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1.
The solubility of rutile has been determined in a series of compositions in the K2O-Al2O3-SiO2 system ( + Al2O3) = 0.38–0.90), and the CaO-Al2O3-SiO2 system (). Isothermal results in the KAS system at 1325°C, 1400°C, and 1475°C show rutile solubility to be a strong function of the ratio. For example, at 1475°C the amount of TiO2 required for rutile saturation varies from 9.5 wt% () to 11.5 wt% () to 41.2 wt% (). In the CAS system at 1475°C, rutile solubility is not a strong function of . The amount of TiO2 required for saturation varies from 14 wt% () to 16.2 wt% ().The solubility changes in KAS melts are interpreted to be due to the formation of strong complexes between Ti and K+ in excess of that needed to charge balance Al3+. The suggested stoichiometry of this complex is K2Ti2O5 or K2Ti3O7. In CAS melts, the data suggest that Ca2+ in excess of A13+ is not as effective at complexing with Ti as is K+. The greater solubility of rutile in CAS melts when is less than 0.54 compared to KAS melts of equal ratio results primarily from competition between Ti and Al for complexing cations (Ca vs. K).TiKβ x-ray emission spectra of KAS glasses () with 7 mole% added TiO2, rutile, and Ba2TiO4, demonstrate that the average Ti-O bond length in these glasses is equal to that of rutile rather than Ba2TiO4, implying that Ti in these compositions is 6-fold rather than 4-fold coordinated. Re-examination of published spectroscopic data in light of these results and the solubility data, suggests that the 6-fold coordination polyhedron of Ti is highly distorted, with at least one Ti-O bond grossly undersatisfied in terms of Pauling's rules. 相似文献
2.
, and ratios have been measured on the same samples for carbonatite complexes. The results show that besides the ‘carbonatite box’ of Tayloret al. (1967) there exist higher δ18O and δ13C values than can be explained by late magmatic or deuteric processes. These processes correspond to high concentrations of CO2 and lead to big enrichments in 18O and 13C as well as in some ‘volatile’ elements. Strontium results are consistent with a model of selective contamination of deep-seated material by highly radiogenic strontium. The whole study leads to the opinion that parent magmas of carbonatites differentiated in a crustal environment with or without significant contamination. 相似文献
3.
CaCO3Ca(OH)2CaS serves as a model system for sulfide solubility in carbonatite magmas. Experiments at 1 kbar delineate fields for primary crystallization of CaCO3, Ca(OH)2 and CaS. The three fields meet at a ternary eutectic at 652°C with liquid composition (wt%): CaCO3 = 46.1%, Ca(OH)2 = 51.9%, CaS = 2.0%. Two crystallization sequences are possible for liquids that precipitate calcite, depending upon whether the liquid is on the low-CaS side, or the high-CaS side of the line connecting CaCO3 to the eutectic liquid. Low-CaS liquids precipitate no sulfide until the eutectic temperature is reached leading to sulfide enrichment. The higher-CaS liquids precipitate some sulfide above the eutectic temperature, but the sulfide content of the melt is not greatly depleted as the eutectic temperature is approached. Theoretical considerations indicate that sulfide solubility in carbonate melts will be directly proportional to and inversely proportional to ; it also is likely to be directly proportional to melt basicity, defined here by . A strong similarity exists in the processes which control sulfide solubility in carbonate and in silicate melts. By analogy with silicates, ferrous iron, which was absent in our experiments, may also exert an important influence on sulfide solubility in natural carbonatite magmas. 相似文献
4.
Calculations based on approximately 350 new measurements (CaT-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 KC, KA, and KV respectively, for the reaction CaCO3(s) = Ca2+ + CO2?3: 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 logKCahco+3 = 1.11 ± 0.07 at 25°C. The CaCO03 association constant was measured potentiometrically to be between 5 and 80°C, yielding logKCaCO03 = 3.22 ± 0.14 at 25°C.The CO2-H2O equilibria have been critically evaluated and new empirical expressions for the temperature dependence of KH, K1 and K2 are , 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
5.
The isotopic ratios and show an annual periodicity in the coral Montastrea annularis from Bermuda, Jamaica and Barbados. The abundances of 18O and 13C are positively correlated in the Jamaica and Barbados samples, but inversely related in the Bermuda sample. Annual high density growth bands are formed during the season of warmest water temperature at all 3 sites and are enriched in 16O. M. Annularis has a constant displacement from oxygen isotopic equilibrium and accurately records seasonal temperature variations via the temperature-dependent aragonite-water fractionation factor. Light intensity, through the activity of the coral's endosymbiotic algae, regulates the depth-dependent and seasonal variations in the skeletal carbon isotopic composition. 相似文献
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7.
Numerical modeling of the terrestrial oxygen budget based on the revised δ13Ccarb record by Veizeret al. (1980) has shown that total photosynthetic oxygen has varied between ±7% and ±10% of its average reservoir size (～3.2 × 1022 g) during the last 800 myr as a result of oscillations of the sedimentary reservoir of organic carbon. Calculated curves of oxygen evolution display a distinct minimum in the Early Paleozoic framed by two maxima in the Latest Proterozoic and the Mesozoic. The sympathetic relationship observed between the curves of total oxygen evolution and respective functions for the partial reservoir of sulfate-bound oxygen suggests that the O2 required for an additional conversion of sulfide to sulfate was most probably provided by excess burial of organic carbon, the results of the modeling thus adding credence to current interpretations proposed for the negative correlation between the secular and trends. 相似文献
8.
Equations are developed for calculating the density of aluminosilicate liquids as a function of composition and temperature. The mean molar volume at reference temperature Tr, is given by , 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 is the composition-dependent apparent partial molar volume of Al2O3. The thermal expansion coefficient of aluminosilicate liquids is given by , where terms are constants independent of temperature and composition, and 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) = Vrexp[α(T-Tr)], where Tr = 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 and an average absolute difference of 0.90% for 248 experimental observations. The compositional dependence of is discussed in terms of several possible interpretations of the structural role of Al3+ in aluminosilicate melts. 相似文献
9.
Small live individuals of Globigerinoides sacculifer which were cultured in the laboratory reached maturity and produced garnets. Fifty to ninety percent of their skeleton weight was deposited under controlled water temperature (14° to 30°C) and water isotopic composition, and a correction was made to account for the isotopic composition of the original skeleton using control groups.Comparison of. the actual growth temperatures with the calculated temperature based on paleotemperature equations for inorganic CaCO3 indicate that the foraminifera precipitate their CaCO3 in isotopic equilibrium. Comparison with equations developed for biogenic calcite give a similarly good fit. Linear regression with Craig's (1965) equation yields: where t is the actual growth temperature and Is the calculated paleotemperature. The intercept and the slope of this linear equation show that the familiar paleotemperature equation developed originally for mollusca carbonate, is equally applicable for the planktonic foraminifer G. sacculifer.Second order regression of the culture temperature and the delta difference (δ18Oc ? δ18Ow) yield a correlation coefficient of r = 0.95: and δ18Ow are the estimated temperature, the isotopic composition of the shell carbonate and the sea water respectively.A possible cause for nonequilibnum isotopic compositions reported earlier for living planktonic foraminifera is the improper combustion of the organic matter. 相似文献
10.
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 () ranged from 1.0 to 0.2.At P < 4 kbar the stability temperature (T) of pargasite decreases with decreasing at constant P. Above P ? 4 kbar stability T increases as is decreased below one, passes through a T maximum and then decreases with a further decrease in . This behavior is due to a decrease in the H2O content of the silicate liquid as decreases. The magnitude of the T maximum increases from about 10°C (relative to the stability T for ) at P = 5 kbar to about 30°C at P = 8 kbar, and the position of the maximum shifts from at P = 5 kbar to 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 at high P and T, hornblende can be an important phase in igneous processes even at relatively low H2O fugacities. 相似文献
11.
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 () and compressibilty () in water and seawater have been tabulated for some ions from 0 to 50°C. The compressibility change is quite large (~10 × 10?3 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 Ksp versus P and molal volume data (Macdonald and North, 1974; North, 1974). Calculated values of 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
12.
The reaction between hydrous iron oxides and aqueous sulfide species was studied at estuarine conditions of pH, total sulfide, and ionic strength to determine the kinetics and formation mechanism of the initial iron sulfide. Total, dissolved and acid extractable sulfide, thiosulfate, sulfate, and elemental sulfur were determined by spectrophotometric methods. Polysulfides, S42? and S52?, were determined from ultraviolet absorbance measurements and equilibrium calculations, while product hydroxyl ion was determined from pH measurements and solution buffer capacity.Elemental sulfur, as free and polysulfide sulfur, was 86% of the sulfide oxidation products; the remainder was thiosulfate. Rate expressions for the reduction and precipitation reactions were determined from analysis of electron balance and acid extractable iron monosulfide vs time, respectively, by the initial rate method. The rate of iron reduction in moles/liter/minute was given by where St was the total dissolved sulfide concentration, (H+) the hydrogen ion activity, both in moles/ liter; and AFeOOH the goethite specific surface area in square meters/liter. The rate constant, k, was 0.017 ± 0.002m?2 min?1. The rate of reduction was apparently determined by the rate of dissolution of the surface layer of ferrous hydroxide. The rate expression for the precipitation reaction was where was the rate of precipitation of acid extractable iron monosulfide in moles/liter/minute, and k = 82 ± 18 mol?1l2m?2 min?1.A model is proposed with the following steps: protonation of goethite surface layer; exchange of bisulfide for hydroxide in the mobile layer; reduction of surface ferric ions of goethite by dissolved bisulfide species which produces ferrous hydroxide surface layer elemental sulfur and thiosulfate; dissolution of surface layer of ferrous hydroxide; and precipitation of dissolved ferrous specie and aqueous bisulfide ion. 相似文献
13.
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 mFe3+ is the molal concentration of uncomplexed ferric iron, k is the rate constant and 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 ratio, they appear to be more reactive per unit mass than the higher temperature types. 相似文献
14.
In a soil developed on the Cretaceous chalk of the Eastern Paris basin, calcite dissolution begins at the surface. The soil water is rapidly saturated in calcite. Calcite dissolution follows two different pathways according to seasonal pedoclimatic conditions.During winter: the soil is only partly saturated in water and the CO2 partial pressure is low (Ca 10?3 atm.). As a consequence total inorganic dissolved carbon (TIDC) is a hundred times the carbon content of the gaseous phase. Equilibrium is usually observed between the two phases. It is a closed system. The measured carbon 14 activity (87,5%) and 13C content () of the drainage water are very close to theoretical values calculated for an ideal mixing system between gaseous and mineral phases (respectively characterized by the following isotopic values: ; ; ; ).During spring and summer: the soil moisture decreases, the input of biogenic CO2 induces an increase of the soil CO2 partial pressure (Ca from 3.10?3 atm to 7.10?3 atm). The carbon content of the gaseous phase is higher by an order of magnitude compared to winter conditions. Therefore the aqueous phase is undersaturated in CO2 with respect to the latter. This disequilibrium occurs as a result of unbalanced rates of CO2 dissolution and CO2 effusion toward atmosphère. It is an open system. The carbon isotopic ratio of the aqueous phase is regulated by that of the gaseous phase, as demonstrated by the agreement between measured and calculated isotopic compositions (respectively δL mes = from ?9,4%0 to ?11,5%0, δl calc = from ?9,8%0 to ?13,9%0 AL mes = 119%, AL calc = from 119% to 125%).The solutions originating from both systems (open and closed) move downwards without significant mixing together. It has also been observed that no significant variation of the TIDC isotopic composition occurs during precipitation of secondary calcite. 相似文献
15.
Mechanisms and kinetics of aqueous oxidation-reduction and dissolved O2 interaction in the presence of augite, biotite and hornblende were studied in oxic and anoxic solutions at pH 1–9 at 25°C. Oxidation of surface iron on the minerals coincided with both surface release of Fe+2 and by reduction of Fe+3 in solution. Reaction with iron silicates consumed dissolved oxygen at a rate that increased with decreasing pH. Both Fe+3 and O2 consumption were shown to be controlled by coupled electron-cation transfer reactions of the form; and where M is a cation of charge +z. The spontaneous reduction of aqueous Fe+3in the presence of precipitated Fe(OH)3bracketed the surface oxidation standard half cell between +0.33 and +0.52 volts. Concurrent hydrolysis reactions involving cation release from the iron silicates were suppressed by the above reactions. Calculated oxidation depths in the minerals varied between 12 and 80Å and were apparently controlled by rates of solid-state cation diffusion. 相似文献
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17.
Precambrian sedimentary carbonates: carbon and oxygen isotope geochemistry and implications for the terrestrial oxygen budget 总被引：2，自引：0，他引：2
Carbon isotope values of 260 Precambrian limestones and dolomites (most of them being substantially unaltered) have yielded an overall mean of vs. PDB; the corresponding oxygen values average at vs. SMOW. Like the overall mean, the δ 13C values furnished by individual carbonate occurrences are, as a rule, fairly “modern” and almost constant as from the very beginning of the sedimentary record. A remarkable exception are the “heavy” dolomites of the Middle Precambrian Lomagundi Group, Rhodesia, with vs. PDB. As a result of our measurements, the sporadic occurrence in the geological past of anomalously heavy carbonates seems to be established.The approximate constancy around zero per mill of the δ 13C values of marine carbonates through geologic time would imply a corresponding constancy of the relative proportion of organic carbon in the total sedimentary carbon reservoir since about 3.3 · 109 y ago (with Corg/Ctotal ? 0.2). Utilizing this ratio and current models for the accumulation of the sedimentary mass as a function of time, we get a reasonable approximation for the absolute quantity of organic carbon buried in sediments and, accordingly, of photosynthetic oxygen released. Within the constraints of our model (based on a terrestrial degassing constant λ = 1.16 · 10?9 y?1) close to 80% of the amount of oxygen contained in the present oxygen budget should have been released prior to 3 · 109 y ago. Since geological evidence indicates an O2-deficient environment during the Early and most parts of the Middle Precambrian, there is reason to believe that the distribution of this oxygen between the “bound” and the “molecular” reservoir was different from that of today (with effective O2-consuming reactions bringing about an instantaneous transfer to the crust of any molecular oxygen released). Accordingly, the amount of Corg in the ancient sedimentary reservoir as derived from our isotope data is just a measure of the gross amount of photosynthetic oxygen produced, withholding any information as to how this oxygen was partitioned between the principal geochemical reservoirs. As a whole, the carbon isotope data accrued provide evidence of an extremely early origin of life on Earth since the impact of organic carbon on the geochemical carbon cycle can be traced back to almost 3.5 · 109y. 相似文献
18.
David B. Wenner 《Geochimica et cosmochimica acta》1979,43(4):603-614
, and analyses were made of 14 whole rock and 28 mineral samples of rodingites associated dominantly with lizardite-chrysotile serpentinites from the West Coast of the U.S.A., New Zealand, and the Northern Appalachian Mtns. The δD values of the rodingite minerals are in three groupings: 5 monomineralic veins of pectolite, ?281 to ?429; 8 monomineralic veins of xonotlite, ?112 to ?135; all other minerals, including hydrogarnet, idocrase, prehnite, actinolite, nephrite, and chlorite, ?34 to ?80. Most calcites in rodingites have δ18O (+9.3 to +14.4) and (δ13C (?6.7 to +0.9) values similar to calcites in other Franciscan rocks, but distinct from the very low temperature calcite veins in serpentinites. The data, combined with δ18O values of xonotlite (+5.7 to +10.9) and pectolite (+8.9 to +12.4) suggest formation from meteoric-type waters at low temperatures; the depletion of pectolite, however, is anomalous. Rodingite whole rock values range from δ18O = +4.1 to +11.5 and δD = ?50 to ?86; one sample containing minor amounts of lizardite-chrysotile serpentinite has δD = ?92, outside this range. However, most rodingites of basaltic or gabbroic parentage are more restricted in δ18O (+4.1 to +8.6). Such a wide range in δ18O is consistent with the idea that most rodingites form over a relatively broad range of hydrothermal temperatures. Hydrogen isotopic data for most rodingite minerals (except xonotlite and pectolite) and for whole rocks are suggestive of non-meteoric waters. These data overlap those observed for veins of hydrous minerals found in Franciscan igneous rocks studied by Margaritz and Taylor (1976, Geochim. Cosmochim. Acta40, 215–234), possibly suggesting evolved D-enriched, connate type metamorphic waters generated during high P, low T Franciscan-type metamorphism at temperatures (250–500°C) comparable to estimates based on mineral stabilities. Such an interpretation is supported by the and data for calcite in rodingites.The isotope data appear to contradict some of the conclusions derived from geologic and petrologic studies that indicate concomitant metasomatism and serpentinization of their presently observed host rock. These data appear most consistent with the interpretation that most rodingite minerals, with the exception of late-stage veins of xonotlite and possibly pectolite, may involve metasomatism in association with antigorite serpentinization of ultramafic rock. Subsequent upward tectonic transport in many instances may result in incorporation of the rodingites into their presently observed lizarditechrysotile host rock during or subsequent to pervasive shallow level serpentinization by meteoric waters. 相似文献
19.
The geochemical history of Lake Lisan, the Pleistocene precursor of the Dead Sea, has been studied by geological, chemical and isotopic methods.Aragonite laminae from the Lisan Formation yielded (equivalent) Sr/Ca ratios in the range 0.5 × 10?2?1 × 10?2, Na/Ca ratios from 3.6 × 10?3 to 9.2 × 10?3, values between 1.5 and 7%. and from ?7.7 to 3.4%..The distribution coefficient of Na+ between aragonite and aqueous solutions, , is experimentally shown to be very sensitive to salinity and nearly temperature independent. Thus, Na/Ca in aragonite serves as a paleosalinity indicator.Sr/Ca ratios and values in aragonite provide good long-term monitors of a lake's evolution. They show Lake Lisan to be well mixed, highly evaporated and saline. Except for a diluted surface layer, the salinity of the lake was half that of the present Dead Sea (15 vs 31%).Lake Lisan evolved from a small, yet deep, hypersaline Dead Sea-like, water body. This initial lake was rapidly filled-up to its highest stand by fresh waters and existed for about 40,000 yr before shrinking back to the present Dead Sea. The chemistry of Lake Lisan at its stable stand represented a material balance between a Jordan-like input, an original large mass of salts and a chemical removal of aragonite. The weighted average depth of Lake Lisan is calculated, on a geochemical basis, to have been at least 400, preferably 600 m.The oxygen isotopic composition of Lake Lisan water, which was higher by at least 3%. than that of the Dead Sea, was probably dictated by a higher rate of evaporation.Na/Ca ratios in aragonite, which correlate well with values, but change frequently in time, reflect the existence of a short lived upper water layer of varying salinity in Lake Lisan. 相似文献
20.
The following equation has been previously developed for the drag coefficient of a sphere. In this work the authors propose a power series expansion for C0 in terms of the Reynolds number: A fifth-order polynomial permits obtaining the drag coefficient and the settling velocity of a sphere, up to a Reynolds number of 3 × 105, with an average relative error of about 2%. 相似文献