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.     

Strain rate effect on the compressive strength of frozen sand

Cylindrical specimens of fine Ottawa sand (A.S.T.M. designation C-109), compacted at the optimum moisture content and saturated before unidirectional freezing, have been tested in uniaxial compression at a cold room temperature of —5.5°C and strain rates between 10⁻⁷ and 10⁻² s⁻¹. The results agree with an extrapolation of data obtained by Sayles and Epanchin [1], but are much higher than those obtained by both Goughnour and Andersland [2] and Perkins and Ruedrich [3] at strain rates below 10⁻⁵ s⁻¹. There is evidence that this may be due to variation in total moisture (ice) content, the conditions under which the specimens were frozen (closed system or an open system) and to the end effects at the platen—specimen interface.     

Gum rosin (colophony): A suitable material for thermomechanical modelling of the lithosphere

We investigate the use of a ductile material with temperature-sensitive viscosity for thermomechanical modelling of the lithosphere. First, we consider the scaling of mechanical and thermal properties. For a normal field of gravity, the balance of stresses and body forces sets the stress scale, in proportion to the linear dimensions and the densities. The equation of thermal conduction sets the time scale. The activation enthalpy for creep sets the temperature scale; but the thermal expansivity provides an additional constraint on this temperature scale.

Gum rosin appears to be a suitable material for lithospheric modelling. We have measured its flow properties, at various temperatures, in a specially designed rotary viscometer with unusually low machine friction. The rosin is almost Newtonian. Strain rate depends upon stress to the power n, where 1.0 <n < 1.14. The viscosity varies over 5 orders of magnitude, from about 10² Pa s at 80°C, to about 10⁷ Pa s at 40°C. The activation enthalphy is thus about 250 kJ/mol. Measured with a needle probe, the thermal conductivity is 0.113 ± 0.001 W m⁻¹K⁻¹; the thermal diffusivity, (6±3) ×10⁻⁷ m² s⁻¹. Calculated from X-ray profiles, the thermal expansivity is about 3 × 10⁻⁴ K⁻¹. These thermal and mechanical properties make gum rosin suitable for thermomechanical models, where linear dimensions scale down by a factor of 10⁶; time, by 10¹¹; viscosity, by 10¹⁷; and temperature change, by 10¹.     

Petrology of the Hopen mangerite-charnockite intrusion, Lofoten, north Norway

The Hopen massif, intrusive age 1900 m.y., exposed area 15 km², in the Lofoten-Vesterålen granulite facies province has the mineral assemblages: (1) mesoperthite+plagioclase (An_7–20)+quartz+clinopyroxene (Di_20–25)+orthopyroxene En_15–25+opaques±minor amphibole±minor biotite; (2) mesoperthite+plagioclase (An <2)+quartz+clinopyroxene (Di <10)+olivine Fe lt;5)+opaques. By using mineral and whole rock analyses, the crystallization conditions were estimated to be 1000°C, 12 kb load pressure and an oxygen fugacity approximately corresponding to the WM buffer. Rocks with the assemblage of type (2) contain secondary orthoferrosilite (Fe_0.90–0.95Mn_0.04–0.07Mg_0.01Ca_0.01)₂Si₂O₆, generated by reactions involving fayalite, magnetite and quartz at 800°C, 10kb load pressure and at oxygen fugacities approaching QFM buffer conditions. Subsequent to a crustal thickening, the mangeritic rocks in Lofoten-Vesterålen were emplaced in a tensional environment comparable with modern continental rifts. A ‘gabbro pillow’ magma chamber at the crustal base is proposed as parental magma for the mangeritic rocks, of which the Hopen massif represents a late differentiation.     

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).     

Water-enhanced dynamic recrystallization and solution transfer in experimentally deformed carnallite

Cylindrical samples of polycrystalline carnallite (KMgCl₃, 6H₂O) were deformed in a triaxial apparatus at 60°C, at confining pressures between 0.1 and 31 MPa and at strain rates between 10⁻⁴ and 10⁻⁸ s⁻¹. In a number of cases, small amounts of saturated carnallite brine were added. Samples without added brine deform by intracrystalline slip, mechanical twinning, cracking, and by frictional sliding on crack surfaces. Stress-strain curves of these samples are strongly dependent on confining pressure. Addition of brine has a dramatic effect on both microstructural development and mechanical properties. Grain-boundary migration is strongly enhanced. At lower strain rates, additional intracrystalline effects start to appear, together with the onset of solution transfer. Rapid compaction in samples deformed with added brine causes high fluid pressures to develop. At higher strain rates addition of brine results in a decrease of the flow stress by a factor of two. This weakening will increase even further at strain rates below about 10⁻⁹ s⁻¹, when solution transfer becomes rate controlling. It is argued that deformation of carnallite in nature is adequately described by the flow law found for samples deformed with added brine.     

Variation in element release rate from different mineral size fractions from the B horizon of a granitic podzol

Far-from-equilibrium batch dissolution experiments were carried out on the 2000–500, 500–250, 250–53 and 53–2 μm size fractions of the mineral component of the B horizon of a granitic iron humus podzol after removal of organic matter and secondary precipitates. The different size fractions were mineralogically and chemically similar, the main minerals present being quartz, alkali and plagioclase feldspar, biotite and chlorite. Specific surface area increased with decreasing grain size. The measured element release rates decreased in the order 53–2>>>2000–500>500–250>250–53 μm. Surface area normalised element release rates from the 2000–500, 500–250 and 250–53 μm size fractions (0.6–77×10⁻¹⁴ mol/m²/s) were intermediate between literature reported surface area normalised dissolution rates for monomineralic powders of feldspar (0.1–0.01×10⁻¹⁴ mol/m²/s) and sheet silicates (100×10⁻¹⁴ mol/m²/s) dissolving under similar conditions. Element release rates from the 53–2 μm fraction (400–3000×10⁻¹⁴ mol/m²/s) were a factor of 4–30 larger than literature reported values for sheet silicates. The large element release rate of the 53–2 μm fraction means that, despite the small mass fraction of 53–2 μm sized particles present in the soil, dissolution of this fraction is the most important for element release into the soil. A theoretical model predicted similar (within a factor of <2) bulk element release rates for all the mineral powders if observed thicknesses of sheet silicate grains were used as input parameters. Decreasing element release rates with decreasing grain size were only predicted if the thickness of sheet silicates in the powders was held constant. A significantly larger release rate for the 53–2 μm fraction relative to the other size fractions was only predicted if either surface roughness was set several orders of magnitude higher for sheet silicates and several orders of magnitude lower for quartz and feldspars in the 53–2 μm fraction compared to the other size fractions or if the sheet silicate thickness input in the 53–2 μm fraction was set unrealistically low. It is therefore hypothesised that the reason for the unpredicted large release rate from the 52–3 μm size fraction is due to one or more of the following reasons: (1) the greater reactivity of the smaller particles due to surface free energy effects, (2) the lack of proportionality between the BET surface area used to normalise the release rates and the actual reactive surface area of the grains and, (3) the presence of traces quantities of reactive minerals which were undetected in the 53–2 μm fraction but were entirely absent in the coarser fractions.     

Partitioning coefficients between olivine and silicate melts

Variation of Nernst partition coefficients (D) between olivine and silicate melts cannot be neglected when modeling partial melting and fractional crystallization. Published natural and experimental ^{olivine/liquid}D data were examined for covariation with pressure, temperature, olivine forsterite content, and melt SiO₂, H₂O, MgO and MgO/MgO + FeO^total. Values of ^{olivine/liquid}D generally increase with decreasing temperature and melt MgO content, and with increasing melt SiO₂ content, but generally show poor correlations with other variables. Multi-element ^{olivine/liquid}D profiles calculated from regressions of D REE–Sc–Y vs. melt MgO content are compared to results of the Lattice Strain Model to link melt MgO and: D₀ (the strain compensated partition coefficient), E_M³⁺ (Young's Modulus), and r₀ (the size of the M site). Ln D₀ varies linearly with Ln MgO in the melt; E_M³⁺ varies linearly with melt MgO, with a dog-leg at ca. 1.5% MgO; and r₀ remains constant at 0.807 Å. These equations are then used to calculate ^{olivine/liquid}D for these elements using the Lattice Strain Model. These empirical parameterizations of ^{olivine/liquid}D variations yield results comparable to experimental or natural partitioning data, and can easily be integrated into existing trace element modeling algorithms. The ^{olivine/liquid}D data suggest that basaltic melts in equilibrium with pure olivine may acquire small negative Ta–Hf–Zr–Ti anomalies, but that negative Nb anomalies are unlikely to develop. Misfits between results of the Lattice Strain Model and most light rare earth and large ion lithophile partitioning data suggest that kinetic effects may limit the lower value of D for extremely incompatible elements in natural situations characterized by high cooling/crystallization rates.     

Evolution of mineral–fluid interfaces studied at pressure with synchrotron X-ray techniques

In situ measurements of mineral surface evolution during the process of pressure solution are possible with the high brightness of synchrotron X-ray sources. This capability has been explored through the use of newly developed reaction vessels that allow transmission of the incident and scattered X-ray beam through a low atomic weight piston. Several new vessels are described, along with details of computational algorithms that are used to simulate X-ray scattering in this unconventional geometry. Results using calcite (CaCO₃) and halite (NaCl) as reactant crystals are presented and compared to other atomic-scale measurements of surface dissolution processes. Calcite was reacted with an unsaturated fluid at 30 bars of pressure for approximately 24 h. During reaction the root mean square surface roughness (σ) evolved from 13.7 Å (± 0.5 Å) to 19.5 Å (± 1.0 Å), giving a roughening rate of: dσ/dt = +6.3 × 10^− 5 Å s^− 1. This is consistent with other measurements made with free calcite surfaces and is driven almost entirely by chemical disequilibrium. Analysis of the surface ex situ post-reaction gives an identical σ value, showing that the in situ measurements are well-constrained. Experiments also at 30 bars but in a saturated solution indicate that the calcite surface does not significantly roughen, giving the result that pressure solution of calcite at this pressure cannot be monitored in experiments of several days duration. Experiments with halite, a much more reactive phase, in saturated solutions showed the reflectivity profile to be dynamic on a time scale of hours. This experiment was left to reach equilibrium over 108 days and then re-analyzed, showing that σ had increased from 34 Å (± 2 Å) to 41 Å (± 2 Å), giving a roughening rate of: dσ/dt ≤ +6.4 × 10^− 7 Å s^− 1. This is two orders of magnitude smaller than the calcite roughening rate caused by chemical disequilibrium and provides the first direct in situ atomic-scale measurement of the rate of surface roughening due to pressure solution.     

Compositions of magmas and carbonate–silicate liquid immiscibility in the Vulture alkaline igneous complex, Italy

This paper presents a study of melt and fluid inclusions in minerals of an olivine-leucite phonolitic nephelinite bomb from the Monticchio Lake Formation, Vulture. The rock contains 50 vol.% clinopyroxene, 12% leucite, 10% alkali feldspars, 8% hauyne/sodalite, 7.5% nepheline, 4.5% apatite, 3.2% olivine, 2% opaques, 2.6% plagioclase, and < 1% amphibole. We distinguished three generations of clinopyroxene differing in composition and morphology. All the phenocrysts bear primary and secondary melt and fluid inclusions, which recorded successive stages of melt evolution. The most primitive melts were found in the most magnesian olivine and the earliest clinopyroxene phenocrysts. The melts are near primary mantle liquids and are rich in Ca, Mg and incompatible and volatile elements. Thermometric experiments with the melt inclusions suggested that melt crystallization began at temperatures of about 1200 °C. Because of the partial leakage of all primary fluid inclusions, the pressure of crystallization is constrained only to minimum of 3.5 kbar. Combined silicate–carbonate melt inclusions were found in apatite phenocrysts. They are indicative of carbonate–silicate liquid immiscibility, which occurred during magma evolution. Large hydrous secondary melt inclusions were found in olivine and clinopyroxene. The inclusions in the phenocrysts recorded an open-system magma evolution during its rise towards the surface including crystallization, degassing, oxidation, and liquid immiscibility processes.     

Dissolution kinetics of experimentally shocked silicate minerals

The effect of lattice strain on mineral dissolution rates was examined by comparing the dissolution rates of shocked and unshocked minerals. Labradorite, oligoclase and hornblende were explosively shocked at mean pressures ranging from 4 to 22 GPa. The labradorite was examined with transmission electron microscopy to estimate the density of dislocations produced by the shock-loading experiment. Subsamples of the labradorite were then thermally annealed to remove some of the dislocations, and to evaluate the importance of such thermal pre-treatment in preparing mineral surfaces for experiments. The dissolution rates of these minerals were measured in batch experiments at pH-values of 2.7 and 4.0.

Shock-loading did not produce extremely high dislocation densities in the labradorite. The density of dislocations in the unshocked labradorite is ≤ 10¹⁰ m⁻². After shocking, the density increases to 10¹²-10¹³ m⁻². The distribution of dislocations is heterogeneous, and the amount of deformation does not increase substantially with shock pressure. These results are highly atypical of shock-modified minerals, where relatively low shock pressures usually induce high ( 10¹⁵ m⁻²) densities of dislocations. Thermal annealing for 1 hr. at 900°C in a dry furnace removes many dislocations from the shocked labradorite.

The difference in observed dissolution rates between shocked and unshocked minerals appears to have a weak correlation with the increase in the density of dislocations on the mineral surface. The unshocked and shocked oligoclase and hornblende samples exhibit limited dissolution enhancement at pH 4.0. Increasing the density of dislocations by several orders of magnitude with shock-loading causes a relatively small increase in dissolution rates for these silicate minerals. These results suggest that the surface dislocations produced by the shock treatment are not the primary sites for dissolution reactions.     

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.     

The usability of bottom ash as an engineering material when amended with different matrices

This study aims at investigating the utilization of bottom ash obtained from four different power stations as a construction fill and landfill bottom liner. For the matrix material, commercial powdered bentonite, construction lime and natural clay were used. Compaction tests (Standard Proctor and vibratory hammer) were carried out on the different ratios of bottom ash and matrix material. The optimum water content ranged from 40 to 45% yielding a dry density mostly ca 1 Mg m⁻³. Uniaxial compressive strength of mixtures ranges from 0.1 to 0.5 kgf cm⁻² which showed a 3–20-fold increase when tested on 28-day cured specimens. Triaxial compression tests yield varying rates of shear strength which also showed as high as an 11-fold increase for cured specimens. The hydraulic conductivity of those mixtures was mostly ca 10⁻⁴ cm s⁻¹, which is not considered to be low enough for landfill lining. Leaching tests using deionized water were also performed to investigate the possible effect of leachate produced from the mixtures on the environment. In conclusion a light density and environmentally friendly mixture is determined and proposed as construction filler.     

Extracting olivine (Fo–Fa) compositions from Raman spectral peak positions

The dominant feature of the olivine Raman spectrum is a doublet that occurs in the spectral region of 815–825 cm⁻¹ (DB1) and 838–857 cm⁻¹ (DB2). These features arise from coupled symmetric and asymmetric stretching vibrational modes of the constituent SiO₄ tetrahedra. The frequencies of both peaks show monotonic shifts following cation substitution between forsterite and fayalite. We present a calibration for extracting olivine Fo contents (Fo = Mg/(Mg + Fe) molar ratio; Fo_0–100) from the peak positions of this doublet, permitting estimates of chemical composition from Raman spectra (acquired in the laboratory or field) as well as providing information on crystal structure (distinction of polymorphs). Eight samples spanning the compositional range from forsterite to fayalite were used to develop the calibration equations for the DB1 and DB2 peaks individually and together. The data indicate that the DB1 peak is more reliable for calculating the compositions of Fe-rich olivine but that the DB2 peak is better for magnesian compositions. The two-peak calibration overcomes the limitations of the single-peak calibrations and is capable of calculating olivine compositions to within ±10 Fo units.     

In situ determination of long-term basaltic glass dissolution in the unsaturated zone

Maximum in situ weathering rates of basaltic glass measured at the El Malpais National Monument in New Mexico are on the order of 2–5×10⁻¹⁹ mol/cm² s. Rates were calculated from backscattered electron (BSE) imaging of weathered porosity and are equivalent to 1.7–5% of the surface per 1000 years. Weathering is independent of glass composition but appears to increase with flow elevation at El Malpais. Measured rates represent weathering over 3000 years and are substantially lower than glass dissolution rates measured in the laboratory over much shorter time spans. Basaltic glass is a close chemical analogue to glass hosts proposed for encapsulation of high-level nuclear wastes. Radionuclide release rates predicted from the basis of in situ field rates are substantially less than those predicted from short-term laboratory experiments.     

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.     

Commingling and mixing of S-type peraluminous, ultrapotassic and basaltic magmas in the Cayconi volcanic field, Cordillera de Carabaya, SE Peru

The Cayconi district of the Cordillera de Carabaya, SE Peru, exposes a remnant of an upper Oligocene–Lower Miocene (22.2–24.4 Ma) volcanic field, comprising a diverse assemblage of S-type silicic and calc-alkaline basaltic to andesitic flows, members of the Picotani Group of the Central Andean Inner Arc. Basaltic flows containing olivine, plagioclase, clinopyroxene, ilmenite and glass, and glassy rhyolitic agglutinates with phenocrystic quartz, cordierite, plagioclase, sanidine, ilmenite and apatite, respectively exhibit mineralogical and geochemical features characteristic of medium-K mafic and Lachlan S-type silicic lavas. Cordierite-bearing dacitic agglomerates and lavas, however, are characterized by dispersed, melanocratic micro-enclaves and phenocrysts set in a fine-grained quartzo-feldspathic matrix. They contain a bimodal mica population, comprising phlogopite and biotite, as well as complexly zoned, sieve-textured plagioclase grains, sector-zoned cordierite, sanidine, quartz, irregular patches of replaced olivine, clinopyroxene and orthopyroxene and accessory phases including zircon, monazite, ilmenite and chromite. The coexistence of minerals not in mutual equilibrium and the growth/dissolution textures exhibited by plagioclase are features indicative of magmatic commingling and mixing. Trachytic-textured andesite flows interlayered with olivine+plagioclase–glomerophyric, calc-alkaline basalts have a phenocrystic assemblage of resorbed orthopyroxene and plagioclase and exhibit melanocratic groundmass patches of microphenocrystic phlogopite, Ca-rich sanidine, ilmenite and aluminous spinel. The mineralogical and mineral chemical relationships in both the dacites and the trachytic-textured andesites imply subvolcanic mixing between distinct ultrapotassic mafic melts, not represented by exposed rock types, and both the S-type silicic and calc-alkaline mafic magmas. Such mixing relationships are commonly observed in the Oligo-Miocene rocks of the Cordillera de Carabaya, suggesting that the S-type rocks in this area and, by extension, elsewhere derive their unusually high K₂O, Ba, Sr, Cr and Ni concentrations from commingling and mixing with diverse, mantle-derived potassic mafic magmas.     

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.     

Determining mineral weathering rates based on solid and solute weathering gradients and velocities: application to biotite weathering in saprolites

Chemical weathering gradients are defined by the changes in the measured elemental concentrations in solids and pore waters with depth in soils and regoliths. An increase in the mineral weathering rate increases the change in these concentrations with depth while increases in the weathering velocity decrease the change. The solid-state weathering velocity is the rate at which the weathering front propagates through the regolith and the solute weathering velocity is equivalent to the rate of pore water infiltration. These relationships provide a unifying approach to calculating both solid and solute weathering rates from the respective ratios of the weathering velocities and gradients. Contemporary weathering rates based on solute residence times can be directly compared to long-term past weathering based on changes in regolith composition. Both rates incorporate identical parameters describing mineral abundance, stoichiometry, and surface area.

Weathering gradients were used to calculate biotite weathering rates in saprolitic regoliths in the Piedmont of Northern Georgia, USA and in Luquillo Mountains of Puerto Rico. Solid-state weathering gradients for Mg and K at Panola produced reaction rates of 3 to 6×10⁻¹⁷ mol m⁻² s⁻¹ for biotite. Faster weathering rates of 1.8 to 3.6×10⁻¹⁶ mol m⁻² s⁻¹ are calculated based on Mg and K pore water gradients in the Rio Icacos regolith. The relative rates are in agreement with a warmer and wetter tropical climate in Puerto Rico. Both natural rates are three to six orders of magnitude slower than reported experimental rates of biotite weathering.     

Mantle metasomatism and magma formation in continental lithosphere: Data on xenoliths in alkali basalts from the Makhtesh Ramon,Negev desert,Israel

Mantle xenoliths (lherzolites, clinopyroxene dunites, wehrlites, and clinopyroxenites) in the Early Cretaceous volcanic rocks of Makhtesh Ramon (alkali olivine basalts, basanites, and nephelinites) represent metasomatized mantle, which served as a source of basaltic melts. The xenoliths bear signs of partial melting and previous metasomatic transformations. The latter include the replacement of orthopyroxene by clinopyroxene in the lherzolites and, respectively, the wide development of wehrlites and olivine clinopyoroxenites. Metasomatic alteration of the peridotites is accompanied by a sharp decrease in Mg, Cr, and Ni, and increase of Ti, Al, Ca contents and ³⁺Fe/²⁺Fe ratio, as well as the growth of trace V, Sc, Zr, Nb, and Y contents. The compositional features of the rocks such as the growth of ³⁺Fe/²⁺Fe and the wide development of Ti-magnetite in combination with the complete absence of sulfides indicate the high oxygen fugacity during metasomatism and the low sulfur concentration, which is a distinctive signature of fluid mode during formation of the Makhtesh Ramon alkali basaltic magma. Partial melting of peridotites and clinopyroxenites is accompanied by the formation of basanite or alkali basaltic melt. Clino- and orthopyroxenes are subjected to melting. The crystallization products of melt preserved in the mantle rock are localized in the interstices and consist mainly of fine-grained clinopyroxene, which together with Ti-magnetite, ilmenite, amphibole, rhenite, feldspar, and nepheline, is cemented by glass corresponding to quartz–orthopyroxene, olivine–orthopyroxene, quartz–feldspar, or nepheline–feldspar mixtures of the corresponding normative minerals. The mineral assemblages of xenoliths correspond to high temperatures. The high-Al and high-Ti clinopyroxene, calcium olivine, feldspar, and feldspathoids, amphibole, Ti-magnetite, and ilmenite are formed at 900–1000°. The study of melt and fluid inclusions in minerals from xenoliths indicate liquidus temperatures of 1200–1250°C, solidus temperatures of 1000–1100°C, and pressure of 5.9–9.5 kbar. Based on the amphibole–plagioclase barometer, amphibole and coexisting plagioclase were crystallized in clinopyroxenites at 6.5–7.0 kbar.