Strontium diffusion in sanidine and albite, and general comments on strontium diffusion in alkali feldspars

Strontium chemical diffusion has been measured in albite and sanidine under dry, 1 atm, and QFM buffered conditions. Strontium oxide-aluminosilicate powdered sources were used to introduce the diffusant and Rutherford Backscattering Spectroscopy (RBS) used to measure diffusion profiles. For the 1 atm experiments, the following Arrhenius relations were obtained:

Sanidine (Or₆₁), temperature range 725–1075°C, diffusion normal to (001): D=8.4 exp(−450±13 kJ mol⁻¹/RT) m²s⁻¹. Albite (Or₁), temperature range 675–1025°C, diffusion normal to (001): D=2.9 × exp(−224±11 kJ mol⁻¹/RT) m²s⁻¹.

The alkali feldspars in this and earlier work display a broad range of activation energies for Sr diffusion, which may be a consequence of the thermodynamic non-ideality of the alkali feldspar system and/or the mixed alkali effect.     

Effect of Fe on garnet–melt trace element partitioning: experiments in FCMAS and quantification of crystal-chemical controls in natural systems

Garnet–melt trace element partitioning experiments were performed in the system FeO–CaO–MgO–Al₂O₃–SiO₂ (FCMAS) at 3 GPa and 1540°C, aimed specifically at studying the effect of garnet Fe²⁺ content on partition coefficients (D^Grt/Melt). D^Grt/Melt, measured by SIMS, for trivalent elements entering the garnet X-site show a small but significant dependence on garnet almandine content. This dependence is rationalised using the lattice strain model of Blundy and Wood [Blundy, J.D., Wood, B.J., 1994. Prediction of crystal–melt partition coefficients from elastic moduli. Nature 372, 452–454], which describes partitioning of an element i with radius r_i and valency Z in terms of three parameters: the effective radius of the site r₀(Z), the strain-free partition coefficient D₀(Z) for a cation with radius r₀(Z), and the apparent compressibility of the garnet X-site given by its Young's modulus E_X(Z). Combination of these results with data in Fe-free systems [Van Westrenen, W., Blundy, J.D., Wood, B.J., 1999. Crystal-chemical controls on trace element partitioning between garnet and anhydrous silicate melt. Am. Mineral. 84, 838–847] and crystal structure data for spessartine, andradite, and uvarovite, leads to the following equations for r₀(3+) and E_X(3+) as a function of garnet composition (X) and pressure (P):

r₀(3+) [Å]=0.930X_Py+0.993X_Gr+0.916X_Alm+0.946X_Spes+1.05(X_And+X_Uv)−0.005(P [GPa]−3.0)(±0.005 Å)

E_X(3+) [GPa]=3.5×10¹²(1.38+r₀(3+) [Å])^−26.7(±30 GPa)

Accuracy of these equations is shown by application to the existing garnet–melt partitioning database, covering a wide range of P and T conditions (1.8 GPa<P<5.0 GPa; 975°C<T<1640°C). D^Grt/Melt for all 3+ elements entering the X-site (REE, Sc and Y) are predicted to within 10–40% at given P, T, and X, when D^Grt/Melt for just one of these elements is known. In the absence of such knowledge, relative element fractionation (e.g. D_Sm^Grt/Melt/D_Nd^Grt/Melt) can be predicted. As an example, we predict that during partial melting of garnet peridotite, group A eclogite, and garnet pyroxenite, r₀(3+) for garnets ranges from 0.939±0.005 to 0.953±0.009 Å. These values are consistently smaller than the ionic radius of the heaviest REE, Lu. The above equations quantify the crystal-chemical controls on garnet–melt partitioning for the REE, Y and Sc. As such, they represent a major advance en route to predicting D^Grt/Melt for these elements as a function of P, T and X.     

Oxidative dissolution of pyritic sludge from the Aznalcóllar mine (SW Spain)

As a result of the collapse of a mine tailing dam, a large extension of the Guadiamar valley was covered with a layer of pyritic sludge. Despite the removal of most of the sludge, a small amount remained in the soil, constituting a potential risk of water contamination. The kinetics of the sludge oxidation was studied by means of laboratory flow-through experiments at different pH and oxygen pressures. The sludge is composed mainly of pyrite (76%), together with quartz, gypsum, clays, and sulphides of zinc, copper, and lead. Trace elements, such as arsenic and cadmium, also constitute a potential source of pollution. The sludge is fine grained (median of 12 μm) and exhibits a large surface (BET area of 1.4±0.2 m² g⁻¹).

The dissolution rate law of sludge obtained is r=10^{−6.1(±0.3)} [O₂(aq)]^0.41(±0.04) a_H+^0.09(±0.06) g_sludge m⁻² s⁻¹ (22 °C, pH=2.5–4.7). The dissolution rate law of pyrite obtained is r=10^{−7.8(±0.3)} [O₂(aq)]^0.50(±0.04) a_H+^0.10(±0.08) mol m⁻² s⁻¹ (22 °C, pH=2.5–4.7). Under the same experimental conditions, sphalerite dissolved faster than pyrite but chalcopyrite dissolves at a rate similar to that of pyrite. No clear dependence on pH or oxygen pressure was observed. Only galena dissolution seemed to be promoted by proton activity. Arsenic and antimony were released consistently with sulphate, except at low pH conditions under which they were released faster, suggesting that additional sources other than pyrite such as arsenopyrite could be present in the sludge. Cobalt dissolved congruently with pyrite, but Tl and Cd seemed to be related to galena and sphalerite, respectively.

A mechanism for pyrite dissolution where the rate-limiting step is the surface oxidation of sulphide to sulphate after the adsorption of O₂ onto pyrite surface is proposed.     

Marcasite precipitation from hydrothermal solutions

Pyrite and marcasite were precipitated by both slow addition of aqueous Fe²⁺ and SiO₃²⁻ to an H₂S solution and by mixing aqueous Fe²⁺ and Na₂S₄ solutions at 75°C. H₂S₂ or HS₂⁻ and H₂S₄ or HS₄⁻ were formed in the S₂O₃²⁻ and Na₂S₄ experiments, respectively. Marcasite formed at pH < pK₁ of the polysulfide species present (for H₂S₂, pK₁ = 5.0; for H₂S₄, pK₁ = 3.8 at 25°C). Marcasite forms when the neutral sulfane is the dominant polysulfide, whereas pyrite forms when mono-or divalent polysulfides are dominant. In natural solutions where H₂S₂ and HS₂ are likely to be the dominant polysulfides, marcasite will form only below pH 5 at all temperatures.

The pH-dependent precipitation of pyrite and marcasite may be caused by electrostatic interactions between polysulfide species and pyrite or marcasite growth surfaces: the protonated ends of H₂S₂ and HS₂ are repelled from pyrite growth sites but not from marcasite growth sites. The negative ions HS₂ and S₂²⁻ are strongly attracted to the positive pyrite growth sites. Masking of 1π_g^* electrons in the S₂ group by the protons makes HS₂ and H₂S₂ isoelectronic with AsS²⁻ and As₂²⁻, respectively ( et al., 1981). Thus, the loellingitederivative structure (marcasite) results when both ends of the polysulfide are protonated.

Marcasite occurs abundantly only for conditions below pH 5 and where H₂S₂ was formed near the site of deposition by either partial oxidation of aqueous H₂S by O₂ or by the reaction of higher oxidation state sulfur species that are reactive with H₂S at the conditions of formation e.g., S₂O₃²⁻ but not SO₄²⁻. The temperature of formation of natural marcasite may be as high as 240°C ( and , 1985), but preservation on a multimillion-year scale seems to require post-depositional temperatures of below about 160°C ( , 1973; and , 1985).     

Competition between enzymatic and abiotic reduction of uranium(VI) under iron reducing conditions

Reduction of U(VI) under iron reducing conditions was studied in a model system containing the dissimilatory metal-reducing bacterium Shewanella putrefaciens and colloidal hematite. We focused on the competition between direct enzymatic uranium reduction and abiotic reduction of U(VI) by Fe(II), catalyzed by the hematite surface, at relatively low U(VI) concentrations (< 0.5 μM) compared to the concentrations of ferric iron (> 10 mM). Under these conditions surface catalyzed reduction by Fe(II), which was produced by dissimilatory iron reduction, was the dominant pathway for uranium reduction. Reduction kinetics of U(VI) were identical to those in abiotic controls to which soluble Fe(II) was added. Strong adsorption of U(VI) at the hematite surface apparently favored the abiotic pathway by reducing the availability of U(VI) to the bacteria. In control experiments, lacking either hematite or bacteria, the addition of 45 mM dissolved bicarbonate markedly slowed down U(VI) reduction. The inhibition of enzymatic U(VI) reduction and abiotic, surface catalyzed U(VI) reduction by the bicarbonate amendments is consistent with the formation of aqueous uranyl-carbonate complexes. Surprisingly, however, more U(VI) was reduced when dissolved bicarbonate was added to experimental systems containing both bacteria and hematite. The enhanced U(VI) reduction was attributed to the formation of magnetite, which was observed in experiments. Biogenic magnetite produced as a result of dissimilatory iron reduction may be an important agent of uranium immobilization in natural environments.     

High-resolution methane profiles across anoxic brine–seawater boundaries in the Atlantis-II, Discovery, and Kebrit Deeps (Red Sea)

A decrease in temperature (ΔT up to 45.5 °C) and chloride concentration (ΔCl up to 4.65 mol/l) characterises the brine–seawater boundary in the Atlantis-II, Discovery, and Kebrit Deeps of the Red Sea, where redox conditions change from anoxic to oxic over a boundary layer several meters thick. High-resolution (100 cm) profiles of the methane concentration, stable carbon isotope ratio of methane, and redox-sensitive tracers (O₂, Mn⁴⁺/Mn²⁺, Fe³⁺/Fe²⁺, and SO₄²⁻) were measured across the brine–seawater boundary layer to investigate methane fluxes and secondary methane oxidation processes.

Substantial amounts of thermogenic hydrocarbons are found in the deep brines (mostly methane, with a maximum concentration up to 4.8×10⁵ nmol/l), and steep methane concentration gradients mainly controlled by diffusive flow characterize the brine–seawater boundary (maximum of 2×10⁵ nmol/l/m in Kebrit Deep). However, locally the actual methane concentration profiles deviate from theoretical diffusion-controlled concentration profiles and extremely positive δ¹³C–CH₄ values can be found (up to +49‰ PDB in the Discovery Deep). Both, the actual CH₄ concentration profiles and the carbon-13 enrichment in the residual CH₄ of the Atlantis-II and Discovery Deeps indicate consumption (oxidation) of ¹²C-rich CH₄ under suboxic conditions (probably utilizing readily available—up to 2000 μmol/l—Mn(IV)-oxihydroxides as electron acceptor). Thus, a combined diffusion–oxidation model was used to calculate methane fluxes of 0.3–393 kg/year across the brine–seawater boundary layer. Assuming steady-state conditions, this slow loss of methane from the brines into the Red Sea bottom water reflects a low thermogenic hydrocarbon input into the deep brines.     

Dissolution/precipitation kinetics of boehmite and gibbsite: Application of a pH-relaxation technique to study near-equilibrium rates

The dissolution and precipitation rates of boehmite, AlOOH, at 100.3 °C and limited precipitation kinetics of gibbsite, Al(OH)₃, at 50.0 °C were measured in neutral to basic solutions at 0.1 molal ionic strength (NaCl + NaOH + NaAl(OH)₄) near-equilibrium using a pH-jump technique with a hydrogen-electrode concentration cell. This approach allowed relatively rapid reactions to be studied from under- and over-saturation by continuous in situ pH monitoring after addition of basic or acidic titrant, respectively, to a pre-equilibrated, well-stirred suspension of the solid powder. The magnitude of each perturbation was kept small to maintain near-equilibrium conditions. For the case of boehmite, multiple pH-jumps at different starting pHs from over- and under-saturated solutions gave the same observed, first order rate constant consistent with the simple or elementary reaction: .

This relaxation technique allowed us to apply a steady-state approximation to the change in aluminum concentration within the overall principle of detailed balancing and gave a resulting mean rate constant, (2.2 ± 0.3) × 10⁻⁵ kg m⁻² s⁻¹, corresponding to a 1σ uncertainty of 15%, in good agreement with those obtained from the traditional approach of considering the rate of reaction as a function of saturation index. Using the more traditional treatment, all dissolution and precipitation data for boehmite at 100.3 °C were found to follow closely the simple rate expression:

R_net,boehmite=10^-5.485{m_OH^-}{1-exp(ΔG_r/RT)}, with R_net in units of mol m⁻² s⁻¹. This is consistent with Transition State Theory for a reversible elementary reaction that is first order in OH⁻ concentration involving a single critical activated complex. The relationship applies over the experimental ΔG_r range of 0.4–5.5 kJ mol⁻¹ for precipitation and −0.1 to −1.9 kJ mol⁻¹ for dissolution, and the pH_m ≡ −log(mH⁺) range of 6–9.6. The gibbsite precipitation data at 50 °C could also be treated adequately with the same model:R_net,gibbsite=10^-5.86{m_OH^-}{1-exp(ΔG_r/RT)}, over a more limited experimental range of ΔG_r (0.7–3.7 kJ mol⁻¹) and pH_m (8.2–9.7).     

Solubility of silica polymorphs in electrolyte solutions, I. Activity coefficient of aqueous silica from 25° to 250°C, Pitzer''s parameterisation

Within the framework of Pitzer's specific interaction model, interaction parameters for aqueous silica in concentrated electrolyte solutions have been derived from Marshall and co-authors amorphous silica solubility measurements. The values, at 25°C, of the Pitzer interaction parameter (λ_SiO2(aq)−i) determined in this study are the following: 0.092 (i = Na⁺), 0.032 (K⁺), 0.165 (Li⁺), 0.292 (Ca²⁺, Mg²⁺), −0.139 (SO₄²⁻), and −0.009 (NO₃⁻). A set of polynomial equations has been derived which can be used to calculate λ_SiO2(aq)−i for these ions at any temperature up to 250°C. A linear relationship between the aqueous silica-ion interaction parameters (λ_SiO2(aq)−i) and the surface electrostatic field (Z_i/r_e,i) of ions was obtained. This empirical equation can be used to estimate, in first approximation, λ_SiO2(aq)−i if no measurements are available. From this parameterisation, the calculated activity coefficient of aqueous silica is 2.52 at 25°C and 1.45 at 250°C in 5 m NaCl solution. At lower concentrations, e.g. 2 m NaCl, the activity coefficient of silica is 1.45 at 25°C and 1.2 at 250°C. Hence, in practice, it is necessary to take into account the activity coefficient of aqueous silica (λ_SiO2(aq)≠1) in hydrothermal solutions and basinal brines where the ionic strength exceeds 1. A comparison of measured [Marshall, W.L., Chen, C.-T.A., 1982. Amorphous silica solubilities, V. Prediction of solubility behaviour in aqueous mixed electrolyte solutions to 300°C. Geochim. Cosmochim. Acta 46, 289–291.] and computed amorphous silica solubility, using this parameterisation, shows a good agreement. Because the effect of individual ions on silicate and silica polymorph solubilities are additive, the present study has permitted to derive Pitzer interaction parameters that allow a precise computation of γ_SiO2(aq) in the Na---K---Ca---Mg---Cl---SO₄---HCO₃---SiO₂---H₂O system, over a large range of salt concentrations and up to temperatures of 250°C.     

Fluid-bearing alkaline carbonate melts as the medium for the formation of diamonds in the Earth''s mantle: an experimental study

We have experimentally studied the formation of diamonds in alkaline carbonate–carbon and carbonate–fluid–carbon systems at 5.7–7.0 GPa and 1150–1700 °C, using a split-sphere multi-anvil apparatus (BARS). The starting carbonate and fluid-generating materials were placed into Pt and Au ampoules. The main specific feature of the studied systems is a long period of induction, which precedes the nucleation and growth of diamonds. The period of induction considerably increases with decreasing P and T, but decreases when adding a C–O–H fluid to the system. In the range of P and T corresponding to the formation of diamonds in nature, this period lasts for tens of hours. The reactivity of the studied systems with respect to the diamond nucleation and growth decreases in this sequence: Na₂CO₃–H₂C₂O₄·2H₂O–C>K₂CO₃–H₂C₂O₄·2H₂O–C>>Na₂CO₃–C>K₂CO₃–C. The diamond morphology is independent of P and T, and is mainly governed by the composition of the crystallization medium. The stable growth form is a cubo-octahedron in the Na₂CO₃ melt, and an octahedron in the K₂CO₃ melt. Regardless of the composition of the carbonate melt, only octahedral diamond crystals formed in the presence of the C–O–H fluid. The growth rates of diamond varied in the range from 1.7 μm/h at 1420 °C to 0.1–0.01 μm/h at 1150 °C, and were used to estimate, for the first time, the possible duration of the crystallization of natural diamonds. From the analysis of the experimental results and the petrological evidence for the formation of diamonds in nature, we suggest that fluid-bearing alkaline carbonate melts are, most likely, the medium for the nucleation and growth of diamonds in the Earth's upper mantle.     

Status report on stability of K-rich phases at mantle conditions

Experimental research on K-rich phases and observations from diamond inclusions, UHP metamorphic rocks, and xenoliths provide insights about the hosts for potassium at mantle conditions. K-rich clinopyroxene (Kcpx–KM³⁺Si₂O₆) can be an important component in clinopyroxenes at P>4 GPa, dependent upon coexisting K-bearing phases (solid or liquid) but not, apparently, upon temperature. Maximum Kcpx content can reach 25 mol%, with 17 mol% the highest reported in nature. Partitioning ^(K)D_(cpx/liquid) above 7 GPa=0.1–0.2 require ultrapotassic liquids to form highly potassic cpx or critical solid reactions, e.g., between Kspar and Di. Phlogopite can be stable to about 8 GPa at 1250 °C where either amphibole or liquid forms. When fluorine is present, it generally increases in Phl upon increasing P (and probably T) to about 6 GPa, but reactions forming amphibole and/or KMgF₃ limit F content between 6 and 8 GPa. The perovskite KMgF₃ is stable up to 10 GPa and 1400 °C as subsolidus breakdown products of phlogopite upon increasing P. ^(M4)K-substituted potassic richterite (ideally K(KCa)Mg₅Si₈O₂₂(OH,F)₂) is produced in K-rich peridotites above 6 GPa and in Di+Phl from 6 to 13 GPa. K content of amphibole is positively correlated with P; Al and F content decrease with P. In the system 1Kspar+1H₂O K-cymrite (hydrous hexasanidine–KAlSi₃O₈·nH₂O–Kcym) is stable from 2.5 GPa at 400 to 1200 °C and 9 GPa; Kcym can be a supersolidus phase. Formation of Kcym is sensitive to water content, not forming within experiments with H₂O2O>Kspar. Phase X, a potassium di-magnesium acid disilicate ((K_1−x−n)₂(Mg_1−nM_n³⁺)₂Si₂O₇H_2x), forms in mafic compositions at T=1150–1400 °C and P=9–17 GPa and is a potential host for K and H₂O at mantle conditions with a low-T geotherm or in subducting slabs. The composition of phase-X is not fixed but actually represents a solid solution in the stoichiometries □₂Mg₂Si₂O₇H₂–(K□)Mg₂Si₂O₇H–K₂Mg₂Si₂O₇ (□=vacancy), apparently stable only near the central composition. K-hollandite, KAlSi₃O₈, is possibly the most important K-rich phase at very high pressure, as it appears to be stable to conditions near the core–mantle boundary, 95 GPa and 2300 °C. Other K-rich phases are considered.     

Temperature independent thermal expansivities of sodium aluminosilicate melts between 713 and 1835 K

The thermal expansivities of eight sodium aluminosilicate liquids were derived from the slope of new volume data at low temperatures (713−1072 K) combined with the high temperature (1300−1835 K) volume measurements of Stein et al. (1986) on the same liquids. Melt compositions range from 47−71 wt% SiO₂, 0−31 wt% A1203, and 17−33 wt% Na₂O; the volume of albite supercooled liquid at 1092 K was also determined. The low temperature volumes were derived from measurements of the glass density of each sample at 298 K, followed by measurements of the glass thermal expansion coefficient from 298 K to the respective glass transition interval. This technique takes advantage of the fact that the volume of a glass is equal to the volume of the corresponding liquid at the limiting fictive temperature (T′_f), and that T′_f can be approximated as the onset of the rapid rise in thermal expansion at the glass transition in a heating curve (Moynihan, 1995). No assumptions were made regarding the equivalence of enthalpy and volume relaxation through the glass transition. The propagated error on the volume of each supercooled liquid at T′_f is 0.25%. Combination of these low temperature data with the high temperature measurements of Stein et al. (1986) allowed a constant thermal expansivity of each liquid to be derived over a wide temperature interval (763−1001 degrees) with a fitted 1σ error of 0.6–4.6%; in every case, no temperature dependence to dV/dT^liq could be resolved. Calibration of a linear model equation leads to fitted values ± 1σ (units of cm³/mole) for (26.91 ± .04), (37.49 ± .12), (26.48 ± .06) at 1373 K, and (7.64 ± .08 × 10^-3 cm³/mole-K). The results indicate that neither Si02 nor Al₂O₃ contribute to the thermal expansivity of the liquids, and that dV/dT^liq is independent of temperature between 713–1835 K over a wide range of liquid composition. Calculated volumes based on this model recover both low and high temperature measurements with a standard deviation <0.25%, whereas values of dV/dT^liq can be predicted within 5.6%.     

Solubility of cassiterite in evolved granitic melts: effect of T, fO2, and additional volatiles

The aim of this experimental study was to determine the solubility of cassiterite in natural topaz- and cassiterite-bearing granite melts at temperatures close to the solidus. Profiles of Sn concentrations at glass–crystal (SnO₂) interface were determined following the method of (Harrison, T.M., Watson, E.B., 1983. Kinetics of zircon dissolution and zirconium diffusion in granitic melts of variable water content. Contributions to Mineralogy and Petrology 84, 66–72). The cassiterite concentration calculated at the SnO₂–glass interface is the SnO₂ solubility. Experiments were performed at 700–850 °C and 2 kbar using a natural F-bearing peraluminous granitic melt with 2.8 wt.% normative corundum. Slightly H₂O-undersaturated to H₂O-saturated melt compositions were chosen in order to minimize the loss of Sn to the noble element capsule walls. At the nickel–nickel oxide assemblage (Ni–NiO) oxygen fugacity buffer, the solubility of cassiterite in melts containing 1.12 wt.% F increases from 0.32 to 1.20 wt.% SnO₂ with an increasing temperature from 700 to 850 °C. At the Ni–NiO buffer and a given corundum content, SnO₂ solubility increases by 10% to 20% relative to an increase of F from 0 to 1.12 wt.%. SnO₂ solubility increases by 20% relative to increasing Cl content from 0 to 0.37 wt.% in synthetic granitic melts at 850 °C. We show that Cl is at least as important as F in controlling SnO₂ solubility in evolved peraluminous melts at oxygen fugacities close to the Ni–NiO buffer. In addition to the strong effects of temperature and fO₂ on SnO₂ solubility, an additional controlling parameter is the amount of excess Al (corundum content). At Ni–NiO and 850 °C, SnO₂ solubility increases from 0.47 to 1.10 wt.% SnO₂ as the normative corundum content increases from 0.1 to 2.8 wt.%. At oxidizing conditions (Ni–NiO +2 to +3), Sn is mainly incorporated as Sn⁴⁺ and the effect of excess Al seems to be significantly weaker than at reducing conditions.     

Ocean crust vein mineral deposition: Rb/Sr ages, U-Th-Pb geochemistry, and duration of circulation at DSDP sites 261, 462 and 516

Cation exchange experiments (ammonium acetate and cation resin) on celadonite-smectite vein minerals from three DSDP holes demonstrate selective removal of common Sr relative to Rb and radiogenic Sr. This technique increases the Rb/Sr ratio by factors of 2.3 to 22 without significantly altering the age of the minerals, allowing easier and more precise dating of such vein minerals. The ages determined by this technique (site 261—121.4 ±1.6 m.y.; site 462A—105.1 ±2.8 m.y.; site 516F—69.9 ±2.4 m.y.) are 34, 54 and 18 m.y. younger, respectively, than the age of crust formation at the site; in the case of site 462A, the young age is clearly related to off-ridge emplacement of a massive sill/flow complex. At the other sites, either the hydrothermal circulation systems persisted longer than for normal crust (10–15 m.y.), or were reactivated by off-ridge igneous activity.

Celadonites show U and Pb contents and Pb isotopic compositions little changed from their basalt precursors, while Th contents are significantly lower. Celadonites thus have unusually high alkali/U,Th ratios and low Th/U ratios. If this celadonite alteration signature is significantly imprinted on oceanic crust as a whole, it will lead to very distinctive Pb isotope signatures for any hot spot magmas which contain a component of aged subducted recycled oceanic crust.

Initial Sr isotope ratios of ocean crust vein minerals (smectite, celadonite, zeolite, calcite) are intermediate between primary basalt values and contemporary sea water values and indicate formation under seawaterdominated systems with effective water/rock ratios of 20–200.     

A three-dimensional method for calculating independent chemical U/Pb- and Th/Pb-ages of accessory minerals

Previous theoretical considerations on the chemical U---Th-total Pb dating method failed to distinguish between thorogenic and uranogenic lead. However, it can be shown that the data points are located on a plane in the three-dimensional ThO₂, PbO, UO₂ space. The calculation of the best-fit plane yields a slope in the ThO₂---PbO and UO₂---PbO coordinate projections, and an initial PbO value. From the two slopes, Th/Pb- and U/Pb-ages can be calculated independently.

The method described in this paper is applied to monazites from the Hercynian G4-granite of the Fichtelgebirge (Germany). Th/Pb- and U/Pb-ages were calculated at 323 ± 20 Ma and 304 ± 15 Ma, respectively. The intercept value close to zero indicates that no significant amounts of common lead are present in the monazites studied.     

Micro-XANES determination of ferric iron and its application in thermobarometry

Micro-X-ray absorption near-edge structure (XANES) analysis was employed to determine the content of ferric iron in minerals formed in ultrahigh-pressure (UHP) eclogites. It is observed that omphacite and phengite contain significant amounts of Fe³⁺/Fe_tot (0.2–0.6), whereas only very low contents are present in garnet (Fe³⁺/Fe_tot=0.0–0.03), the latter being consistent with results from stoichiometric charge-balance calculations. Furthermore, considerable variations in the Fe³⁺/Fe_tot ratios of omphacite and phengite are observed depending on the textural sites and local bulk chemistry (eclogite and calc-silicate matrix) within one thin section. The oxidation state of isofacial minerals is thus likely to depend on the local fluid composition, which, in the studied case, is controlled by calcareous and meta-basic mineral compositions. These first in-situ measurements of ferric iron in an eclogite sample from the Dabie Shan, E China, are used to recalculate geothermobarometric data. Calculations demonstrate that the temperature during UHP metamorphism was as high as 780 °C, about 80–100 °C higher than previously estimated. Temperatures based on charge balance calculations often give erroneous results. Pressure estimates are in good agreement with former results and confirm metamorphism in the stability field of diamond (43.7 kbar at 750 °C). These P–T data result in a geothermal gradient of ca. 6 °C/km during UHP metamorphism in the Dabie Shan. However, accounting for ferric iron contents in geothermobarometry creates new difficulties inasmuch as calibrations of geothermometers may not be correctable for Fe³⁺ and the actual effect on Mg–Fe²⁺ partitioning is unknown. The present study further shows that micro-XANES is a promising technique for the in situ determination of ferric iron contents without destroying the textural context of the sample: a clear advantage compared to bulk methods.     

Fluid inclusions in Scourian granulites from the Lewisian complex of NW Scotland: evidence for CO2-rich fluid in Late Archaean high-grade metamorphism

In this paper the first fluid-inclusion data are presented from Late Archaean Scourian granulites of the Lewisian complex of mainland northwest Scotland. Pure CO₂ or CO₂-dominated fluid inclusions are moderately abundant in pristine granulites. These inclusions show homogenization temperatures ranging from − 54 to + 10 °C with a very prominent histogram peak at − 16 to − 32 °C. Isochores corresponding to this main histogram peak agree with P-T estimates for granulite-facies recrystallization during the Badcallian (750–800 °C, 7–8 kbar) as well as with Inverian P-T conditions (550–600 °C, 5 kbar). The maximum densities encountered could correspond to fluids trapped during an early, higher P-T phase of the Badcallian metamorphism (900–1000 °C, 11–12 kbar). Homogenization temperatures substantially higher than the main histogram peak may represent Laxfordian reworking (≤ 500 °C, < 4 kbar). In the pristine granulites, aqueous fluid inclusions are of very subordinate importance and occur only along late secondary healed fractures. In rocks which have been retrograded to amphibolite facies from Inverian and/or Laxfordian shear zones, CO₂ inclusions are conspicuously absent; only secondary aqueous inclusions are present, presumably related to post-granulite hydration processes. These data illustrate the importance of CO₂-rich fluids for the petrogenesis of Late Archaean granulites, and demonstrate that early fluid inclusions may survive subsequent metamorphic processes as long as no new fluid is introduced into the system.     

The late Cretaceous lithospheric mantle beneath the Central Andes: Evidence from phase equilibria and composition of mantle xenoliths

Temperature estimates and chemical composition of mantle xenoliths from the Cretaceous rift system of NW Argentina (26°S) constrain the rift evolution and chemical and physical properties of the lithospheric mantle at the eastern edge of the Cenozoic Andean plateau. The xenolith suite comprises mainly spinel lherzolite and subordinate pyroxenite and carbonatized lherzolite. The spinel lherzolite xenoliths equilibrated at high-T (most samples >1000 °C) and P below garnet-in. The Sm–Nd systematics of compositionally unzoned clino- and orthopyroxene indicate a Cretaceous minimum age for the high-T regime, i.e., the asthenosphere/lithosphere thermal boundary was at ca. 70 km depth in the Cretaceous rift. Major elements and Cr, Ni, Co and V contents of the xenoliths range between values of primitive and depleted mantle. Calculated densities based on the bulk composition of the xenoliths are <3280 kg/m³ for the estimated P–T conditions and indicate a buoyant, stable upper mantle lithosphere. The well-equilibrated metamorphic fabric and mineral paragenesis with the general lack of high-T hydrous phases did not preserve traces of metasomatism in the mantle xenoliths. Late Mesozoic metasomatism, however, is obvious in the gradual enrichment of Sr, U, Th and light to medium REE and changes in the radiogenic isotope composition of an originally depleted mantle. These changes are independent of the degree of depletion evidenced by major element composition. ¹⁴³Nd/¹⁴⁴Nd_i ratios of clinopyroxene from the main group of xenoliths decrease with increasing Nd content from >0.5130 (depleted samples) to ca. 0.5127 (enriched samples). ⁸⁷Sr/⁸⁶Sr_i ratios (0.7127–0.7131, depleted samples; 0.7130–0.7134, enriched samples) show no variation with variable Sr contents. Pb_i isotope ratios of the enriched samples are rather radiogenic (²⁰⁶Pb/²⁰⁴Pb_i 18.8–20.6, ²⁰⁷Pb/²⁰⁴Pb_i 15.6–15.7, ²⁰⁸Pb/²⁰⁴Pb_i 38.6–47) compared with the Pb isotope signature of the depleted samples. The large scatter and high values of ²⁰⁸Pb/²⁰⁴Pb_i ratios of many xenoliths indicates at least two Pb sources that are characterized by similar U/Pb but by different Th/Pb ratios. The dominant mantle type in the investigated system is depleted mantle according to its Sr and Nd isotopic composition with relatively radiogenic Pb isotope ratios. This mantle is different from the Pacific MORB source and old subcontinental mantle from the adjacent Brazilian Shield. Its composition probably reflects material influx into the mantle wedge during various episodes of subduction that commenced in early Paleozoic or even earlier. Old subcontinental mantle was already replaced in the Paleozoic, but some inheritance from old mantle lithosphere is represented by rare xenoliths with isotope signatures indicating a Proterozoic origin.     

Equilibria in the system Au–Ag–S–fluid: computed and experimental data

We present results of computations on the interaction of solid-phase electrum–argentite–pyrite (weight ratios 210⁻⁵/ 210⁻³/1 and 210⁻⁵/410⁻²/1) association with Cl-containing aqueous moderately acid solutions (0.5m NaCl, pH = 3.08) at 300 °C and 500 bars. These data are a physicochemical basis for predicting the geochemical behavior of Au and Ag during the hydrothermal-metasomatic transformation of Au-Ag-pyrite. We also propose a technique of study of this process based on the phase equilibria of the subsystem Au–Ag–S with the aqueous solution at different liquid/solid (l/s) ratios, with the use of new graphic diagrams. The relationship of the composition of the solid-phase association with l/s ratio in real boundary conditions (Au = 17 ppm, mAu/mAg = 10^–3.57–10^–2.28) is shown. The maximum l/s values for complete leaching of gold and silver (l/smax = 200–800) are estimated. It has been established that argentite is the first to dissolve when mAu/mAg(s) > mAu/mAg(sol), and electrum, when mAu/mAg(s) < mAu/mAg(sol).

The experimental results showed that at 300 °C, the conversion of electrum (N_Au = 300‰) nonequilibrated with pyrite into an Au-richer form (N_Au = 730‰) and argentite follows an intricate kinetic scheme. Using the Pilling-Bedwords kinetic equation for processing data yielded the process rate constant K = 2.8(±0.5)10⁻⁵ g²cm⁻⁴day⁻¹. With this equation, the time of the complete conversion of 200 μm thick flat gold grains is 604 days. These data evidence a significant role of kinetic factors in hydrothermal-metasomatic processes involving native gold, which requires combination of thermodynamic and kinetic approaches on the construction of geologo-genetic models for hydrothermal sulfide formation.     

Metamorphic evolution, mineral chemistry and thermobarometry of schists and orthogneisses hosting ultra-high pressure eclogites in the Dabieshan of central China

As is typical of ultra-high pressure (UHP) terrains, the regional extent of the UHP terrain in the Dabieshan of central China is highly speculative, since the volume of eclogites and paragneisses preserving unequivocal evidence of coesite and/or diamond stability is very small. By contrast, the common garnet (X_Mn=0.18–0.45)–phengite (Si=3.2–3.35)–zoned epidote (Ps_38–97)–biotite–titanite–two feldspars–quartz assemblages in the more extensive orthogneisses have been previously thought to have formed under low P–T conditions of ca. 400±50°C at 4 kbar. However, certain orthogneiss samples preserve garnets with X_Ca up to 0.50, rutile inclusions within titanite or epidote and relict phengite inclusions within epidote with Si contents p.f.u. of up to 3.49 — overlapping with the highest values (3.49–3.62) recorded for phengites in samples of undoubted UHP schists. These and other mineral composition features (such as A-site deficiencies in the highest Si phengites, Na in garnets linked to Y+Yb substitution and Al F Ti₋₁ O₋₁ substitution in titanites) are taken to be pointers towards the orthogneisses having experienced a similar metamorphic evolution to the associated UHP schists and eclogites. Re-evaluated garnet–phengite and garnet–biotite Fe/Mg exchange thermometry and calculated 5 rutile+3 grossular+2SiO₂+H₂O=5 titanite+2 zoisite equilibria indicate that the orthogneisses may indeed have followed a common subduction-related clockwise P–T path with the UHP paragneisses and eclogites through conditions of P_max at ca. 690°C–715°C and 36 kbar to T_max at ca. 710°C–755°C and 18 kbar, prior to extensive re-crystallisation and re-equilibration of these ductile orthogneisses at ca. 400°C–450°C and 6 kbar. The consequential conclusion, that it is no longer necessary to resort to models of tectonic juxtapositioning to explain the spatial association of these Dabieshan orthogneisses with undoubted UHP lithologies, has far-reaching implications for the interpretation of controversial gneiss–eclogite relationships in other UHP metamorphic terrains.     

A mechanism of shape-transformation of quartz inclusions in albite of regional metamorphic rocks

The process of shape-transformation of quartz inclusions from polyhedral to spherical grains in albite single crystals during metamorphism is mainly controlled by the grain boundary diffusion of oxygen along the quartz/albite interface to reduce the interfacial free energy. The rate of the process, which is represented by the growth rate of the curvature of the edge surface of the grain, depends significantly on temperature and on the grain size of the quartz inclusion. The relations between temperature, T, the time, t_r, and the critical radius, R_c, which is equal to the radius of maximum spherical grains, are given by log R_c = −0.11E_b/RT + 0.25log t_r + C, in which E_b is the activation energy of the grain boundary diffusion of oxygen along the quartz/albite interface and C is a material constant.

The mean critical radius of spherical quartz inclusions in albite is 5 μm for the upper chlorite zone and garnet zone, 10 μm for the lower biotite zone, and 20 μm for the upper biotite zone in the Sambagawa metamorphic terrain. The mean values of the critical radii of spherical quartz inclusions in oligoclase of the Ryoke metamorphic rocks is about 5 μm for the chlorite zone and about 10–20 μm for the sillimanite zone.

Assuming temperatures of about 350°C for the upper chlorite and garnet zones, 400°C for the lower biotite zone, 550°C for the upper biotite zone, and 700°C for the sillimanite zone, the activation energy for the grain boundary diffusion of oxygen along the quartz/plagioclase interfase is estimated to be about 30 kcal/mol.