The supply and accumulation of silica in the marine environment

Rivers and submarine hydrothermal emanations supply 6.1 × 10¹⁴g SiO₂/yr to the marine environment. Approximately two-thirds of the silica supplied to the marine environment can be accounted for in continental margin and deep-sea deposits. Siliceous deep-sea sediments located beneath the Antarctic Polar Front (Convergence) account for over a fourth (1.6 × 10¹⁴g SiO₂/yr) of the silica supplied to the oceans. Deep-sea sediment accumulation rates beneath the Polar Front are highest in the South Atlantic with values as large as 53cm/kyr during the last 18.000 yr. Siliceous sediments in the Bering Sea, Sea of Okhotsk, and Subarctic North Pacific accumulate 0.6 × 10¹⁴g SiO₂/yr or 10% of the dissolved silica input to the oceans. The accumulation of biogenic silica in estuarine deposits removes a maximum of 0.8 × 10¹⁴g SiO₂/yr. Although estuarine silica versus salinity plots indicate extensive removal of riverine silica from surface waters, the removal rates must be considered as maximum values because of dissolution of siliceous material in estuarine sediments and bottom waters. Siliceous sediments from continental margin upwelling areas (e.g. Gulf of California, Walvis Bay, or Peru-Chile coast) have the highest biogenic silica accumulation rates in the marine environment (69 g SiO₂ cm²/kyr). Despite the rapid accumulation of biogenic silica, upwelling areas account for less than 5% of the silica supplied to the marine environment because they are confined laterally to such small areas.     

Kaolin Occurrences in the Erenler Dagi Volcanics,Southwest Konya Province,Turkey

Mainly calc-alkaline, andesitic, and dacitic volcanics from different late Miocene-Pliocene eruption centers crop out WSW of Konya, and locally are interbedded with lacustrine sediments. Hydrothermal alteration within these rocks is widespread. In addition to kaolinite, other major alteration products include halloysite, alunite, cristobalite, quartz, illite, montmorillonite, and zeolitegroup minerals. Based on the cristobalite-quartz relationship, the kaolinization temperature is estimated as ～100°C.

The samples were mineralogically and chemically examined using XRD, SEM-EDS, IR, DTA-TG, and XRF. The crystallinity of the kaolinite is moderate, and shows structural disorder. Both the kaolinite and halloysite are almost stoichometric. Kaolinization generally led to Al₂O₃ increases and release of alkalies, alkaline earths, most of the Fe₂O₃, and SiO₂. SiO₂ and Al₂O₃ contents are low, and LOI is very high for halloysite deposits relative to kaolin occurrences. The kaolinite-alunite assemblages indicate that pH of the altering solutions initially was ～4. SEM investigation demonstrates that kaolinite has booklet texture, whereas halloysite is acicular to needleshaped. The chemical, mineralogic, and firing properties of the kaolin deposits are appropriate for use as refractory raw material. The Erenler Dagi kaolin deposits are excellent examples of the acid-sulfate type of hydrothermal alteration. The findings of the study may be useful in exploration for similar hydrothermal mineral occurrences worldwide.     

Kinetics of silica oligomerization and nanocolloid formation as a function of pH and ionic strength at 25°C

Rate laws reported for the oligomerization of silica in natural environments are often contradictory, and the kinetics of monosilicic acid condensation are poorly understood. Here we present rate expressions that systematically describe the initial oligomerization of silica in terms of concentration of initial silica, ionic strength, and pH for a natural brine solution. The oligomerization of silica in dilute aqueous solutions was examined in solutions with ionic strengths of 0.01 and 0.24 molal, from pH 3 to 11, and with initial silica concentrations of 4.2, 12.5, and 20.8 millimolal (250, 750, and 1250 ppm SiO₂ respectively). The decrease in concentration of molybdate-reactive silica was monitored over time to determine the extent of oligomerization. This decrease in concentration of molybdate-reactive silica is accompanied by the appearance of a transient population of nanocolloidal particles with diameter ∼3 nm, as determined by atomic force microscopy (AFM). The oligomerization rate increases as pH approaches near neutral and as ionic strength increases. Early in the reaction where the concentration of molybdate-reactive silica, [SiO₂]_n≤3, is assumed to equal the concentration of monosilicic acid, [H₄SiO₄], the rate of change of monosilicic acid as a function of time, R, shows a fourth-order dependence:

R=k₄⁴[H₄SiO₄]     

The effect of titanium and phosphorus on ferric/ferrous ratio in silicate melts: an experimental study

The effect of TiO₂ and P₂O₅ on the ferric/ferrous ratio in silicate melts was investigated in model silicate melts at air conditions in the temperature range 1,400–1,550 °C at 1-atm total pressure. The base composition of the anorthite–diopside eutectic composition was modified with 10 wt % Fe₂O₃ and variable amounts of TiO₂ (up to 30 wt %) or P₂O₅ (up to 20 wt %). Some compositions also contained higher SiO₂ concentrations to compare the role of SiO₂, TiO₂, and P₂O₅ on the Fe³⁺/Fe²⁺ ratio. The ferric/ferrous ratio in experimental glasses was analyzed using a wet chemical technique with colorimetric detection of ferrous iron. It is shown that at constant temperature, an increase in SiO₂, TiO₂, and P₂O₅ content results in a decrease in the ferric/ferrous ratio. The effects of TiO₂ and SiO₂ on the Fe³⁺/Fe²⁺ ratio was found to be almost identical. In contrast, adding P₂O₅ was found to decrease ferric/ferrous ratio much more effectively than adding silica. The results were compared with the predictions from the published empirical equations forecasting Fe³⁺/Fe²⁺ ratio. It was demonstrated that the effects of TiO₂ are minor but that the effects of P₂O₅ should be included in models to better describe ferric/ferrous ratio in phosphorus-bearing silicate melts. Based on our observations, the determination of the prevailing fO₂ in magmas from the Fe³⁺/Fe²⁺ ratio in natural glasses using empirical equations published so far is discussed critically.     

Modeling the kinetics of silica nanocolloid formation and precipitation in geologically relevant aqueous solutions

The kinetics of the formation and precipitation of nanocolloidal silica from geologically relevant aqueous solutions is investigated. Changes in monomeric (SiO_2(mono)), nanocolloidal (SiO_2(nano)) and precipitated silica (SiO_2(ppt)) concentrations in aqueous solutions from pH 3 to 7, ionic strengths (IS) of 0.01 and 0.24 molal, and initial SiO₂ concentrations of 20.8, 12.5 and 4.2 mmolal (reported in [Icopini, G.A., Brantley, S.L., Heaney, P.J., 2005. Kinetics of silica oligomerization and nanocolloid formation as a function of pH and ionic strength at 25 °C. Geochim. Cosmochim. Acta69(2), 293-303.]) were fit using two kinetic models. The first model, termed the concentration model, is taken from Icopini et al. (2005) and assumes that the rate of change of SiO_2(mono) as a function of time has a fourth-order dependence on the concentration of SiO_2(mono) in solution. The second model, termed the supersaturation model, incorporates the equilibrium concentration of amorphous silica and predicts that polymerization will be a function of the degree of silica supersaturation in solution with respect to amorphous silica. While both models generally predicted similar rate constants for a given set of experimental conditions, the supersaturation model described the long-term equilibrium behavior of the SiO_2(mono) fraction more accurately, resulting in significantly better fits of the monomeric data. No difference was seen between the model fits of the nanocolloidal silica fraction. At lower pH values (3-4), a metastable equilibrium was observed between SiO_2(mono) and SiO_2(nano). This equilibrium SiO_2(mono) concentration was found to be 6 mmolal, or three times the reported solubility of bulk amorphous silica under the experimental conditions studied and corresponds to the predicted solubility of amorphous silica colloids approximately 3 nm in diameter. Atomic force microscopy was used to determine the average size of the primary nanocolloidal particles to be ∼3 nm, which is in direct agreement with the solubility calculations. Larger aggregates of the primary nanocolloids were also observed to range in size from 30 to 40 nm. This work provides the first kinetic models describing the formation and evolution of nanocolloidal silica in environmentally relevant aqueous solutions. Results indicate that nanocolloidal silica is an important species at low pH and neutral pH at low ionic strengths and may play a more important role in geochemical cycles in natural aqueous systems than previously considered.     

Effects of the degree of polymerization on the structure of sodium silicate and aluminosilicate glasses and melts: An O NMR study

Revealing the atomic structure and disorder in oxide glasses, including sodium silicates and aluminosilicates, with varying degrees of polymerization, is a challenging problem in high-temperature geochemistry as well as glass science. Here, we report ¹⁷O MAS and 3QMAS NMR spectra for binary sodium silicate and ternary sodium aluminosilicate glasses with varying degrees of polymerization (Na₂O/SiO₂ ratio and Na₂O/Al₂O₃ ratio), revealing in detail the extent of disorder (network connectivity and topological disorder) and variations of NMR parameters with the glass composition. In binary sodium silicate glasses [Na₂O-k(SiO₂)], the fraction of non-bridging oxygens (NBOs, Na-O-Si) increases with the Na₂O/SiO₂ ratio (k), as predicted from the composition. The ¹⁷O isotropic chemical shifts (¹⁷O δ_iso) for both bridging oxygen (BO) and NBO increase by about 10-15 ppm with the SiO₂ content (for k = 1-3). The quadrupolar coupling products of BOs and NBOs also increase with the SiO₂ content. These trends suggest that both NBOs and BOs strongly interact with Na; therefore, the Na distributions around BOs and NBOs are likely to be relatively homogenous for the glass compositions studied here, placing some qualitative limits on the extent of segregation of alkali channels from silica-enriched regions as suggested by modified random-network models. The peak width (in the isotropic dimension) and thus bond angle and length distributions of Si-O-Si and Na-O-Si increase with the SiO₂ content, indicating an increase in the topological disorder with the degree of polymerization. In the ternary aluminosilicate glasses [Na₂O]_x[Al₂O₃]_1−xSiO₂, the NBO fraction decreases while the Al-O-Si and Al-O-Al fractions apparently increase with increasing Al₂O₃ content. The variation of oxygen cluster populations suggests that deviation from “Al avoidance” is more apparent near the charge-balanced join (Na/Al = 1). The Si-O-Si fraction, which is closely related to the activity coefficient of silica, would decrease with increasing Al₂O₃ content at a constant mole fraction of SiO₂. Therefore, the activity of silica may decrease from depolymerized binary silicates to fully polymerized sodium aluminosilicate glasses at a constant mole fraction of SiO₂.     

Experimental modeling of Au and Pt coupled transport by chloride hydrothermal fluids at 350–450°C and 500–1000 bar

The coupled solubility of Au_(cr) and Pt_(cr) has been measured in acidic chloride solutions at 350–450°С and 0.5 and 1 kb using the autoclave technique with determination of dissolved metal contents after quenching. The constants of the reaction combining the dominant species of Au and Pt in high-temperature hydrothermal fluids (K_(Au–Pt)) have been determined: 2 Au_(cr) + PtCl₄^2- = Pt_(cr) + 2AuCl₂^-; log K_(Au–Pt) =–1.02 ± 0.25 (450°С, 1 kb), 0.09 ± 0.15 (450°С, 0.5 kb), and –1.31 ± 0.20 (350°С, 1 kb). It has been established that the factors affecting the Au/Pt concentration ratio in hydrothermal fluids and precipitated ores are temperature, pressure, redox potential, and sulfur fugacity. An increase in temperature results in an increase in the Au/Pt concentration ratio (up to ~550°С at P = 1 kb). A decrease in pressure and redox potential leads to enrichment of fluid in Au. An increase in sulfur fugacity in the stability field of Pt sulfides results in increase in the Au/Pt concentration ratio. Native platinum is replaced by sulfide mineral in low-temperature systems enriched in Pt (relative to Au).     

A simple predictive model of quartz solubility in water-salt-CO2 systems at temperatures up to 1000 °C and pressures up to 1000 MPa

Knowledge of the solubility of quartz over a broad spectrum of aqueous fluid compositions and T-P conditions is essential to our understanding of water-rock interaction in the Earth’s crust. We propose an equation to compute the molality of aqueous silica, m_SiO2(aq), mol·(kg H₂O)⁻¹, in equilibrium with quartz and water-salt-CO₂ fluids, as follows:

     

An experimental study of the solubility of baddeleyite (ZrO2) in fluoride-bearing solutions at elevated temperature

The solubility of baddeleyite (ZrO₂) and the speciation of zirconium have been investigated in HF-bearing aqueous solutions at temperatures up to 400 °C and pressures up to 700 bar. The data obtained suggest that in HF-bearing solutions zirconium is transported mainly in the form of the hydroxyfluoride species ZrF(OH)₃° and ZrF₂(OH)₂°. Formation constants determined for these species (Zr⁴⁺ + nF⁻ + mOH⁻ = ZrF_n(OH)_m°) range from 43.7 at 100 °C to 46.41 at 400 °C for ZrF(OH)₃°, and from 37.25 at 100 °C to 43.88 at 400 °C for ZrF₂(OH)₂°.Although the solubility of ZrO₂ is retrograde with respect to temperature, the measured concentrations of Zr are orders of magnitude higher than those predicted from theoretical extrapolations based on simple fluoride species (ZrF³⁺-ZrF₆²⁻). Model calculations performed for zircon show that zirconium can be transported by aqueous fluids in concentrations sufficient to account for the concentration of this metal at conditions commonly encountered in fluoride-rich natural hydrothermal systems.     

Thermodynamic properties of H4SiO4 in the ideal gas state as evaluated from experimental data

Solid phases of silicon dioxide react with water vapor with the formation of hydroxides and oxyhydroxides of silica. Recent transpiration and mass-spectrometric studies convincingly demonstrate that H₄SiO₄ is the predominant form of silica in vapor phase at water pressure in excess of 10⁻² MPa. Available literature transpiration and solubility data for the reactions of solid SiO₂ phases and low-density water, extending from 424 to 1661 K, are employed for the determination of Δ_fG⁰, Δ_fH⁰ and S⁰ of H₄SiO₄ in the ideal gas state at 298.15 K, 0.1 MPa. In total, there are 102 data points from seven literature sources. The resulting values of the thermodynamic functions of H₄SiO₄(g) are: Δ_fG⁰ = −1238.51 ± 3.0 kJ mol⁻¹, Δ_fH⁰ = −1340.68 ± 3.5 kJ mol⁻¹ and S⁰ = 347.78 ± 6.2 J K⁻¹ mol⁻¹. These values agree quantitatively with one set of ab initio calculations. The relatively large uncertainties are mainly due to conflicting data for H₄SiO₄(g) from various sources, and new determinations of would be helpful. The thermodynamic properties of this species, H₄SiO₄(g), are necessary for realistic modeling of silica transport in a low-density water phase. Applications of this analysis may include the processes of silicates condensation in the primordial solar nebula, the precipitation of silica in steam-rich geothermal systems and the corrosion of SiO₂-containing alloys and ceramics in moist environments.     

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

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.     

Determination of the first ionization constant of silicic acid from quartz solubility in borate buffer solutions to 350°C

The solubility of quartz has been determined in borax buffer solutions having total boron concentrations of 0.10, 0.20, 0.40 and 0.60 mol kg^?1 and over the temperature range 130–350°C at the saturated vapour pressure of the system. The first ionization constant of silicic acid was calculated from the solubility data and varied from ?logK₁ = 8.88 (± 0.15) at 130°C to ?logK₁ = 10.06 (± 0.20) at 350°C. The solubility of quartz in these solutions was due to the presence of the three species, H₄SiO₄, H₃SiO₄^? and NaH₃SiO₄°. The equilibrium constant for the reaction, Na⁺ + H₃SiO₄^? = NaH₃SiO₄° extended from log K_as = 1.18?1.40 (± 0.20) over the temperature interval 135–301°C. The formation of NaH₃SiO₄° ion pairs was concluded to contribute significantly to the solubility of quartz in alkaline hydrothermal solutions when pH > 8 and sodium concentration exceeds 0.10 mol kg^?1.     

Vent fluid chemistry of the Rainbow hydrothermal system (36°N, MAR): Phase equilibria and in situ pH controls on subseafloor alteration processes

The Rainbow hydrothermal field is located at 36°13.8′N-33°54.15′W at 2300 m depth on the western flank of a non-volcanic ridge between the South AMAR and AMAR segments of the Mid-Atlantic Ridge. The hydrothermal field consists of 10-15 active chimneys that emit high-temperature (∼365 °C) fluid. In July 2008, vent fluids were sampled during cruise KNOX18RR, providing a rich dataset that extends in time information on subseafloor chemical and physical processes controlling vent fluid chemistry at Rainbow. Data suggest that the Mg concentration of the hydrothermal end-member is not zero, but rather 1.5-2 mmol/kg. This surprising result may be caused by a combination of factors including moderately low dissolved silica, low pH, and elevated chloride of the hydrothermal fluid. Combining end-member Mg data with analogous data for dissolved Fe, Si, Al, Ca, and H₂, permits calculation of mineral saturation states for minerals thought appropriate for ultramafic-hosted hydrothermal systems at temperatures and pressures in keeping with constraints imposed by field observations. These data indicate that chlorite solid solution, talc, and magnetite achieve saturation in Rainbow vent fluid at a similar pH_(T,P) (400 °C, 500 bar) of approximately 4.95, while higher pH values are indicated for serpentine, suggesting that serpentine may not coexist with the former assemblage at depth at Rainbow. The high Fe/Mg ratio of the Rainbow vent fluid notwithstanding, the mole fraction of clinochlore and chamosite components of chlorite solid solution at depth are predicted to be 0.78 and 0.22, respectively. In situ pH measurements made at Rainbow vents are in good agreement with pH_(T,P) values estimated from mineral solubility calculations, when the in situ pH data are adjusted for temperature and pressure. Calculations further indicate that pH_(T,P) and dissolved H₂ are extremely sensitive to changes in dissolved silica owing to constraints imposed by chlorite solid solution-fluid equilibria. Indeed, the predicted correlation between dissolved silica and H₂ defines a trend that is in good agreement with vent fluid data from Rainbow and other high-temperature ultramafic-hosted hydrothermal systems. We speculate that the moderate concentrations of dissolved silica in vent fluids from these systems result from hydrothermal alteration of plagioclase and olivine in the form of subsurface gabbroic intrusions, which, in turn are variably replaced by chlorite + magnetite + talc ± tremolite, with important implications for pH lowering, dissolved sulfide concentrations, and metal mobility.     

On the relationship between refractive index and density for SiO2 polymorphs

The Gladstone-Dale law (specific refraction) and the Drude law (molecular refraction) for silica polymorphs, at “sodium light” (λ _D =0.5893 μm), are derived from simple atomic properties of SiO₂ complex (atomic weight, first ionization potential). The considerations are based on the Lorentz electron theory of solids. The characteristic frequency (or eigenfrequency) v ₀ of elementary electron oscillators (in energy units, hv) is identified with the band gap E _G of a solid; on the other hand, this E _G -gap is identified with the single ionization potential \(\tilde U\) of non-free atoms. For \(\tilde U\) =E _G =10.2 eV (energy gap of quartz, see Nitsan and Shankland 1976b) the Gladstone-Dale law, or specific refraction, is (n?1)/ρ=0.208 cm³/g, where n and ρ are the refractive index and the density of medium, respectively. According to empirical data, the average value of the specific refraction of pure SiO₂ polymorphs (except stishovite-high density phase of silica) is (〈n〉?1)/ρ=0.207±0.001 (〈n〉 denotes the mean refractive index of crystal). For stishovite the Drude law (n ²?1)/ρ=0.542 cm³/g is valid under an assumption that the first ionization potential \(\tilde U\) =E _G ≈9 eV; this result is good agreement with the empirical value (〈n〉²?1)/ρ=0.536 cm³/g.     

Experimental determination of argon solubility in silicate melts: An assessment of the effects of liquid composition and temperature

The argon solubility of 38 liquids in the system Na₂O-CaO-MgO-Al₂O₃-SiO₂ (NCMAS) has been determined at 1873 K and 1 bar, the argon concentration of presaturated glasses being measured using a static mass spectrometer. For compositions in the subsystem diopside (CaMgSi₂O₆), nepheline (NaAlSiO₄), albite (NaAlSi₃O₈), anorthite (CaAl₂Si₂O₈), argon solubility is generally a linear function of the relative proportion of each end member, solubility being lowest in diopside melt (1.53 10⁻⁵ cm³ STP · g⁻¹ · bar⁻¹) and highest in albite melt (2.88 10⁻⁴ cm³ STP · g⁻¹ · bar⁻¹). For the tectosilicate joins studied (SiO₂-Na₂Al₂O₄, SiO₂-CaAl₂O₄, SiO₂-MgAl₂O₄) solubility decreases with decreasing silica content in all cases, being highest for Na-bearing liquids and lowest for Mg-bearing liquids at constant molar silica content. Where comparison is possible our results are in good agreement with data from the literature. When our data are considered in isolation we find that argon solubility shows an excellent correlation with calculated ionic porosity. The covariation of argon solubility and liquid density is also reasonable, that with molar volume less convincing and that with polymerization state (as defined by the ratio of the number of nonbridging oxygens and tetrahedral network forming cations; NBO/T) nonexistent. However, when our data are combined with those from the literature no well constrained correlation between argon solubility and ionic porosity is apparent. Based upon this observation and consideration of the temperature dependence of noble gas solubility it is concluded that ionic porosity is not a universally applicable parameter which may be used to predict noble gas solubility as a function of composition, temperature and pressure. Two new models for calculating argon solubility are proposed, both employing the notion of partial molar argon solubilities. The first uses oxide components, for which partial molar argon solubility is directly proportional to partial molar ionic porosity calculated at 1873 K, irrespective of the temperature of experimental equilibration. The second model, which offers the best fit to the available data, employs tetrahedral units rather than oxides as the proposed melt components. This latter model successfully accounts for reported argon solubilities in simple Al-free systems, in simple Al-bearing systems and in natural liquids. This is interpreted to infer that argon is incorporated in large sites in the liquid structure (such as the space within rings of n-tetrahedra) although further work is required to understand the quantitative links between melt structure and noble gas solubility.     

Determination of Gibbs free energies of formation for the silicates MnSiO3, Mn2SiO4 and Mn7SiO12 in the temperature range 1000–1350 K by solid state emf measurements

Standard Gibbs free energies of formation (A _f G⁰) for the minerals rhodonite (MnSiO₃), tephroite (Mn₂SiO₄) and braunite (Mn₇SiO₁₂) have been determined by measuring the oxygen fugacities of the following redox equilibria: 3Mn₂SiO₄(s)+1/2O₂(g)3MnSiO₃(s)+Mn₃O₄(s) MnSi0₃(s)+2Mn₃O₄(s)+1/2₂O₂(g)Mn₇SiO₁₂(s) and 7MnSiO₃(s)+3/2O₂(gMn₇SiO₁₂)(s)+6SiO₂(s) The measurements were performed by means of the solid-state emf technique involving calcia-stabilized zirconia as electrolyte material. The temperature range covered was 1000–1350 K.The results obtained were used to construct a diagram at 1200 K with the axes lgf(O₂)-molar ratio Si/(Si+Mn) to indicate the stability ranges of the manganese silicates.     

Crystal chemical properties of synthetic lazulite–scorzalite solid-solution series

Members of the lazulite–scorzalite (MgAl₂- (PO₄)₂(OH)₂-FeAl₂(PO₄)₂(OH)₂) solid-solution series were synthesized in compositional steps of 12.5?mol% at T?=?485?°C and P?=?0.3?GPa under hydrothermal conditions and controlled oxygen fugacities of the Ni/NiO-buffer. X-ray powder diffraction and ⁵⁷Fe-Mössbauer studies show that under these conditions a complete solid-solution series is formed which is characterized by the substitution of Mg²⁺ and Fe²⁺ on the octahedral Me ²⁺ site. The ⁵⁷Fe-Mössbauer spectra which reveal the presence of both ferrous and ferric iron and the compositional data were interpreted in terms of a defect model with a distribution of the ferric ions over both the Me ²⁺ and the Al³⁺ positions and vacancies on the Me ²⁺ site. The ⁵⁷Fe-Mössbauer parameters of the synthetic compounds correspond to those of natural lazulites except for the total absorption ratio of the ferric iron A(Fe³⁺)/(A(Fe³⁺)+A(Fe²⁺)), which is significantly higher in natural lazulites of the same composition. The total absorption ratio of the ferric iron increases from 4% in pure scorzalite to 15% in a Mg-rich solid-solution with x _Fe ?=?12(1)%     

Steady-state kinetics and equilibrium between ground water and granitic rock

A hypothesis is presented that the dissolution of albite includes the exchange of sodium for hydrogen ion in a surface layer of the mineral and the structural collapse of the residual anionic lattice of the layer. The ion exchange is described by the first law of diffusion (D_25°C = 3 × 10^?22 and 1.5 × 10^?20 cm²sec^?1 at P_CO2 = 0 and 26.2 atm, respectively). The surface residual layer reaches a steady-state thickness ranging from n × 10^?8 to n × 10^?5 cm according to the temperature and P_CO2. The increase in aqueous sodium with time in a continuous ground-water system is described by a simple exponential equation. The equation is used to estimate the percolation time of ground water from the data on the chemical composition of a water sample. The probable times range from 14 to 3840 days for various ground-water systems and are compared to the times of percolation calculated from the geothermal and hydraulic data. Both estimates are found to be in general agreement. The concentrations of Al and Si in cold water from granitic rocks are shown to be controlled by the chemical equilibrium with respect to an aged aluminosilicate. The aluminosilicate precipitates from ground water as an amorphous isoelectric solid. Its chemical composition is represented by a simplified stoichiometric formula [Al(OH)₃](_1?x)[SiO₂]_x and varies linearly with pH of the solution. The atoms of Al, O and H tend to occupy a fixed position in the solid given by the gibbsite structure upon aging in the field. The solubility product of the solid is estimated from the published data on experimental and field research into the dissolution of feldspars: logK = (1 ? x) × log [Al³⁺] + xlog [H₄SiO₄] ? (3 ? 3x) log [H⁺] = 8.56 ? 11.26x, where x is the molar fraction of silica in the aluminosilicate.