Calcite and aragonite precipitation from seawater solutions of various salinities: Precipitation rates and overgrowth compositions

The reaction rate and composition of calcite and aragonite overgrowths precipitated from seawater solutions of various salinities (i.e. S=5, 15, 25, 35, 44) were determined at 25°C and 10^−2.5-atm. CO₂ partial pressure using a constant disequilibrium seeded technique. The rate data were fitted to an empirical rate law of the form:

logR=n(ω_{c(or a)}-1)+logk

where n is the empirical reaction order; and k is the rate constant. Calcite precipitation rates in seawater solutions do not vary appreciably as a result of salinity variations over the range investigated, while those for aragonite show an increase in going from the higher (i.e. S=35, 44) to the lower (i.e. S=5, 15, 25) salinity range. This study also confirms previously published findings that above a given saturation state (i.e. Ω_c>/2.6) aragonite precipitates more rapidly than calcite at 25°C.

The incorporation of Sr²⁺ in aragonite and Mg²⁺ in calcite overgrowths are independent of the precipitation rate. The partition coefficient of Sr²⁺ in aragonite is approximately equal to unity and is unaffected by salinity variations between 5 and 44. However, the Mg²⁺ partition coefficient in calcite, increases with decreasing salinity of the parent seawater solutions, possibly as a result of variations in the sulfate content of the solutions and solids.

The experimental results were discussed in the context of a number of geological environments.     

Spinel–sapphirine–quartz bearing composite inclusion within garnet from an ultrahigh-temperature pelitic granulite: Implications for metamorphic history and P–T path

We report here a multiphase mineral inclusion composed of quartz, plagioclase, K-feldspar, sapphirine, spinel, orthopyroxene, and biotite, in porphyroblastic garnet within a pelitic granulite from Rajapalaiyam in the Madurai Granulite Block, southern India. In this unique textural association, hitherto unreported in previous studies, sapphirine shows four occurrences: (1) as anhedral mineral between spinel and quartz (Spr-1), (2) subhedral to euhedral needles mantled by quartz (Spr-2), (3) subhedral to anhedral mineral in orthopyroxene, and (4) isolated inclusion with quartz (Spr-4). Spr-1, Spr-2, and Spr-4 show direct grain contact with quartz, providing evidence for ultrahigh-temperature (UHT) metamorphism at temperatures exceeding 1000 °C. Associated orthopyroxene shows high Mg/(Fe + Mg) ratio ( 0.75) and Al₂O₃ content (up to 9.6 wt.%), also suggesting T > 1050 °C and P > 10 kbar during peak metamorphism.

Coarse spinel (Spl-1) with irregular grain morphology and adjacent quartz grains are separated by thin films of Spr-1 and K-feldspar, suggesting that Spl-1 and quartz were in equilibrium before the stability of Spr-1 + quartz. This texture implies that the P–T conditions of the rock shifted from the stability field of spinel + quartz to sapphirine + quartz. Petrogenetic grid considerations based on available data from the FMAS system favour exhumation along a counterclockwise P–T trajectory. The irregular shape of the inclusion and chemistry of the inclusion minerals are markedly different from the matrix phases suggesting the possibility that the inclusion minerals could have equilibrated from cordierite-bearing silicate-melt pockets during the garnet growth at extreme UHT conditions.     

Pb and rare earth element diffusion in xenotime

Diffusion of Pb and the rare earth elements Sm, Dy and Yb have been characterized in synthetic xenotime under dry conditions. The synthetic xenotime was grown via a Na₂CO₃–MoO₃ flux method. The sources of diffusant for the rare earth diffusion experiments were REE phosphate powders, with experiments run using sources containing a single REE. For Pb, the source consisted a mixture of YPO₄ and PbTiO₃. Experiments were performed by placing source and xenotime in Pt capsules, and annealing capsules in 1 atm furnaces for times ranging from 30 min to several weeks, at temperatures from 1000 to 1500 °C. The REE and Pb distributions in the xenotime were profiled by Rutherford Backscattering Spectrometry (RBS).The following Arrhenius relations are obtained for diffusion in xenotime, normal to (101):

Diffusivities among the REE do not differ greatly in xenotime over the investigated temperature range, in contrast to findings for the REE in zircon [Cherniak, D.J., Hanchar, J.M., Watson, E.B., 1997. Rare earth diffusion in zircon. Chem. Geol. 134, 289–301.], where the LREE diffuse more slowly, and with higher activation energies for diffusion, than the heavier rare earths. In zircon, these differences among diffusion of the rare earths are attributed to the relatively large size of the REE with respect to Zr, for which they likely substitute in the zircon lattice. With the systematic increase in ionic radius from the heavy to lighter REE, this size mismatch becomes more pronounced and diffusivities of the LREE are as consequence slower. Although xenotime is isostructural with zircon, the REE are more closely matched in size to Y, so in xenotime this effect appears much smaller and the REE diffuse at similar rates. In addition, the process of diffusion in xenotime likely involves simple REE^+ 3 → Y^+ 3 exchange, without charge compensation as needed for REE^+ 3 → Zr^+ 4 exchange in zircon. This latter factor may also contribute to the large activation energies for diffusion of the REE in zircon (i.e., 691–841 kJ mol^− 1, [Cherniak, D.J., Hanchar, J.M., Watson, E.B., 1997. Rare earth diffusion in zircon. Chem. Geol. 134, 289–301.]), in comparison with those for xenotime.For Pb, the following Arrhenius relation is obtained (also normal to (101)):

These measurements suggest that Pb diffusion in xenotime is quite slow, even slower than Pb diffusion in monazite and zircon, and considerably slower than diffusion of the REE in xenotime. Xenotime may therefore be even more retentive of Pb isotope signatures than either monazite or zircon in cases where Pb isotopes are altered solely by volume diffusion. However, because the activation energy for Pb diffusion in xenotime is lower than those for monazite and zircon, Pb diffusion may be somewhat faster at many temperatures of geologic interest in xenotime than in monazite or zircon.     

Diffusion of helium in zircon and apatite

Diffusion of helium has been characterized in natural zircon and apatite. Polished slabs of zircon and apatite, oriented either normal or parallel to c were implanted with 100 keV ³He at a dose of 5 × 10^{15 3} He/cm². Diffusion experiments on implanted zircon and apatite were run in Pt capsules in 1-atm furnaces. ³He distributions following experiments were measured with Nuclear Reaction Analysis using the reaction ³He(d,p)⁴He. For diffusion in zircon we obtain the following Arrhenius relations:

Although activation energies for diffusion normal and parallel to c are comparable, there is marked diffusional anisotropy, with diffusion parallel to c nearly 2 orders of magnitude faster than transport normal to c. These diffusivities bracket the range of values determined for He diffusion in zircon in bulk-release experiments, although the role of anisotropy could not be directly evaluated in those measurements.In apatite, the following Arrhenius relation was obtained over the temperature range of 148–449 °C for diffusion normal to c:

In contrast to zircon, apatite shows little evidence of anisotropy. He diffusivities obtained in this study fall about an order of magnitude lower than diffusivities measured through bulk release of He through step-heating, and within an order of magnitude of determinations where ion implantation was used to introduce helium and He distributions measured with elastic recoil detection.Since the diffusion of He in zircon exhibits such pronounced anisotropy, helium diffusional loss and closure cannot be modeled with simple spherical geometries and the assumption of isotropic diffusion. A finite-element code (CYLMOD) has recently been created to simulate diffusion in cylindrical geometry with differing radial and axial diffusion coefficients. We present some applications of the code in evaluating helium lost from zircon grains as a function of grain size and length to diameter ratios, and consider the effects of “shape anisotropy”, where diffusion is isotropic (as in the case of apatite) but shapes of crystal grains or fragments may depart significantly from spherical geometry.     

Cretaceous isochron ages from K–Ar and Ar / Ar dating of eclogitic rocks in the Tso Morari Complex, western Himalaya, India

The Tso Morari Complex, which is thought to be originally the margin of the Indian continent, is composed of pelitic gneisses and schists including mafic rock lenses (eclogites and basic schists). Eclogites studied here have the mineral assemblage Grt + Omp + Ca-Amp + Zo + Phn + Pg + Qtz + Rt. They also have coesite pseudomorph in garnet and quartz rods in omphacite, suggesting a record of ultrahigh-pressure metamorphism. They occur only in the cores of meter-scale mafic rock lenses intercalated with the pelitic schists. Small mafic lenses and the rim parts of large lenses have been strongly deformed to form the foliation parallel to that of the pelitic schists and show the mineral assemblages of upper greenschist to amphibolite facies metamorphism. The garnet–omphacite thermometry and the univariant reaction relations for jadeite formation give 13–21 kbar at 600 °C and 16–18 kbar at 750 °C for the eclogite formation using the jadeite content of clinopyroxene (X_Jd = 0.48).

Phengites in pelitic schists show variable Si / Al and Na / K ratios among grains as well as within single grains, and give K–Ar ages of 50–87 Ma. The pelitic schist with paragonite and phengite yielded K–Ar ages of 83.5 Ma (K = 4.9 wt.%) for paragonite–phengite mixture and 85.3 Ma (K = 7.8 wt.%) for phengite and an isochron age of 91 ± 13 Ma from the two dataset. The eclogite gives a plateau age of 132 Ma in Ar/Ar step-heating analyses using single phengite grain and an inverse isochron age of 130 ± 39 Ma with an initial ⁴⁰Ar / ³⁶Ar ratio of 434 ± 90 in Ar/Ar spot analyses of phengites and paragonites. The Cretaceous isochron ages are interpreted to represent the timing of early stage of exhumation of the eclogitic rocks assuming revised high closure temperature (500 °C) for phengite K–Ar system. The phengites in pelitic schists have experienced retrograde reaction which modified their chemistry during intense deformation associated with the exhumation of these rocks with the release of significant radiogenic ⁴⁰Ar from the crystals. The argon release took place in the schists that experienced the retrogression to upper greenschist facies metamorphisms from the eclogite facies conditions.     

Corundum + quartz and Mg-staurolite bearing granulite from the Limpopo Belt, southern Africa: Implications for a P–T path

A new occurrence of the rare corundum + quartz assemblage and magnesian staurolite has been found in a gedrite–garnet rock from the Central Zone of the Neoarchean Limpopo Belt in Zimbabwe. Poikiloblastic garnet in the sample contains numerous inclusions of corundum + quartz ± sillimanite, magnesian staurolite + sapphirine ± orthopyroxene, and sapphirine + sillimanite assemblages, as well as monophase inclusions. Corundum, often containing subhedral to rounded quartz, occurs as subhedral to euhedral inclusions in the garnet. Quartz and corundum occur in direct grain contact with no evidence of a reaction texture. The textures and Fe–Mg ratios of staurolite inclusions and the host garnet suggest a prograde dehydration reaction of St → Grt + Crn + Qtz + H₂O to give the corundum + quartz assemblage. Peak conditions of 890–930 °C at 9–10 kbar are obtained from orthopyroxene + sapphirine and garnet + staurolite assemblages. A clockwise P–T path is inferred, with peak conditions being followed by retrograde conditions of 4–6 kbar and 500–570 °C. The presence of unusually magnesian staurolite (Mg / [Fe + Mg] = 0.47–0.53) and corundum + garnet assemblages provides evidence for early high-pressure metamorphism in the Central Zone, possibly close to eclogite facies. The prograde high-pressure event followed by high- to ultrahigh-temperature metamorphism and rapid uplifting of the Limpopo Belt could have occurred as a result of Neoarchean collisional orogeny involving the Zimbabwe and Kaapvaal Cratons.     

Reactions and textures in grossular–wollastonite–scapolite calc–silicate granulites from Maligawila, Sri Lanka: evidence for high-temperature isobaric cooling in the meta-sediments of the Highland Complex

Grossular–wollastonite–scapolite calc–silicate granulites from Maligawila in the Buttala klippe, which form part of the overthrusted rocks of the Highland Complex of Sri Lanka, preserve a number of spectacular coronas and replacement textures that could be effectively used to infer their P–T–fluid history. These textures include coronas of garnet, garnet–quartz, and garnet–quartz–calcite at the grain boundaries of wollastonite, scapolite, and calcite as well as calcite–plagioclase and calcite–quartz symplectites or finer grains after scapolite and wollastonite respectively. Other textures include a double rind of coronal scapolite and coronal garnet between matrix garnet and calcite. The reactions that produced these coronas and replacement textures, except those involving clinopyroxene, are modelled in the CaO–Al₂O₃–SiO₂–CO₂ system using the reduced activities. Calculated examples of T–X_CO2 and P–X_CO2 projections indicate that the peak metamorphic temperature of about 900–875 °C at a pressure of 9 kbar and the peak metamorphic fluid composition is constrained to be low in X_CO2 (0.1<X_CO2<0.30). Interpretation of the textural features on the basis of the partial grids revealed that the calc–silicate granulites underwent high-temperature isobaric cooling, from about 900–875 °C to a temperature below 675 °C, following the peak metamorphism. The late-stage cooling was accompanied by an influx of hydrous fluids. The calc–silicate granulites provide evidence for high-temperature isobaric cooling in the meta-sediments of the Highland Complex, earlier considered by some workers to be confined exclusively to the meta-igneous rocks. The coronal scapolite may have formed under open-system metasomatism.     

Thermodynamic modelling of C–O–H fluids

H₂O, CO₂, CH₄, CO, H₂ and O₂ are the most important species in crustal fluids. The composition of these C–O–H fluids can be calculated if the pressure, temperature, carbon activity, and either the oxygen fugacity or the atomic H/O ratio of the fluid is known. The calculation methods are discussed and calculation results are illustrated with isobaric T–X_i, P–T, and isobaric–isothermal ternary C–O–H diagrams. Fluid inclusion compositions, in particular, the X_CO2/(X_CO2+X_CH4) ratio, can be used for C–O–H model calculations. However, care should be taken about possible post-entrapment changes, which may have modified the chemical composition of the fluid inclusion.     

Partial melting and P–T evolution of the Kodaikanal Metapelite Belt, southern India

The Kodaikanal region of the Madurai Block in southern India exposes a segment of high-grade metamorphic rocks dominated by an aluminous garnet–cordierite–spinel–sillimanite–quartz migmatite suite, designated herein as the Kodaikanal Metapelite Belt (KMB). These rocks were subjected to extreme crustal metamorphism during the Late Neoproterozoic despite the lack of diagnostic ultrahigh-temperature assemblages. The rocks preserve microstructural evidence demonstrating initial-heating, dehydration melting to generate the peak metamorphic assemblage and later retrogression of the residual assemblages with remaining melt. The peak metamorphic assemblage is interpreted to be garnet + sillimanite + K-feldspar + spinel + Fe–Ti oxide + quartz + melt, which indicates pressure–temperature (P–T) conditions around 950–1000 °C and 7–8 kbar based on calculated phase diagrams. A clockwise P–T path is proposed by integrating microstructural information with pseudosections. We show that evidence for extreme crustal metamorphism at ultrahigh-temperature conditions can be extracted even in the cases where the rocks lack diagnostic ultrahigh-temperature mineral assemblages. Our approach confirms the widespread regional occurrence of UHT metamorphism in the Madurai Block during Gondwana assembly and point out the need for similar studies on adjacent continental fragments.     

Experimental calibration of oxygen isotope fractionation between quartz and zircon

We report the results of an experimental calibration of oxygen isotope fractionation between quartz and zircon. Data were collected from 700 to 1000 °C, 10–20 kbar, and in some experiments the oxygen fugacity was buffered at the fayalite–magnetite–quartz equilibrium. Oxygen isotope fractionation shows no clear dependence on oxygen fugacity or pressure. Unexpectedly, some high-temperature data (900–1000 °C) show evidence for disequilibrium oxygen isotope partitioning. This is based in part on ion microprobe data from these samples that indicate some high-temperature quartz grains may be isotopically zoned. Excluding data that probably represent non-equilibrium conditions, our preferred calibration for oxygen isotope fractionation between quartz and zircon can be described by:

This relationship can be used to calculate fractionation factors between zircon and other minerals. In addition, results have been used to calculate WR/melt–zircon fractionations during magma differentiation. Modeling demonstrates that silicic magmas show relatively small changes in δ¹⁸O values during differentiation, though late-stage mafic residuals capable of zircon saturation contain elevated δ¹⁸O values. However, residuals also have larger predicted melt–zircon fractionations meaning zircons will not record enriched δ¹⁸O values generally attributed to a granitic protolith. These results agree with data from natural samples if the zircon fractionation factor presented here or from natural studies is applied.     

Solubility and dissolution rate of silica in acid fluoride solutions

We performed 57 batch reactor experiments in acidic fluoride solutions to measure the dissolution rate of quartz. These rate data along with rate data from published studies were fit using multiple linear regression to produce the following non-unique rate law for quartz

where 10^−5.13 < a_HF < 10^1.60, −0.28 < pH < 7.18, and 298 < T < 373 K. Similarly, 97 amorphous silica dissolution rate data from published studies were fit by multiple linear regression to produce the following non-unique rate law for amorphous silica

where 10^−2.37 < a_HF < 10^1.61, −0.32 < pH < 4.76 and 296 < T < 343 K. Regression of the rates versus other combinations of solution species, e.g.  + H⁺, F⁻ + H⁺, HF + , HF + F⁻, or  + F⁻, produced equally good fits. Any of these rate laws can be interpreted to mean that the rate-determining step for silica dissolution in fluoride solutions involves a coordinated attack of a Lewis acid, on the bridging O atom and a Lewis base on the Si atom. This allows a redistribution of electrons from the Si–O bond to form a O–H group and a Si–FH group.     

Distribution of Fe and Mg between coexisting garnet and hornblende in synthetic and natural systems: an empirical calibration of the garnet–hornblende Fe–Mg geothermometer

Multiple regression analysis of a compilation of the Fe²⁺–Mg distribution between garnet and hornblende from experimental runs on basaltic to intermediate compositions (n=22) and coexisting garnet–clinopyroxene–hornblende from natural (intermediate to basaltic) rocks (n=43) has been performed to define ln K_{D(Fe²⁺/Mg)}^Grt–Hbl as a function of temperature and garnet composition. The regression of data covering a large span in pressure (5–16 kbar), temperature (515–1025°C) and composition yields the ln K_{D(Fe²⁺/Mg)}^Grt–Hbl–P–T compositional relationship (r²=0.93):

where

Application of this expression to natural garnet–hornblende pairs in intermediate to basaltic and semipelitic rock types from various settings gives temperatures that are consistent with other methods.     

An empirical sapphirine-spinel Mg---Fe exchange thermometer and its application to high grade xenoliths in the Popes Harbour dyke, Nova Scotia, Canada

Spinel-sapphirine-corundum-rutile parageneses in metapelitic xenoliths from the lamprophyric Popes Harbour dyke are enclosed by feldspathic (±rare quartz) haloes that embay aluminosilicates and biotite. These feldspathic haloes contain plagioclase (An_20–40) and/or an alkali or ternary (hypersolvus) feldspar, and show a variety of igneous and devitrification textures, suggesting an anatectic origin. The spinel-bearing parageneses are interpreted as the refractory residue formed by the incongruent melting of biotite, aluminosilicates and associated phases.

Equilibration temperatures of these assemblages are estimated from an empirical sapphirine-spinel Mg---Fe exchange thermometer derived from literature data on both silica-saturated and undersaturated sapphirine granulites. Linear regression (R=0.81) of the calibrant data yields the expression T(°C) = [800 + (228^*InKd)] − 273 where

Kd=(X^sp_Fe/X^sp_Mg)/(X^sa_Fe/X^sa_Mg)

Precision is estimated at ± 100°C, but will likely be less for highly oxidized sapphirine granulites owing to (1) errors in the stoichiometric estimation of X_Fe³⁺ from microprobe data and (2) the formation of magnetite at the expense of spinel or sapphirine, leading to an increase in X_Mg in either or both phases during cooling. Application of this expression to the reduced (graphite-bearing) Popes Harbour xenoliths yields T of 725–795°C. Anatexis is attributed to thermal metamorphism by the lamprophyric magma prior to and/or during entrainment of xenolith material in the dyke. Higher-T assemblages were quenched before the xenoliths attained thermal equilibrium with the magma, consequently prograde reaction textures and compositional zoning patterns are preserved.     

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.     

Comparative study of the kinetics and mechanisms of dissolution of carbonate minerals

The influence of pH on the rate of dissolution of various carbonates (calcite, aragonite, witherite, magnesite and dolomite) has been investigated at 25°C using a continuous fluidized bed reactor. The general rate dependence on pH observed for the simple carbonates is very similar and is in agreement with the results observed for calcite and aragonite by L.N. Plummer and coworkers. However, the rate of dissolution of magnesite is approximately four orders of magnitude lower than calcite.

For simple carbonates, the elementary steps involved in the dissolution reaction are:

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where M represents the metal ion which can be Ca, Mg and Ba. According to the stoichiometry of the three reaction steps and the thermodynamic constraints, the total forward and backward rates can be expressed as:

R_f=k₁a_H+k₂a_H2CO3^*+K₃

r_b=k_-1^aM²+^aHCO₃^-+k_-2^aHCO3^-+k_{-3^aM²+^aCO3^2-}

The rate constants (k₁, k₂, k₃ and k₋₃) determined with our experimental results for calcite, aragonite and witherite show that the dissolution rates are similar for these three minerals and that the nature of the cations does not play a significant role. The good agreement between the K_sp calculated from the measured k₃/k₋₃ ratio and the theromodynamic value suggests that our dissolution mechanism is coherent.

The rate dependence on pH of the dissolution of dolomite obeys a fractional order at low pH's and confirms previously published observations therein. However, the two-step reaction mechanism proposed does not explain the fractional reaction order observed, which is likely due to a more complex surface reaction.     

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.     

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).     

Permeability of compacted granule–clay mixtures

Achieving a sufficiently low permeability for the aggregate-clay mixtures, whether used as the core of embankment dam or soil liner, is essential. The study illustrates the role of granule (bead or aggregate) content and size, confining stress and fabric anisotropy on the permeability of ceramic bead–lean clay and aggregate-fat clay mixtures. It is shown that depending on the plasticity of the clay, the permeability may decrease or increase with bead/aggregate content. The permeability also decreases when either granule size or confining stress increases. It is found that the permeability is affected by fabric anisotropy in such a manner that its value in the horizontal direction (k_h) is more than that in the vertical direction (k_v), however, k_h/k_v decreases towards 1 for bead contents equal to or below 40%. In high bead content mixtures (i.e., 60% beads) k_h/k_v reaches as high as 3 with an increase in the confining stress. The concept of the development of heterogeneous field of density in the clay is also used to demonstrate the impact of granule size and fabric anisotropy on the permeability.     

Oxygen isotopic fractionation during inorganic calcite precipitation ― Effects of temperature, precipitation rate and pH

Stable oxygen isotopic fractionation during inorganic calcite precipitation was experimentally studied by spontaneous precipitation at various pH (8.3 < pH < 10.5), precipitation rates (1.8 < log R < 4.4 μmol m^− 2 h^− 1) and temperatures (5, 25, and 40 °C) using the CO₂ diffusion technique.The results show that the apparent stable oxygen isotopic fractionation factor between calcite and water (α_{calcite–water}) is affected by temperature, the pH of the solution, and the precipitation rate of calcite. Isotopic equilibrium is not maintained during spontaneous precipitation from the solution. Under isotopic non-equilibrium conditions, at a constant temperature and precipitation rate, apparent 1000lnα_{calcite–water} decreases with increasing pH of the solution. If the temperature and pH are held constant, apparent 1000lnα_{calcite–water} values decrease with elevated precipitation rates of calcite. At pH = 8.3, oxygen isotopic fractionation between inorganically precipitated calcite and water as a function of the precipitation rate (R) can be described by the expressions

at 5, 25, and 40 °C, respectively.The impact of precipitation rate on 1000lnα_{calcite–water} value in our experiments clearly indicates a kinetic effect on oxygen isotopic fractionation during calcite precipitation from aqueous solution, even if calcite precipitated slowly from aqueous solution at the given temperature range. Our results support Coplen's work [Coplen T. B. (2007) Calibration of the calcite–water oxygen isotope geothermometer at Devils Hole, Nevada, a natural laboratory. Geochim. Cosmochim. Acta 71, 3948–3957], which indicates that the equilibrium oxygen isotopic fractionation factor might be greater than the commonly accepted value.     

H2O diffusion models in rhyolitic melt with new high pressure data

Water diffusion in silicate melts is important for understanding bubble growth in magma, magma degassing and eruption dynamics of volcanos. Previous studies have made significant progress on water diffusion in silicate melts, especially rhyolitic melt. However, the pressure dependence of H₂O diffusion is not constrained satisfactorily. We investigated H₂O diffusion in rhyolitic melt at 0.95–1.9 GPa and 407–1629 °C, and 0.2–5.2 wt.% total water (H₂O_t) content with the diffusion-couple method in a piston-cylinder apparatus. Compared to previous data at 0.1–500 MPa, H₂O diffusivity is smaller at higher pressures, indicating a negative pressure effect. This pressure effect is more pronounced at low temperatures. Assuming H₂O diffusion in rhyolitic melt is controlled by the mobility of molecular H₂O (H₂O_m), the diffusivity of H₂O_m (D_H2Om) at H₂O_t ≤ 7.7 wt.%, 403–1629 °C, and ≤ 1.9 GPa is given by

D_H2Om=D₀exp(aX),