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1.
Partially serpentinized dunites and wehrlites comprise the bulk of the cumulate ultramafic unit at the North Arm Mountain massif of the Bay of Islands ophiolite complex, Newfoundland. In a suite of 59 dunites and werhlites from the base of the unit, the serpentinized portions consist of lizardite + chrysotile + brucite + (accessory) magnetite. The ratio of (lizardite + chrysotile) to brucite = ~8:2 (weight percent). Petrographic observations show that most serpentinization occurred at the expense of olivine; only limited amounts of clinopyroxene were serpentized. An estimated volume increase of 32% accompanied serpentinization of the peridotites. Reconstructions of the primary modal proportions of wehrlites (made taking this volume increase into account) contain an average of 6% more clinopyroxene and 6% less olivine than do modal reconstructions that ignore the volume increase. Mass balance calculations provide no clear evidence for appreciable metasomatism of Al2O3, CaO, FeO, MgO, or SiO2 during Serpentinization. The presence of brucite, the evidence that most serpentinization occurred at the expense of olivine, and the lack of appreciable metasomatism, suggest that the primary reaction that controlled serpentinization of the peridotites is: 2Mg2SiO2 + 3H2O ? Mg3Si2O5(OH)4 + Mg(OH)2. olivine added serpentine brucite  相似文献   

2.
Speciation of aqueous magnesium in the system MgO-SiO2-H2O-HCl in supercritical aqueous fluids has been investigated using standard rapid-quench hydrothermal techniques and a modification of the Ag + AgCl buffer method (Frantz and Eugster, 1973. Am. J. Sci.267, 268–286). A concentric double-capsule charge was utilized. The outer gold capsule contained the assemblage talc + quartz + Ag + AgCl + H2O-MgCl2 fluid; the inner platinum capsule, Ag + AgCl + H2O-HCl fluid. During the experiments, ?H2 and thus ?HCl equilibrated between the two capsules. After quenching, measurement of the chloride concentration in the fluid in the inner capsule and total magnesium in the fluid in the outer capsule defines the concentrations of HCl and Mg that coexist with talc + quartz in the outer capsule. Changes in the measured molality of HCl as a function of the total magnesium concentration at constant P and T were used to identify the predominant species of magnesium in the hydrothermal fluid. Experimental results showed that at 2000 bar, MgCl°2 is the predominant species above 550°C and Mg2+, below 400°C. Data at intermediate temperatures when combined with the dissociation constant for HCl were used to obtain the dissociation constant for MgCl°2. The results of these experiments were combined with results from experiments using Ag + AgCl in conjunction with the oxygen buffer, hematite-magnetite, to obtain the equilibrium constant for the reaction 13 Talc + 2HC1° H2O MgCl°2 + 43 Quartz + 43 H2O from which the difference in Gibbs free energy of MgCl°2 and HC1° was obtained as a function of temperature at 1000, 1500 and 2000 bar pressure, Solubility constants for brucite. forsterite, chrysotile, and talc were calculated.  相似文献   

3.
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 (mMgCl2mHCl2) 2.57, 1.71, 0.73; Tr-Ta-Qz and Di-Tr-Qz (mCaCl2mMgCl2mHCl2) 4.98, 3.99, 2.21 and 7.29, 5.30, 3.56; WoDi-Qz (mCaCl2mMgCl2) 3.30, 3.00, 2.79: Wo-Qz (mCaCl2mHCl2) 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 CaMg 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   

4.
Determination of amorphous silica solubility in acidified ferric nitrate solutions confirms the presence of ferric silicate complexing. A dissociation constant for the reaction:
FeH3SiO42+Fe3+ + H3SiO4?
of 10?9.8 ± 0.3 pK units at room temperature (22 ± 3°C) is obtained, in close agreement with reported values at 25°C corrected to zero ionic strength of 10?9.9 by Weber and Stumm and 10?9.5 by Olson and O'Melia. Iron-silicate complexing may be of significance to the mobilization of silica in acid waters associated with oxidizing sulphide deposits and coal strip mining and the precipitation of secondary silicate mineral phases.  相似文献   

5.
The chemistry of seawater at conditions of 350° to 500°C, 220 to 1000 bars (22 to 100 MPa) is controlled by reactions involving magnesium hydroxide sulfate (MHSH) and anhydrite. During progressive heating from 350° to 500°C at 1000 bars (100 MPa), MHSH with a MgSO4 ratio of 1.25 is formed via precipitation from solution and via reaction of solution with pre-existing anhydrite. During adiabatic expansion the MHSH extracts additional SO4 from seawater and converts to a stoichiometry in which MgSO4 = 1.16. These reactions control and greatly change the concentrations of Ca, Mg, SO4 in solution and produce significant ionizable hydrogen, attaining 11.7 mmoles kg?1 at maximum conditions.  相似文献   

6.
7.
The crystal chemistry of a naturally occurring magnesium hydroxide sulfate hydrate, MgSO4 · 13 Mg(OH2) · 13 H2O (designated MHSH(23)), and a number of existing and predicted compounds which are structurally related to MHSH(23) are discussed. An x-ray diffraction powder pattern for MHSH(23) is calculated from single crystal data to aid in the identification of this phase, recently found associated with active hydrothermal vents along the East Pacific Rise. It is suggested that this MHSH-type crystal structure can have a variable composition due to a novel chemical substitution, Mg2+ → 2 H+, which this particular structure may be able to accommodate. In relation to this, a method for determining the stoichiometry of MHSH crystals via density measurements is also proposed. Finally, the leaching properties of heated seawater, instrumental in the genesis of metalliferous deposits on the sea-floor, may be due in part to the growth of MHSH-type phases in certain seawater-rock systems.  相似文献   

8.
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 (δtidc13C = ?12,2%0) 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: δG13C = ?21,5%0; AG14C = 118%; δM13C = +2,9%0; AM14C = 28%).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   

9.
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 (DFo-lGe) of 0.68 ± 0.06. For the melt composition range studied, DFo-lGe is virtually constant in isothermal series of experiments, and shows only minor overall temperature dependence. The exchange reaction partition coefficient KD = (Mg2GeO4)Fo(SiO2)l(Mg2SiO4)Fo(GeO2)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 (DFo-lGe = 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 GeSi remains nearly constant.  相似文献   

10.
This study presents data from experiments investigating carbon isotope exchange between carbonate solution and solid calcite using carbon-13 as a tracer. All experiments were done with calcite saturated solutions and results show that a two-step adsorption-recrystallization reaction takes place. Isotope effects are caused by exchange by carbonate on the solid surface with carbon in the aqueous phase. Adsorption reactions are characterized by a maximum isotopic exchange capacity (IEC) on crystal surfaces of about 1011 reaction sites per cm2, following a second order rate law with respect to 13C concentration in solution (constant kex ? 106 cm5 mole?1 s?1 and half-life t12 = 700 s). The adsorption reaction was followed by a first order recrystallization which is characterized by a rate constant of the order of 10?8 s?1 and a t12 of 107 s. Negative isotopic gradient experiments and runs with calcite crystals in Mg2+ spiked solutions provided the preliminary basis for the characterization of the mechanisms of both proposed reactions.  相似文献   

11.
Aragonite mineralization was observed in serpentinized peridotites from the Romanche and Vema Fracture Zones in the Atlantic and the Owen Fracture Zone in the Indian Ocean, either in veins or as radial aggregates in cavities within the serpentinites. Evidence of incipient dissolution of the aragonite crystals was observed in one case. The aragonites tend to have lower Mg content (< 0.03%) and higher Sr content (> 0.95%) relative to other marine aragonites. Their 18O16O, 13C12C and 87Sr86Sr isotopic ratios suggest the aragonite was deposited at ocean floor temperatures from solutions derived from sea water circulating in fissures and fractures within the ultramafic rocks. The 18O16O ratios of the serpentines indicate serpentinization occurred at higher temperatures, probably deeper in the crust. Low-T reactions between circulating seawater and Mg-silicates (primarily serpentine and pyroxenes) caused high pH and enrichment of Mg and Ca in the solution, conditions favoring carbonate precipitation. Aragonite was formed rather than calcite presumably because the high Mg2+ concentration in the solution inhibited calcite precipitation. The high Sr content of the aragonites is probably related, at least in part, to their low temperature of formation. Opaque mineral grains containing over 8% NiO and over 40% MnO were observed concentrated along the margins of some of the aragonite veins, suggesting that Ni is one of the elements mobilized during reactions between ultramafic rocks and circulating seawater.  相似文献   

12.
Optical and analytical studies were performed on 400 N2 + CO2 gas bearing inclusions in dolomites and quartz from Triassic outcrops in northern Tunisia. Other fluids present include brines (NaCl and KCl bearing inclusions) and rare liquid hydrocarbons. At the time of trapping, such fluids were heterogeneous gas + brine mixtures. In hydrocarbon free inclusions the N2(N2+ CO2) mole ratio was determined using two different non-destructive and punctual techniques: Raman microprobe analysis, and optical estimation of the volume ratios of the different phases selected at low temperatures. In the observed range of compositions, the two methods agree reasonably well.The N2 + CO2 inclusions are divided into three classes of composition: (a) N2(N2 + CO2) > 0,57: Liquid nitrogen is always visible at very low temperature and homogenisation occurs in the range ?151°C to ? 147°C (nitrogen critical temperature) dry ice (solid CO2) sublimates between ?75°C and ?60°C; (b) 0,20 < N2(N2 + CO2) ? 0,57: liquid nitrogen is visible at very low temperature but dry ice melts on heating; liquid and gas CO2 homogenise to liquid phase between ?51°C to ?22°C; (c) N2(N2 + CO2) ? 0,20: liquid nitrogen is not visible even at very low temperature (?195°C) and liquid and gas CO2 homogenise to liquid phase between ?22°C and ?15°C. The observed phases changes are used to propose a preliminary phase diagram for the system CO2-N2 at low temperatures.Assuming additivity of partial pressures, isochores for the CO2-N2 inclusions have been computed. The intersection of these isochores with those for brine inclusions in the same samples may give the P and T of trapping of the fluids.  相似文献   

13.
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 (XH2O1fl) ranged from 1.0 to 0.2.At P < 4 kbar the stability temperature (T) of pargasite decreases with decreasing XH2O1fl at constant P. Above P ? 4 kbar stability T increases as XH2O1fl is decreased below one, passes through a T maximum and then decreases with a further decrease in XH2O1fl. This behavior is due to a decrease in the H2O content of the silicate liquid as XH2O1fl decreases. The magnitude of the T maximum increases from about 10°C (relative to the stability T for XH2O1fl= 1) at P = 5 kbar to about 30°C at P = 8 kbar, and the position of the maximum shifts from XH2O1fl ? 0.6 at P = 5 kbar to XH2O1fl? 0.4 at P = 8 kbar.The H2O content of liquid coexisting with pargasite has been estimated as a function of XH2O1fl 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 XH2O1fl at high P and T, hornblende can be an important phase in igneous processes even at relatively low H2O fugacities.  相似文献   

14.
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 d(reduction Fe)dt = kSt0.5(J+)0.5 AFeOOH1 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 d(FeS)dt = kSt1(H+)1 AFeOOH1 where d(FeS)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   

15.
The partitioning of copper and molybdenum between silicate melts and aqueous fluids has been determined at 750°C, and 1.4 Kb. The experiments were conducted in a 12 inch ID, rapid quench, cold seal pressure vessel. The aqueous and glass phase run products were analyzed by atomic absorption spectrophotometry and ion microprobe, respectively. The vapor/melt partition coefficient for copper, DvlCu, defined as the ratio of the concentrations of copper in the vapor to copper in the melt was found to be DvlCu = (9.1 ± 2.5)mvCl at NNO up to at least 4.5 moles of chlorine per kg of solution. The partition coefficient for molybdenum is equal to 2.5 ± 1.6 at NNO and QFM; its value is independent of the fluorine concentration of the melt up to at least 1.7 wt. percent fluorine, and of the chlorine concentration up to at least 4.5 moles of chlorine per kg of solution. Copper is probably present in the univalent state in both the silicate melt and in the associated aqueous phase at NNO; the most important aqueous complex of copper is probably CuCl0. Molybdenum is probably present in the aqueous phase as one or more molybdate species.  相似文献   

16.
17.
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 O2H2S 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 O2H2S 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   

18.
J.G Rønsbo  A.K Pedersen  J Engell 《Lithos》1977,10(3):193-204
Microprobe analyses on a xenocrystic suite of salites, aegirine-augites, aegirines, titan-aegirines and acmites from a lower Tertiary ash layer in northern Denmark are presented. The sodic pyroxenes show an unusual titan-enrichment and up to 42 mol.% of the component NaTi124+M122+Si3O6 (M = Fe2+, Mn or Mg), is estimated. Optical absorption measurements show no evidence for Ti3+. The titan-aegirines were formed during late to post-magmatic crystallization in a system with a high Ti4+/Fe2+ ratio and were followed by acmite showing enrichment in jadeite. Comparison with experimentally investigated titan-aegirine indicates crystallization far below the Mn2O3Mn3O4f02 buffer.  相似文献   

19.
Major and seventeen trace element distribution coefficients between main phenocrysts (olivine, clinopyroxene, amphibole, mica, feldspars and Fe-Ti oxides) and groundmass have been measured in the alkali basalt suite of Chaîne des Puys (Massif Central, France). The suite appears to be a well behaved crystal fractionation series. We pinpoint key elements whose behavior is closely related to the appearance or disappearance of specific crystal phases in the fractionation process. Ta, for instance, clearly indicates the role of hydrous silicates (amphiboles and micas). Distribution coefficients are shown to vary systematically along the differentiation trend. Significantly the hygromagmaphile tendency (Treuilet al., 1979) of U, Th, Ta and La is variable along the series.The mass balance equations,
Di=;xjDjii
where Di and Dji are the bulk and mineral/liquid distribution coefficients respectively, and xj the weight fractions of the fractionating phases, are solved by least square resolution of the overdetermined system, taking into account the analytical errors on data. The solution applied to the Chaîne des Puys suite leads to a coherent and quantitative model of the fractional crystallization process. The suite has apparently evolved in three stages. Each stage is characterized by constant bulk distribution coefficients and a specific mineral assemblage. Amphibole fractionation plays an important role in the early stages. Some intensive parameters (T, ? ?O2, PH2O) as well as f (weight fraction of residual liquid) are also estimated.  相似文献   

20.
A differential rate equation for silica-water reactions from 0–300°C has been derived based on stoichiometry and activities of the reactants in the reaction SiO2(s) + 2H2O(l) = H4SiO4(aq)
(?aH4SiO4?t)P.T.M. = (AM)(γH4SiO4)(k+aSiO2a2H2O ? k_aH4SiO4)
where (AM) = (the relative interfacial area between the solid and aqueous phases/the relative mass of water in the system), and k+ and k? are the rate constants for, respectively, dissolution and precipitation. The rate constant for precipitation of all silica phases is log k? = ? 0.707 ? 2598T(T, K) and Eact for this reaction is 49.8 kJ mol?1. Corresponding equilibrium constants for this reaction with quartz, cristobalite, or amorphous silica were expressed as log K = a + bT + cT. Using K =k+k?, k was expressed as log k + = a + bT + cT and a corresponding activation energy calculated:
  相似文献   

abcEact(kJ mol -1)
Quarts1.174-2.028 x 103-415867.4–76.6
α-Cristobalite-0.7390-358668.7
β-Cristobalite-0.9360-339265.0
Amorphous silica-0.369-7.890 x 10-4343860.9–64.9
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