Stenols and stanols in the oxic and anoxic waters of the Black Sea     

Robert B. Gagosian  Franz Heinzer 《Geochimica et cosmochimica acta》1979,43(4):471-486

Water samples collected from a slope station and two deep stations in the western basin of the Black Sea were analyzed for stenols and stanols by glass capillary gas chromatography. These results were used in conjuction with hydrographic, particulate organic carbon, and chlorophyll a data to better understand sterol sources and their transport and transformation mechanisms in anoxic basins.The total free sterol concentrations found in the surface waters were 450–500 ng/l dropping rapidly to values well below 100 ng/l at depths below the $\text{O}{}_2\text{H}{}_2\text{S}$ interface. In the upper 200 m of the water column a strong association of sterols with particulate matter is suggested. Structural elucidation by a gas chromatograph-mass spectrometer-computer system revealed the presence of at least sixteen different stenols and stanols in the surface waters of the Black Sea. Cholesterol, 24-methylenecholesterol and 24-methylcholesta-5,22-dien-3β-ol were the major sterols in the surface waters. Cholesterol and 24-ethylcholesterol both exhibited a subsurface maximum at the $\text{O}{}_2\text{H}{}_2\text{S}$ interface. In the anoxic deep waters (200–2000 m) only cholesterol and 24-ethylcholesterol were found. Two stenols were found that have not been reported in seawater: a C₂₆ stenol with a saturated C₇H₁₅ side chain (presumably 24-norcholesterol) and 24-ketocholesterol. At least six 5α-stanols could be identified in the surface samples, each of them comprising about 10–20% of the concentration of the corresponding Δ5-stenol. From these comparatively high surface values the stanol concentrations drop rapidly to values near zero at the $\text{O}{}_2\text{H}{}_2\text{S}$ interface. Except for very low concentrations of 5α-cholestanol (< 4ng/l) no other stanols could be detected in the anoxic zone.From this data it appears that no detectable stenol → stanol conversion is occurring at the $\text{O}{}_2\text{H}{}_2\text{S}$ interface or in the deep anoxic waters of the Black Sea.  相似文献   

Distribution,abundance and carbon isotopic composition of gaseous hydrocarbons in Big Soda Lake,Nevada: An alkaline,meromictic lake     

Ronald S. Oremland  David J. Des Marais 《Geochimica et cosmochimica acta》1983,47(12):2107-2114

Distribution and isotopic composition (δ¹³C) of low molecular weight hydrocarbon gases were studied in Big Soda Lake (depth = 64 m), an alkaline, meromictic lake with permanently anoxic bottom waters. Methane increased with depth in the anoxic mixolimnion (depth = 20–35 m), reached uniform concentrations (55 μM/l) in the monimolimnion (35–64 m) and again increased with depth in monimolimnion bottom sediments (>400 μM/kg below 1 m sub-bottom depth). The μ¹³C[CH₄] values in bottom sediment below 1 m sub-bottom depth (<?70 per mil) increased with vertical distance up the core (δ¹³C[CH₄] = ?55 per mil at sediment surface). Monimolimnion δ¹³C[CH₄] values (?55 to ?61 per mil) were greater than most δ¹³C[CH₄] values found in the anoxic mixolimnion (92% of samples had δ¹³C[CH₄] values between ?20 and ?48 per mil). No significant concentrations of ethylene or propylene were found in the lake. However ethane, propane, isobutane and n-butane concentrations all increased with water column depth, with respective maximum concentrations of 260, 80, 23 and 22 nM/l encountered between 50–60 m depth. Concentrations of ethane, propane and butanes decreased with depth in the bottom sediments. Ratios of $\text{CH}{}_4\text{[C}{}_2\text{H}{}_6\text{+ C}{}_3\text{H}{}_8\text{]}$ were high (250–620) in the anoxic mixolimnion, decreased to ~161 in the monimolimnion and increased with depth in the sediment to values as high as 1736. We concluded that methane has a biogenic origin in both the sediments and the anoxic water column and that C₂-C₄ alkanes have biogenic origins in the monimolimnion water and shallow sediments. The changes observed in δ¹³C[CH₄] and $\text{CH}{}_4\text{(C}{}_2\text{H}{}_6\text{+ C}{}_3\text{H}{}_8\text{)}$ with depth in the water column and sediments are probably caused by bacteria] processes. These might include anaerobic methane oxidation and different rates of methanogenesis and C₂ to C₄ alkane production by microorganisms.  相似文献   

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   

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   

Light hydrocarbons in Red Sea brines and sediments     

Roger A. Burke  James M. Brooks  William M. Sackett 《Geochimica et cosmochimica acta》1981,45(5):627-634

Light hydrocarbon (C₁-C₃) concentrations in the water from four Red Sea brine basins (Atlantis II, Suakin, Nereus and Valdivia Deeps) and in sediment pore waters from two of these areas (Atlantis II and Suakin Deeps) are reported. The hydrocarbon gases in the Suakin Deep brine (T = ~ 25°C, $\text{Cl}{}^{\mathrm{?}}\text{= ~ 85‰}$, $\text{CH}{}_4\text{=}\text{~ 71}\text{1}$) are apparently of biogenic origin as evidenced by $\text{C}{}_1\text{(C}{}_2\text{+ C}{}_3$) ratios of ~ 1000. Methane concentrations (6–8 μl/l) in Suakin Deep sediments are nearly equal to those in the brine, suggesting sedimentary interstitial waters may be the source of the brine and associated methane.The Atlantis II Deep has two brine layers with significantly different light hydrocarbon concentrations indicating separate sources. The upper brine (T = ~ 50°C, $\text{Cl}{}^{\mathrm{?}}\text{= ~ 73‰}$, CH₄ = ~ 155 μl/l) gas seems to be of biogenic origin [$\text{C}{}_1\text{(C}{}_2\text{+ C}{}_3\text{) = ~1100}$], whereas the lower brine (T = ~ 61°C, $\text{Cl}{}^{\mathrm{?}}\text{= ~ 155‰}$, CH₄ = ~ 120μl/l) gas is apparently of thermogenic origin [$\text{C}{}_1\text{(C}{}_2\text{+ C}{}_3\text{) = ~ 50}$]. The thermogenic gas resulting from thermal cracking of organic matter in the sedimentary column apparently migrates into the basin with the brine, whereas the biogenic gas is produced in situ or at the seawater-brine interface. Methane concentrations in Atlantis II interstitial waters underlying the lower brine are about one half brine concentrations; this difference possibly reflects the known temporal variations of hydrothermal activity in the basin.  相似文献   

Liquidus relationships in the system CaCO₃Ca(OH)₂CaS and the solubility of sulfur in carbonatite magmas     

George R. Helz  Peter J. Wyllie 《Geochimica et cosmochimica acta》1979,43(2):259-265

CaCO₃Ca(OH)₂CaS 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   

Speciation of boron with Cu2+, Zn2+, Cd2+ and Pb2+ in 0.7 M KNO3 and in sea-water     

Constant M.G. van den Berg 《Geochimica et cosmochimica acta》1984,48(12):2613-2617

The stability constants, $\text{K}{}^1{}_{\mathrm{MB}}$, for borate complexes with the ions of Cu, Pb, Cd and Zn are determined in this work by DPASV in 0.7 M KNO₃ at metal concentrations of 10^?7 M. The acidity constants of the Cu²⁺ ion are determined by DPASV in the same conditions. The following values for log $\text{K}{}^1{}_{\mathrm{MB}}$ () have been obtained: CuB: 3.48, CuB₂: 6.13, PbB: 2.20, PbB₂: 4.41, ZnB: 0.9, ZnB₂: 3.32, CdB: 1.42, and CdB₂: 2.7, while the values for the acidity constants of Cu are $\text{pK}{}^1{}_{\mathrm{CuOH}}\text{= 7.66}$ and . At the low concentration of boron in 35%. S sea-water complexes with borate represent only about 0.2% Cu, 0.03% Pb, 0.02% Zn and 0.003% Cd.  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   

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   

New gas geothermometers for geothermal exploration—calibration and application     

Stefán Arnórsson  Einar Gunnlaugsson 《Geochimica et cosmochimica acta》1985,49(6):1307-1325

Calibration of five gas geothermometers is presented, three of which used CO₂, H₂S and H₂ concentrations in fumarole steam, respectively. The remaining two use $\text{CO}{}_2\text{H}{}_2$ and $\text{H}{}_2\text{S}\text{H}{}_2$ ratios. The calibration is based on the relation between gas content of drillhole discharges and measured aquifer temperatures. After establishing the gas content in the aquifer, gas concentrations were calculated in steam formed by adiabatic boiling of this water to atmospheric pressure to obtain the gas geothermometry functions. It is shown that the concentrations of CO₂, H₂S and H₂ in geothermal reservoir waters are fixed through equilibria with mineral buffers. At temperatures above 230°C epidote + prehnite + calcite + quartz are considered to buffer CO₂. Two buffers are involved for H₂S and H₂ and two functions are, therefore, presented for the geothermometers involving these gases. For waters containing less than about 500 ppm chloride and in the range 230–300°C pyrite + pyrrholite + epidote + prehnite seem to be involved, but pyrite + epidote + prehnite + magnetite or chlorite for waters above 300°C and waters in the range 230–300°C, if containing over about 500 ppm.The gas geothermometers are useful for predicting subsurface temperatures in high-temperature geothermal systems. They are applicable to systems in basaltic to acidic rocks and in sediments with similar composition, but should be used with reservation for systems located in rocks which differ much in composition from the basaltic to acidic ones. The geothermometry results may be used to obtain information on steam condensation in upflow zones, or phase separation at elevated pressures.Measured aquifer temperatures in drillholes and gas geothermometry temperatures, based on data from nearby fumaroles, compare well in the five fields in Iceland considered specifically for the present study as well as in several fields in other countries for which data were inspected. The results of the gas geothermometers also compare well with the results of solute geothermometers and mixing models in three undrilled Icelandic fields.  相似文献   

Densities of Na2O-K2O-CaO-MgO-FeO-Fe2O3-Al2O3-TiO2-SiO2 liquids: New measurements and derived partial molar properties     

《Geochimica et cosmochimica acta》1987,51(11):2931-2946

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The role of CO₂ in the chemical modification of deep continental crust     

William E. Glassley 《Geochimica et cosmochimica acta》1983,47(3):597-616

Compositional differences between granulite facies rocks and equivalent amphibolite facies rocks and the observation of CO₂-rich fluid inclusions in granulites, have led to the suggestion that CO₂ must play a role in modifying the composition of deep continental crust. How CO₂ effects this change has remained unclear. Using the thermodynamic properties of aqueous ions in a fluid of evolving $\text{CO}{}_2\text{H}{}_2\text{O}$ ratio, it is possible to model the incongruent dissolution of feldspars under conditions appropriate for granulite facies metamorphism. The results demonstrate that dissolution will be strongly enhanced at high $\text{CO}{}_2\text{H}{}_2\text{O}$ ratios, with ion solubilities being Na⁺ >K⁺ ? Ca⁺⁺. This enhancement is compatible with the reported compositional contrasts between granulite and amphibolite facies rock, but requires large fluid volumes.To test the dissolution model, a detailed field and petrologic study was conducted in a well exposed granulite facies terrane in West Greenland. Strong correlation between fluid composition and bulk rock chemistry can be documented; CO₂-rich regions contain rocks which consistently have low ratios, while H₂O-rich regions consistently have high ratios. Magnetite rims on sulfide grains are ubiquitous in high regions and are absent in high regions, and they provide evidence that CO₂ was introduced into the region. These correlations and observations are predictable from the properties of the dissolution process. These considerations, along with observations regarding graphite petrogenesis, provide strong arguments that the total fluid volume interacting with the rock during metamorphism was very large, in some cases equaling or exceeding total rock volume. Such large fluid volumes can lead to significant compositional modification of the crust, and will mask the original protolith chemistry. Such processes should lead to Ca- and Al-enriched, Na-, K-, S- and Si-depleted residues in the deep crust.  相似文献   

Some mineral stability relations in the system CaOMgOSiO₂H₂OHCl     

R.W Luce  G.L Cygan  J.J Hemley  W.M D&#x;angelo 《Geochimica et cosmochimica acta》1985,49(2):525-538

Mineral-aqueous solution equilibria for the assemblages talc-quartz, tremolite-talc-quartz, diopside-tremolite-quartz, wollastonite-diopside-quartz and wollastonite-quartz have been studied at 2 kb total pressure, 500° to 700°C and chloride concentrations from 0.03 to 6.0 molal. Most work was at 1 m chloride. Both buffered and unbuffered data were obtained and a recalibration of the Ag-AgCl buffer is presented. Log equilibrium quotients at 500°, 600° and 700°C are respectively: Ta-Qz () 2.57, 1.71, 0.73; Tr-Ta-Qz and Di-Tr-Qz () 4.98, 3.99, 2.21 and 7.29, 5.30, 3.56; WoDi-Qz () 3.30, 3.00, 2.79: Wo-Qz () 5.15, 3.95, 2.68. Mineral stability fields plotted in terms of these concentration data more tangibly represent the compositional character of real systems and the mass transfer capabilities of their fluids than do the analogous theoretical activity diagrams.Overall dissociation constants of MgCl₂ and CaCl₂ were calculated from the experimental data using the calculated ionic activity constants for the reactions and the established dissociation constants of HCl. The negative log values are respectively: 3.88. 6.63, 9.20 for CaCl₂ and 4.60, 7.54, 10.37 for MgCl₂ at 500°, 600° and 700°C, 2 kb. The Ca values are about an order of magnitude more positive than the conductance-derived values by Frantz and Marshall (1982).The phase relations developed in this study have application to the genesis of talc, tremolite, and diopside-bearing assemblages in some regional metamorphic rocks, but more specifically to the calcsilicate skarn assemblages of many metasomatic aureoles. The equilibrium fluids are characterized by high concentrations of Ca relative to Mg and increasing $\text{Ca}\text{Mg}$ ratios with decreasing temperatures. The stability fields of talc, tremolite, and quartz expand relative to those of diopside and wollastonite with decreasing temperature, hence their more common appearance as retrograde products in skarn systems.  相似文献   

The surface chemistry of δMnO2 in major ion sea water     

L.S Balistrieri  J.W Murray 《Geochimica et cosmochimica acta》1982,46(6):1041-1052

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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   

Correction of ground-water chemistry and carbon isotopic composition for effects of CO₂ outgassing     

F.J. Pearson  Donald W. Fisher  L.N. Plummer 《Geochimica et cosmochimica acta》1978,42(12):1799-1807

Direct measurements on water samples from several CO₂-charged warm springs are significantly higher than values calculated from field pH and alkalinity (and other constituents). In addition, calcite saturation indices calculated from field pH and solution composition indicated supersaturation in samples which, on the basis of hydrogeologic concepts, should be near saturation or undersaturated. We attribute these discrepancies to uncertainties in field pH, resulting from CO₂ outgassing during pH measurement. Because samples for direct measurement can be taken with minimal disturbance to the water chemistry, we have used the measured to back calculate an estimate of the field pH and the carbon isotopic composition of the water before outgassing. By reconstructing water chemistry in this way, we find generally consistent grouping of $\text{δ}{}^{13}\text{C}$, pH, and degree of calcite saturation in samples taken from the same source at different times, an observation which we expect based on our understanding of the hydrogeology and geochemistry of the ground-water systems. This suggests that for very careful geochemical work, particularly on ground-waters much above ambient temperature, measurements may provide more information on the system and a better estimate of its state of saturation with respect to carbonate minerals than can field measurements of pH.  相似文献   

A systematic deviation from Na-K-Ca geothermometer below 75°C and above 10−4 atm Pco2     

Tomáš Pačes 《Geochimica et cosmochimica acta》1975,39(4):541-544

If the temperature of ground water is below 75°C and the partial pressure of CO₂ in the aquifer is above 10^?4 atm, a chemical steady-state between water and felsic rocks (rather than chemical equilibrium) may be maintained. The temperature of water in the aquifer may be estimated using a modified form of the Na-K-Ca geothermometer from, . where the departure of the steady-state from equilibrium, $\text{I}$, is a function of : .  相似文献   

Solubility product of galena at 298°K: A possible explanation for apparent supersaturation in nature     

A.D. Uhler  G.R. Helz 《Geochimica et cosmochimica acta》1984,48(6):1155-1160

The synthetic chelating agent ethylenediaminetetraacetic acid (EDTA) has been used to evaluate the stoichiometric solubility product of galena (PbS) at 298°K: $\text{K}{}_{\mathrm{s2}}\text{=}{}^{\mathrm{a}}\text{Pb}{}^{\mathrm{2+}}{}^{\mathrm{a}}\text{HS}{}^{\mathrm{?}}{}^{\mathrm{a}}\text{H}{}^{\mathrm{+}}$ This method circumvents the possible uncertainties in the stoichiometry and stability of lead sulfide complexes. At infinite dilution, $\text{Log K}{}_{\mathrm{s2}}\text{= ?12.25 ±0.17}$, and at an ionic strength corresponding to seawater ($\text{I = 0.7 M}$), $\text{Log K}{}_{\mathrm{s2}}\text{= ?11.73 ± 0.05}$. Using the value of $\text{K}{}_{\mathrm{s2}}$ at infinite dilution, and the free energies of formation of HS^? and Pb²⁺ at 298°K (literature values), the free energy of formation of PbS at 298°K is computed to be $\text{?79.1 ± 0.8 KJ/mol (?18.9 Kcal/mol)}$. Galena is shown to be more than two orders of magnitude more soluble than indicated by calculations based on previous thermodynamic data.  相似文献   

Plutonium and americium in anoxic marine sediments: Evidence against remobitization     

R. Carpenter  T.M. Beasley 《Geochimica et cosmochimica acta》1981,45(10):1917-1930

^{239 + 240}Pu activities of 100–450dpm/kg are found down to 15–18 cm in anoxic Saanich Inlet sediments, with a subsurface maximum in undisturbed deposits. Integrated ^{239 + 240}Pu inventories which overlap delivery estimates are present both in two cores of anoxic sediments from Saanich Inlet and in one core of oxic sediments 65 km away in Dabob Bay, Washington. ${}^{241}\text{Am}{}^{\mathrm{239\; +\; 240}}\text{Pu}$ ratios in Saanich Inlet sediments overlap ratios in unfractionated midnorthern latitude fallout, in oxic sediments from the Washington continental shelf, and in anoxic sediments from two basins off southern California and Mexico. The ${}^{\mathrm{239\; +\; 240}}\text{Pu}{}^{137}\text{Cs}$ ratios in three intervals of Saanich Inlet sediments are also in agreement with ratios previously reported for oxic coastal marine sediments. The Pu inventories, the $\text{Am}\text{Pu}$ and $\text{Pu}\text{Cs}$ ratios, and the Saanich Inlet Dabob Bay comparison all argue that Pu is not rapidly remobilized in anoxic sediments.The subsurface ^{239 + 240}Pu activity maximum is not in agreement with the historical record of peak Pu fallout in 1963–1964 unless our ²¹⁰Pb-derived sedimentation rates are incorrectly high. However, they are in good agreement with previous ²¹⁰Pb and varve chronologies in Saanich Inlet, and also give reasonable dates for times when ^{239 + 240}Pu and SNAP-9A supplied ²³⁸Pu first appear in the sediments. We conclude they properly date the maximum in sedimentary ^{239 + 240}Pu activity at 1970–1973, and seek explanations for the 7–10yr time lag after peak fallout.^{239 + 240}Pu inventories in one core from the eastern basin of the Cariaco Trench and in two cores from Golfo Dulce. an anoxic basin off the Pacific coast of Costa Rica, are also in reasonable agreement with fallout delivery to these latitudes when excess ²¹⁰Pb inventories and fluxes are used to verify recovery of at least a major fraction of the most recently deposited sediments.  相似文献   

Oxygen-isotope variations in sulfate ions in the water of some Italian lakes     

Gianni Cortecci 《Geochimica et cosmochimica acta》1973,37(6):1531-1542

The results obtained by measuring the sulfate content and its $\text{O}{}^{18}\text{O}{}^{16}$ ratios through time in some volcanic, tectonic and dam Italian lakes are reported here. The variations with time of the oxygen isotopic composition of the lake waters are also reported. The measurements refer mainly to surface water; however, a few deep samples were also studied.In the case of all the lakes examined, the variations with time of the oxygen isotopic composition and of the concentration of the dissolved sulfate cannot be explained in terms of the addition and of seasonal variations of the O¹⁸ content of rainwater sulfate. Biological redox processes involving bacterial reduction of sulfate and sulfide oxidation can reasonably account for the results obtained.According to Lloyd (1967), when sulfate is formed by bacterial sulfide oxidation, 68 per cent of the sulfate oxygen is water oxygen, while 32 per cent is dissolved molecular oxygen. The isotopic enrichment of the dissolved molecular oxygen in the lake waters relative to the isotope content of the atmospheric oxygen is mainly related to the biological activity in the waters.Assuming that a stagnation period takes place during summer and fall while a period of strong bio-respiratory activity takes place during winter and spring, it follows that a small isotope fractionation effect on molecular dissolved oxygen can be expected during stagnation while a high isotope fractionation can be expected during winter and spring. The O¹⁸ content of the sulfate dissolved in volcanic and tectonic lakes varies according to this hypothesis. The fact that similar O¹⁸ contents of the dissolved sulfate are or are not found in the same period of different years is probably related to similarities or differences in the climatic conditions.The bio-physical behaviour of the Corbara dam lake is different from that of other lakes. However, because of the continuous feeding by the Tiber River, variations of the sulfate concentration and its oxygen isotopic composition can be caused by the contribution of polluted water.  相似文献