ferrobustamite is partially disordered in Ca-Fe distribution at high temperatures, but the dependence of the configuratonal entropy on temperature cannot be evaluated due to a lack of information. At high temperatures (298–1600 K), the heat capacity of hedenbergite may be represented by the equation C o p (J/mol·K) = 3 l 0.46 + 0.01257 T -2039.93 T −1 2 − 1.84604× l0 6 T −2 "> −12− 1.84604× 10 6 T −2 and the heat capacity of ferrobustamite may be represented by C o p (J/mol·K) = 403.83−0.04444T+ 1.597× 10 −5 T 2 −3757.3T −1 2 "> C o p (J/mol·K)= 403.83−0.04444T+ 1.597× 10 −5 T 2 −3757.3T −12 .

Geochimica et Cosmochimica Acta

Heat capacity and thermodynamic properties of andradite garnet, Ca 3 Fe 2 Si 3 O 12 , between 10 and 1000 K and revised values for ΔfGom (298.15 K) of hedenbergite and wollastonite

The heat capacity of synthetic andradite garnet (Ca 3 Fe 2 Si 3 O 12 ) was measured between 9.6 and 365.5 K by cryogenic adiabatic calorimetry and from 340 to 990 K by differential scanning calorimetry. At 298.15 K C o p , m and S o m are 351.9 ± 0.7 and 316.4 ± 2.0 J/(mol·K), respectively. Andradite has a λ-peak in C o p , m with a maximum at 11.7 ± 0.2 K which is presumably associated with the antiferromagnetic ordering of the magnetic moments of the Fe 3+ ions. The Gibbs free energy of formation, Δ f G o m (298.15 K) of andradite is −5414.8 ± 5.5 kJ/mol and was obtained by combining our entropy and heat capacity data with the known breakdown of andradite to pseudowollastonite and hematite at ≈ 1410 to 1438 K. From a reexamination of the calcite + quartz = wollastonite equilibrium data we obtained Δ f H o m (298.15 K) = − 1634.5 ± 1.8 kJ/mol for wollastonite. Between 300 and 1000 K the molar heat capacity of andradite can be represented by the equation C o p , m = 809.24 - 7.025 × 10−2 T − 7.403 × 10 3 T −0.5 − 6.789 × 10 5 T −2. We have also used our thermochemical data for andradite to estimate the Gibbs free energy of formation of hedenbergite (CaFeSi 2 O 6 ) for which we obtained Δ f G o m (298.15 K ) = −2674.3 ± 5.8 kJ/mol.

Geochimica et Cosmochimica Acta

Geochemistry of the rare earth elements in ferromanganese nodules from DOMES Site A, northern equatorial Pacific

The distribution of rare earth elements (REE) in ferromanganese nodules from DOMES Site A has been determined by instrumental neutron activation methods. The concentrations of the REE vary markedly. Low concentrations characterize samples from a depression (the valley), in which Quaternary sediments are thin or absent; high concentrations are found in samples from the surrounding abyssal hills (the highlands) where the Quaternary sediment section is relatively thick. Moreover, the valley nodules are strongly depleted in the light trivalent REE (LREE) and Ce compared with nodules from the highlands, some of the former showing negative Ce anomalies. The REE abundances in the nodules are strongly influenced by the REE abundances in coexisting bottom water. Some controls on the REE chemistry of bottom waters include: a) the more effective removal of the LREE relative to the HREE from seawater because of the greater degree of complexation of the latter elements with seawater ligands, b) the very efficient oxidative scavenging of Ce on particle surfaces in seawater, and c) the strong depletion of both Ce and the LREE in, or a larger benthic flux of the HREE into, the Antarctic Bottom Water (AABW) which flows through the valley. The distinctive REE chemistry of valley nodules is a function of their growth from geochemically evolved AABW. In contrast, the REE chemistry of highland nodules indicates growth from a local, less evolved seawater source.

Geochimica et Cosmochimica Acta

Pressure-composition relations for coexisting gases and liquids and the critical points in the system NaCl-H 2 O at 450, 475, and 500°C

Pressure-temperature-composition ( P , T , x ) relations for the co-existing vapor and liquid phases in the system NaCl-H 2 O were determined experimentally at 450, 475, and 500°C. Data for each isotherm include P - x relations near the critical point and extend to the three-phase assemblage vapor-liquid-halite on the vapor side. On the liquid side the P - x data range from the critical point to the room-temperature halite saturation point (~25 wt.% NaCl). Critical pressures were calculated from measured pressures and compositions and classical theory. The results generally support the few data points of Urusova (1974, 1975) and Ölander and Liander (1950) but differ markedly from the extensive data of Sourirajan and Kennedy (1962).

Geochimica et Cosmochimica Acta

Observations and controls on the occurrence of inherited zircon in Concord-type granitoids, New Hampshire

U-Pb analyses of zircons separated from two Concord-type plutons near Sunapee and Dixville Notch, New Hampshire, reveal differences in the pattern and magnitude of zircon inheritance which are related to differences in melt chemistry. The Sunapee pluton contains only slightly more Zr than required to saturate the melt at the peak temperature of 700 ± 30° C . Traces of inherited zircon in this separate are inferred to be present as small, largely resorbed grains. In contrast, the Long Mountain pluton, near Dixville Notch, contains about 240% more Zr than required to saturate the melt. Thus, more than half of the Zr existed as stable, inherited zircon crystals during the partial fusion event, consistent with the observation of substantial inheritance in all grain size fractions. Ion probe intra-grain analyses of zircon from the Long Mountain pluton indicate a complex pattern of inheritance with contributions from at least two Proterozoic terrenes and caution against simple interpretations of upper and lower intercepts of chords containing an inherited component. Ion probe analyses of zircons from the Sunapee pluton reveal clear evidence of U loss which results in incorrect apparent conventional U-Pb ages. Ages of crystallization for the Long Mountain and Sunapee pluton are ~350 and 354 ± 5 Ma, respectively. A Sm/Nd measurement for the Long Mountain pluton yields a depleted mantle model age of 1.5 Ga, consistent with the observed inheritance pattern. In contrast, a Sm/Nd model age for the Sunapee pluton is improbably old due to minor monazite fractionation.

Geochimica et Cosmochimica Acta

Thermodynamics of aragonite-strontianite solid solutions: Results from stoichiometric solubility at 25 and 76°C

Dissolution of synthetic strontianite-aragonite solid solutions was followed analytically to stoichiometric saturation using large solid to solution ratios in CO 2 -H 2 O solution at 25 and 76°C. The compositional dependence of the equilibrium constant was calculated from the composition of saturated (stoichiometric) solutions and used to calculate the activities and activity coefficients of CaCO 3 and SrCO 3 in the solid Ca (1− x ) Sr x CO 3 at 25 and 76°C. The results show that the solid-solution is not regular but unsymmetrical. The excess free energy of mixing is closely modeled for all compositions by the relation where A 0 is 8.49 ± 0.30 and 7.71 ± 0.20 KJ/mole and A 1 is −4.51 ± 0.20 and −3.36 ± 0.40 KJ/mole at 25 and 76°C, respectively. The equilibrium constant is denned as a function of the SrCO 3 mole fraction, x , by the relation where R is the gas constant, T is in Kelvins and K A and K S are the aragonite and strontianite equilibrium constants. The experimental results indicate the Henry's law coefficients of SrCO 3 in aragonites containing 0 to 6 mole percent SrCO 3 are approximately 91± 8 and 23 ± 1 at 25 and 76°C, respectively and for strontianites the Henry's law coefficients and applicable compositional ranges are approximately 7.3 ± 0.3 (0.84 ≤ x ≤ 1.00) and 3.3 ± 0.5 (0.50 ≤ x ≤ 1.00) at 25 and 76°C, respectively. Substitution of small amounts of Sr in aragonite and Ca in strontianite initially increases the stability of the solid. The most stable aragonites and strontianites contain 0.58 ± 0.03 and 12.5 ± 1.1 mole percent SrCO 3 and CaCO 3 at 25°C and 3.1 ± 0.3 and 17.2 ± 1.1 mole percent SrCO 3 and CaCO 3 at 76°C, respectively. The spinode occurs over the regions 0.065 ± 0.001 ≤ x ≤ 0.620 ± 0.014 at 25°C and 0.103 ± 0.007 ≤ x ≤ 0.585 ± 0.019 at 76°C where all compositions are unstable. A miscibility gap occurs over the compositional ranges 0.0058 ± 0.0003 ≤ x ≤ 0.875 ± 0.011 at 25°C and 0.031 ± 0.003 ≤ x ≤ 0.828 ± 0.011 at 76°C and is in reasonable agreement with reported compositions of natural aragonites and strontianites. Marine aragonites are neither at equilibrium nor stoichiometric saturation with surface seawater. The experimentally observed distribution coefficient of Sr in aragonite is 12 times larger than the calculated equilibrium value (0.095) at 25°C. Naturally occurring strontianites contain large amounts of calcium primarily because Ca/Sr ratios in natural waters are typically large. Neither equilibrium nor stoichiometric saturation is observed at 76°C during laboratory recrystallization of strontianite-aragonite solid solutions even after apparent 100 percent conversion to a narrow secondary composition and demonstration of a nearly constant composition system for periods of 300 hours.

Geochimica et Cosmochimica Acta