Biogenic hydrocarbon gases and sulfate reduction in the Orca Basin brine     

Denis A Wiesenburg  James M Brooks  Bernie B Bernard 《Geochimica et cosmochimica acta》1985,49(10):2069-2080

The composition of light hydrocarbon gases in the Orca Basin, an anoxic, hypersaline intraslope depression on the continental slope of the northern Gulf of Mexico, indicates that both methane and ethane are biogenic in nature with a $\text{C}{}_1\text{(C}{}_2\text{+ C}{}_3\text{)}$ ratio of 730 and a δ¹³C of methane of ?73%. relative to the PDB standard. The concentrations of methane (750 mM) and ethane (1300 mM) in the Orca Basin brine are higher than any other marine anoxic basin. These high levels result not from high rates of productivity, but from the long residence time of the brine in the basin, due to its high stability toward mixing with overlying seawater ($\text{Δσ}{}_1\text{ΔZ}\text{=}\text{3.2}\text{m}$). Both methane and ethane show well mixed distributions in the brine. These distributions probably result from convective mixing of the isohaline brine pool due to normal heat flow from the basin sediments. Methane and ethane maxima above the pycnocline at the brine/seawater interface reflect in situ production and/or consumption in the aerobic water column. Concurrent maxima in suspended particulate material distributions in this region suggest methane may be produced there in anaerobic microenvironments associated with the suspended matter. Reduced rates of anaerobic decomposition (including sulfate reduction) in the brine sediments are inferred from preserved Sargassum fronds in the sediments, vertical sulfate profiles in most cores, and the sediment organic carbon content which is two to three times higher in sediments below the high salinity brine than in the normal Gulf sediments nearby.  相似文献   

Sedimentary iron monosulfides: Kinetics and mechanism of formation     

Albert J Pyzik  Sheldon E Sommer 《Geochimica et cosmochimica acta》1981,45(5):687-698

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, S₄^2? and S₅^2?, 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 $\text{d(}\text{reduction}\text{Fe)}\text{dt}\text{= kS}{}_{\mathrm{t}}{}^{0.5}\text{(J}{}^{\mathrm{+}}\text{)}{}^{0.5}\text{A}{}_{\mathrm{FeOOH}}{}^1$ where S_t was the total dissolved sulfide concentration, (H⁺) the hydrogen ion activity, both in moles/ liter; and A_FeOOH 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 $\text{d(FeS)}\text{dt}\text{= kS}{}_{\mathrm{t}}{}^1\text{(H}{}^{\mathrm{+}}\text{)}{}^1\text{A}{}_{\mathrm{FeOOH}}{}^1$ where $\text{d(FeS)}\text{dt}$ 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   

Interstitial water chemistry in the sediments of Saanich Inlet     

James W. Murray  Varis Grundmanis  William M. Smethie 《Geochimica et cosmochimica acta》1978,42(7):1011-1026

Measurements of nutrients and trace metals are used to examine the processes controlling their distributions in the interstitial waters of Saanich Inlet. Samples were collected using both in situ and squeezing techniques with excellent agreement. Additional measurements of porosity, organic carbon and sedimentation rate by ²¹⁰Pb are used in conjunction with the nutrient measurements to test the equation for the diagenesis of organic matter in fine-grained, organic-rich and rapidly-accumulating sediments.Organic carbon and sulfate decrease with depth in the sediment whereas ammonia and alkalinity increase. In the zone of sulfate reduction (0–20 cm) the rate constants for sulfate reduction ($\text{k}{}_{\mathrm{s}}$), ammonia production ($\text{k}{}_{\mathrm{N}}$) and organic carbon decomposition ($\text{k}{}_{\mathrm{c}}$) agree within a factor of two. Our calculations indicate, however, that this is fortuitous since the observed decrease in paniculate organic carbon is insufficient to account for the sulfate consumption. Sulfate must also be consumed by reaction with methane diffusing up from the underlying sediments. The rate constant for sulfate reduction using particulate organic carbon is lower than a modelled rate encompassing all organic species, including methane.The rate constant for ammonia production ($\text{k}{}_{\mathrm{N}}$) decreases by an order of magnitude when sulfate is completely depleted and methane production dominates.Thermodynamic calculations suggest that the interstitial waters are saturated or supersaturated with respect to all forms of iron ‘monosulfides’, apatite and rhodochrosite.  相似文献   

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

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

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

Concentration of Mn and separation from Fe in sediments—I. Kinetics and stoichiometry of the reaction between birnessite and dissolved Fe(II) at 10°C     

Dieke Postma 《Geochimica et cosmochimica acta》1985,49(4):1023-1033

Redox reactions between Fe²⁺ in solution and Mn-oxides are proposed as a mechanism for concentration of Mn in sediments both during weathering and diagenesis in marine sediments, e.g. the formation of Mn-nodules.If such a mechanism is to be effective, then reaction rates between Fe²⁺ and Mn-oxides should be fast. The kinetics and stoichiometry of the reaction between dissolved Fe²⁺ and synthetically prepared birnessite (Mn₇O₁₃·5H₂O) were studied experimentally in the pH range 3–6.Results show a stoichiometry which at pH < 4 conforms to a simple reaction between Fe²⁺ and birnessite, releasing Mn²⁺ and Fe³⁺ to the solution. At pH > 4 FeOOH is precipitated and excess Fe²⁺ consumption compared to the theoretical stoichiometry is observed. The excess Fe²⁺ consumption is not due to a formation of a quantitative MnOOH layer but rather to adsorption.Reaction kinetics are very fast at pH < 4 and change at pH 4 to a slower mechanism. At pH > 4 the reaction is fast initially until 17% of the bimessite has dissolved and changes then to a slower stage. The later stage can be described by the equation: $\text{J = km}{}_0\text{(H}{}^{\mathrm{+}}\text{)}{}^{\mathrm{?0.45}}\text{[Fe}{}^{\mathrm{2+}}\text{]}{}^{\mathrm{\gamma }}\text{(}\text{m}\text{m}{}_0\text{)}{}^{\mathrm{\beta }}$ where J is the overall rate of Mn²⁺ release, m₀ and m the mass of birnessite at time t = 0 and t > 0, β = 6.76?0.94 pH and γ has values of 0.76 at pH 5 and 0.39 at pH 6. The rate constant k is 7.2·10^?7 moles s^?1 g^?1 (moles/1)^?0.31 at pH 5 and 9.6·10^?8 moles s^?1 g^?1 (moles/1)^0.06 at pH 6.Diffusion calculations show that the rate is controlled by surface reaction and it is tentatively proposed that the availability of vacancies in octahedral [MnO₆]sheets of the birnessite surface could be rate controlling. It is concluded that reactions between Fe(II) and birnessite, and probably other Mn-oxides, are fast enough to be important in natural environments at the earth surface.  相似文献   

Olivine/silicate melt partitioning of germanium: an example of a nearly constant partition coefficient     

C.J Capobianco  E.B Watson 《Geochimica et cosmochimica acta》1982,46(2):235-240

The partitioning of germanium between forsterite (Fo) and liquids in the diopside-anorthiteforsterite join was investigated by electron microprobe analysis of Ge-doped samples equilibrated at 1300°–1450°C. Germanium is somewhat incompatible in Fo relative to the haplobasaltic melts, with a grand mean for all simple partition coefficients (D_Fo-l^Ge) of 0.68 ± 0.06. For the melt composition range studied, D_Fo-l^Ge is virtually constant in isothermal series of experiments, and shows only minor overall temperature dependence. The exchange reaction partition coefficient $\text{K}{}_{\mathrm{D}}\text{= (}\text{Mg}{}_2\text{GeO}{}_4\text{)}{}_{\mathrm{Fo}}\text{(SiO}{}_2\text{)}{}_{\mathrm{l}}\text{(Mg}{}_2\text{SiO}{}_4\text{)}{}_{\mathrm{Fo}}\text{(GeO}{}_2\text{)}{}_{\mathrm{l}}$] is near unity in all cases, with a grand mean of 0.93 ± 0.11. One exploratory run at 20 kbar yielded a distinctly lower partition coefficient (D_Fo-l^Ge = 0.54 ± 0.04), which confirms the negative pressure dependence predicted by the thermodynamics of Ge ai Si exchange.These new data indicate that absolute Ge enrichment must occur in terrestrial magmas undergoing olivine fractionation, while $\text{Ge}\text{Si}$ remains nearly constant.  相似文献   

Methane solubilities in multisalt solutions     

Patricia A. Byrne  Ronald K. Stoessell 《Geochimica et cosmochimica acta》1982,46(11):2395-2397

Solubilities of methane in multisalt solutions at 550 psia and 25°C can be predicted from single-salt salting coefficients. The ionic strength contribution of the ith salt, I_i, is multiplied by its molal salting coefficient, k_mi, in the following summation over all salts: where m_o and m_s are molal methane solubilities in distilled water and the salt solution, respectively, at the T, P and methane fugacity of interest.This equation predicts methane solubility in multisalt brines containing Na⁺, K⁺, Mg⁺², Ca⁺², Cl^?, SO₄^?2 and CO₃^?2 ions. k_mi values reported by Stoessell and Byrne (1982b) can be used in solubility predictions in brines at earth surface conditions. Prediction in reservoir brines would require determination of k_mi, for the different salts at reservoir temperatures and pressures.  相似文献   

The effect of sulfate on aluminum concentrations in natural waters: some stability relations in the system Al₂O₃-SO₃-H₂O at 298 K     

Darrell Kirk Nordstrom 《Geochimica et cosmochimica acta》1982,46(4):681-692

While gibbsite and kaolinite solubilities usually regulate aluminum concentrations in natural waters, the presence of sulfate can dramatically alter these solubilities under acidic conditions, where other, less soluble minerals can control the aqueous geochemistry of aluminum. The likely candidates include alunogen, Al₂(SO₄)₃ · 17H₂O, alunite, KAl₃(SO₄)₂(OH)₆, jurbanite, Al(SO₄)(OH) · 5H₂O, and basaluminite, Al₄(SO₄)(OH)₁₀ · 5H₂O. An examination of literature values shows that the log $\text{K}{}_{\mathrm{sp}}\text{= ?85.4}$ for alunite and log $\text{K}{}_{\mathrm{sp}}\text{= ?117.7}$ for basaluminite. In this report the log $\text{K}{}_{\mathrm{sp}}\text{= ?7.0}$ is estimated for alunogen and log $\text{K}{}_{\mathrm{sp}}\text{= ?17.8}$ is estimated for jurbanite. The solubility and stability relations among these four minerals and gibbsite are plotted as a function of pH and sulfate activity at 298 K. Alunogen is stable only at pH values too low for any natural waters (<0) and probably only forms as efflorescences from capillary films. Jurbanite is stable from $\text{pH < 0}$ up to the range of 3–5 depending on sulfate activity. Alunite is stable at higher pH values than jurbanite, up to 4–7 depending on sulfate activity. Above these pH limits gibbsite is the most stable phase. Basaluminite, although kinetically favored to precipitate, is metastable for all values of pH and sulfate activity. These equilibrium calculations predict that both sulfate and aluminum can be immobilized in acid waters by the precipitation of aluminum hydroxysulfate minerals.Considerable evidence supports the conclusion that the formation of insoluble aluminum hydroxy-sulfate minerals may be the cause of sulfate retention in soils and sediments, as suggested by Adams and Rawajfih (1977), instead of adsorption.  相似文献   

Amorphous silica solubilities V. Predictions of solubility behavior in aqueous mixed electrolyte solutions to 300°C     

William L Marshall  Chen-Tung A Chen 《Geochimica et cosmochimica acta》1982,46(2):289-291

Solubilities of amorphous silica in several aqueous electrolyte solutions up to 300°C (Marshall, 1980a; Chen and Marshall, 1982) fitted the Setchénow equation, $\text{log(}\text{s}{}^0\text{s}\text{) = D·m}$ as described earlier (Marshall, 1980b) where s⁰ and s are molal solubilities of silica in pure water and salt solution, respectively, m is the molality of salt, and D is a proportionality constant related to the particular salt and temperature. It is now shown that, to a first approximation, the D parameters for various salts at the same temperature are additive. For instance, D(NaCl) ? D(KCl) = D(NaNO₃) ? D(KNO₃) or D(MgSO₄) = D(MgCl₂) + D(Na₂S0₄) ? 2D(NaCl). It also follows that $\text{(}\text{s}{}_0\text{s}\text{) =}\text{∑}\text{i}\text{(D}{}_{\mathrm{i}}\text{m}{}_{\mathrm{i}}\text{)}$.This additivity principle was used to estimate amorphous silica solubilities in mixed NaCl-Na₂SO₄, NaCl-MgCl₂, NaCl-MgSO₄, Na₂SO₄-MgCl₂, Na₂SO₄-MgSO₄, and MgCl₂-MgSO₄ aqueous solutions up to 300°C. The method produces results that agree reasonably well with experimental values and would be useful for predicting silica solubilities, for example, in seawater and its hydrothermal concentrates and in geothermal energy applications.  相似文献   

Fractionation of stable carbon isotopes by marine phytoplankton     

William W. Wong  William M. Sackett 《Geochimica et cosmochimica acta》1978,42(12):1809-1815

Stable carbon isotope fractionation by seventeen species of marine phytoplankton, representing the classes of Bacillariophyceae, Chlorophyceae, Prasinophyceae, Chrysophyceae, Haptophyceae and Dinophyceae have been determined in laboratory culture experiments using bicarbonate enriched artificial sea water. The values (Δ_HCO3^? = δ¹³C of algae vs HCO₃^?) range from ?22.1 to ?35.5%. Nitzschia closterium shows the smallest fractionation of ? 22.1% and Isochrysis galbana, the greatest of ?35.5%,. Since these algae were cultured under identical laboratory conditions, the wide range of Δ_HCO3^? values is seemingly due to the presence of different metabolic pathways within these organisms.A temperature dependent fractionation of 0.36% per °C with decreasing temperatures was measured for Skeletonema costatum whereas, smaller temperature dependencies of ?0.13, +0.15 and ?0.07%. per °C were observed for Dunaliella sp., Monochrysis lutheri and Glenodinium foliaceum, respectively.The consistency of values of Skeletonema costatum, Dunaliella sp. and Monochrysis lutheri grown at salinities of 22, 26, 32 and 36% indicates that natural salinity variations have negligible effects on the isotopic composition of marine phytoplankton.  相似文献   

Precambrian sulfur isotopes and a possible role for sulfite in the evolution of biological sulfate reduction     

G.W. Skyring  T.H. Donnelly 《Precambrian Research》1982,17(1):41-61

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

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

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

Partitioning and transport of metals across the O2H2S interface in a permanently anoxic basin: Framvaren Fjord,Norway     

Lucinda Jacobs  Steven Emerson  Jens Skei 《Geochimica et cosmochimica acta》1985,49(6):1433-1444

The geochemical processes operating on metals in anoxic marine waters influence metal mobility and mode of transport to the sediments in a manner different from that observed in oxic regimes. In order to better understand these processes, dissolved and particulate Mn, Fe, Co, Ni, Cu, Zn, and Cd concentrations were determined in the water column of a permanently anoxic basin, Framvaren Fjord, Norway. Class specific behavior determines the degree to which these metals are involved in the processes of redox cycling at the $\text{O}{}_2\text{H}{}_2\text{S}$ interface and metal sulfide precipitation in the sulfidic water. Metal sulfide precipitation influences the magnitude of metal enrichment in the sediments. The transition metals, Mn, Fe, and Co, show active involvement in redox cycling, characterized by dissolved maxima just below the $\text{O}{}_2\text{H}{}_2\text{S}$ interface. Nickel concentrations appear unaffected by processes influencing the profiles of the other metals. The metals, Cu, Zn, and Cd, display a dramatic solubility decrease across the interface, are not involved in redox cycling, and are enriched in the sediments relative to a lithogenic component by factors of 11, 105, and 420, respectively. Ion activity products of the metals and sulfide provide evidence that chemical equilibria with a pure metal sulfide solid phase is not the dominant process controlling dissolved metal concentrations in the sulfide containing waters.  相似文献   

Aqueous oxidation-reduction kinetics associated with coupled electron-cation transfer from iron-containing silicates at 25°C     

Art F. White  Andy Yee 《Geochimica et cosmochimica acta》1985,49(5):1263-1275

Mechanisms and kinetics of aqueous $\text{Fe}{}^{\mathrm{+2}}\text{Fe}{}^{\mathrm{+3}}$ 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   

Water and magmas; a mixing model     

C.Wayne Burnham 《Geochimica et cosmochimica acta》1975,39(8):1077-1084

A model for the mixing of H₂O and silicate melts has been derived from the experimentally determined effects of H₂O on the viscosity (fluidity), volumes, electrical conductivities, and especially the thermodynamic properties of hydrous aluminosilicate melts. It involves primarily the reaction of H₂O with those O^?2 ions of the melt that are shared (bridging) between adjacent (Al, Si)O₄ tetrahedra to produce OH^? ions. However, in those melts that contain trivalent ions in tetrahedral coordination, such as the Al³⁺ ion in feldspathic melts, the model further involves exchange of a proton from H₂O with a non-tetrahedrally coordinated cation that must be present to balance the net charge on the AlO₄ group. This cation exchange reaction, which goes essentially to completion, results in dissociation of the H₂O and is limited only by the availability of H₂O and the number of exchangeable cations per mole of aluminosilicate.In the system NaAlSi₃O₈-H₂O, upon which this thermodynamic model is based, there is 1 mole of exchangeable cations (Na⁺) per mole (GFW) of NaAlSi₃O₈, consequently ion exchange occurs for H₂O contents up to a 1:1 mole ratio (X^m_w = mole fraction H₂O = 0.5). For mole fractions of H₂O greater than 0.5, no further exchange can occur and the reaction with additional bridging oxygens of the melt produces 2 moles of associated OH^? ions per mole of H₂O dissolved. These reactions lead to a linear dependence of the thermodynamic activity of H₂O (a^m_w) on the square of its mole fraction (X^m_w) for values of X^m_w, up to 0.5 and an exponential dependence on X^m_w at higher H₂O contents. Thus, for values of $\text{X}{}^{\mathrm{m}}{}_{\mathrm{w}}\text{? 0.5, a}{}^{\mathrm{m}}{}_{\mathrm{w}}\text{= k(X}{}^{\mathrm{m}}{}_{\mathrm{w}}\text{)}{}^2$, where k is a Henry's law constant for the dissociated solute.Extension of the thermodynamic model for NaAlSi₃O₈-H₂O to predict H₂O solubilities and other behavior of compositionally more complex aluminosilicate melts (magmas) requires placing these melts on an equimolal basis with NaAlSi₃O₈. This is readily accomplished using chemical analyses of quenched glasses by normalizing to the stoichiometric requirements of NaAlSi₃O₈, first in terms of equal numbers of exchangeable cations for mole fractions of H₂O up to 0.5 and secondly in terms of 8 moles of oxygen for higher H₂O contents. Chemical analyses of three igneous-rock glasses, ranging in composition from tholeiitic basalt to lithium-rich pegmatite, were thus recast and the experimental H₂O solubilities were computed on this equimolal basis. The resulting equimolal solubilities are all the same, within experimental error, as the solubility of H₂O in NaAlSi₃O₈ melt calculated from the thermodynamic relations.The equivalence of equimolal solubilities implies that the Henry's law constant (k), which is a function of temperature and pressure, is independent of aluminosilicate composition over a wide range. Moreover, as a consequence of the Gibbs-Duhem relation and the properties of exact differentials, it is clear that the silicate components of the melt, properly defined, mix ideally. Thus, a relatively simple mixing model for H₂O in silicate melts has led to a quantitative thermodynamic model for magmas that has far-reaching consequences in igneous petrogenesis.  相似文献   

Constantes de formation des complexes hydroxydés de l'aluminium en solution aqueuse de 20 a 70°C     

Yves Couturier  Gil Michard  Gérard Sarazin 《Geochimica et cosmochimica acta》1984,48(4):649-659

Stability constants of hydroxocomplexes of Al(III):Al(OH)²⁺ and A1(OH)₄^? have been measured in the 20–70°C temperature range by reactions involving only dissolved species. The stability constant ${}^1\text{K}{}_1$ of the first complex ion is studied by measuring pH of solutions of aluminium salts at several concentrations. ${}^1\text{β}{}_4$ of aluminate ion is deduced from equilibrium constants of the reaction between the trioxalato aluminium (III) complex ion and Al³⁺ in acid medium, and between the same complex ion and A1(OH)₄^? in alkaline medium. The K values and the associated ΔH are ${}^1\text{K}{}_1\text{= 10}{}^{\mathrm{?5.00}}$ and ΔH₁ = 11.8 Kcal; ${}^1\text{β}{}_4\text{= 10}{}^{\mathrm{?22.20}}$ and ΔH₄ = 42.45 Kcal. These last results are not in agreement with the values of recent tables for $\text{ΔG}{}^0\text{?}$ and $\text{ΔH}{}^0\text{?}$ of Al³⁺ and Al(OH)₄^?. We suggest a consistent set of data for dissolved and solid Al species and for some aluminosilicates.  相似文献   

A valid Margules formulation for an asymmetric ternary solution: revision of the olivine-ilmenite thermometer,with applications     

David J Andersen  Donald H Lindsley 《Geochimica et cosmochimica acta》1981,45(6):847-853

The olivine-ilmenite thermometer of Andersen and Lindsley (1979) was based on an incorrect formulation for the excess free energy of an asymmetric ternary solution. A valid formulation is derived and used to revise the parameters of the olivine-ilmenite thermometer. For olivine and ilmenite that have equilibrated above 700°C, temperature can be calculated from: $\text{T(°C) = ?273 +¦-12549 + P[0.03X}{}_{\mathrm{fa}}\text{+ 0.01099(X}{}_{\mathrm{gk}}\text{?X}{}_{\mathrm{il}}\text{)?0.062] + 10496 X}{}_{\mathrm{fa}}\text{+ 5767(X}{}_{\mathrm{gk}}\text{?X}{}_{\mathrm{il}}\text{) + X}{}_{\mathrm{hem}}\text{(38602?141550X}{}_{\mathrm{il}}\text{?47183X}{}_{\mathrm{gk}}\text{)|/[5.67?R ln K}{}_{\mathrm{D}}\text{+ 6.52X}{}_{\mathrm{fa}}\text{+ 3.09(X}{}_{\mathrm{gk}}\text{?X}{}_{\mathrm{il}}\text{) + X}{}_{\mathrm{hem}}\text{(16.49?109.46 X}{}_{\mathrm{il}}\text{?36.49X}{}_{\mathrm{gk}}\text{)]}$ with $\text{K}{}_{\mathrm{d}}\text{=}\text{(X}{}_{\mathrm{il}}\text{X}{}_{\mathrm{fo}}\text{)}\text{(X}{}_{\mathrm{gk}}\text{X}{}_{\mathrm{fa}}\text{)}$. The revised model gives W^il·gk_G = 5767?3.09T + 0.011P and ΔG_exch = 7301 ? 8.9T ? 0.047P (T in K, P in bars). Applications include Apollo 17 breccias and kimberlites.  相似文献   

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

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

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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.  相似文献   

Evaluation of deep temperatures of hydrothermal systems by a new gas geothermometer     

Franco D&#x;Amore  Costanzo Panichi 《Geochimica et cosmochimica acta》1980,44(3):549-556

The chemical composition of gas mixtures emerging in thermal areas can be used to evaluate the deep thermal temperatures. Chemical analyses of the gas compositions for 34 thermal systems were considered and an empirical relationship developed between the relative concentrations of H₂S, H₂, CH₄ and CO₂ and the reservoir temperature. The evaluated temperatures can be expressed by: $\text{t°C =}\text{24775}\text{α + β + 36.05}\text{?273}$ where $\text{α = 2 log}\text{CH}{}_4\text{CO}{}_2\text{?log}\text{H}{}_2\text{CO}{}_2\text{?3 log}\text{H}{}_2\text{S}\text{CO}{}_2$ (concentrations in % by volume) and β = 7 logP_co2  相似文献