Computational study of tetrahedral Al–Si and octahedral Al–Mg ordering in phengite

 As part of a wider study of the nature and origins of cation order–disorder in micas, a variety of computational techniques have been used to investigate the nature of tetrahedral and octahedral ordering in phengite, K₂ ^[6](Al₃Mg)^[4](Si₇Al)O₂₀(OH)₄. Values of the atomic exchange interaction parameters J _n used to model the energies of order–disorder were calculated. Both tetrahedral Al–Si and octahedral Al–Mg ordering were studied and hence three types of interaction parameter were necessary: for T–T, O–O and T–O interactions (where T denotes tetrahedral sites and O denotes octahedral sites). Values for the T–T and O–O interactions were taken from results on other systems, whilst we calculated new values for the T–O interactions. We have demonstrated that modelling the octahedral and tetrahedral sheets alone and independently produces different results from modelling a whole T–O–T layer, hence justifying the inclusion of the T–O interactions. Simulations of a whole T–O–T layer of phengite indicated the presence of short-range order, but no long-range order was observed. Received: 8 August 2002 / Accepted: 14 February 2003 Acknowledgements The authors are grateful to EPSRC (EJP) and the Royal Society (CIS) for financial support. Monte Carlo simulations were performed on the Mineral Physics Group's Beowulf cluster and the University of Cambridge's High Performance Computing Facility.     

Tortoises and hares: dissolution,erosion and isostasy in landscape evolution

Denudation mechanisms differ fundamentally between limestone and silicate rock types, which are subject to very different rate thresholds and enhancers/inhibitors. Silicates are removed largely by erosion, the mechanical entrainment and transport of particles. This is a relatively high energy, and highly episodic, process which occurs only when a minimum threshold ?ow velocity is exceeded; it is inhibited by vegetation cover and favoured by strongly seasonal runoff. Limestone is removed largely by chemical dissolution at a rate directly proportional to runoff. Dissolution is a relatively low energy process that can occur at any ?ow velocity or in static water; in general it is enhanced by vegetation cover and non‐seasonality of runoff. These contrasting factors in the denudation of silicates versus limestone can produce strikingly uneven rates of surface lowering across a landscape, sometimes akin to the well known ‘tortoise and hare race’, where the slow and steady denudation of limestones may in the long term exceed the sometimes rapid, but often localized and episodic, erosion of silicates. Prolonged exposure of limestone to a humid temperate climate in a tectonically stable environment produces low‐relief corrosion plains in which limestone uplands are anomalous and, in most instances, due to recent unroo?ng from beneath a siliciclastic cover. In a highly seasonal or semi‐arid climate almost the exact inverse may develop, with ‘?ashy’ runoff and sparse vegetation favouring erosion rather than dissolution. Even under a constant humid climate progressive unroo?ng of a thick limestone unit within folded siliciclastics may lead to a topographic inversion over time, with the limestone outcrop always forming a topographic low ?anked by siliciclastic uplands. Valleys will be initiated on anticlinal crests, where the limestone is ?rst unroofed, but progressive lowering of the limestone causes these valleys to migrate to their ?nal position in the synclinal troughs. In humid climates isostatic compensation in response to slow, but continuous, denudation of extensive limestone outcrops may be a signi?cant factor in the development of relief on adjacent, more slowly eroding, silicate outcrops. Copyright © 2004 John Wiley & Sons, Ltd.     

Mise au point d'un milieu de culture pour l'étude de l'altération de silicates en présence de Pseudomonas aeruginosa

The influence of microorganisms on mineral alteration is not easy to determine in environmental conditions, because of the difficulty to raise for comparison purposes an identical but abiotic system. Another problem in this context is the choice of reliable tracers to evaluate the alteration rate of materials during in vitro experiments. To face such difficulties, we elaborated a defined medium allowing both the growth of Pseudomonas aeruginosa and a precise measurement of the elements solubilized from the minerals. Thanks to this medium, we were able to quantitatively determine the amounts of major elements solubilized from the materials in the presence of bacterial growth, compared to a sterile system. Moreover, the analysis by ICP-MS of trace elements was possible after a chromatographic treatment, which selectively eliminated 99% of the sodium content of the medium. To cite this article: G. Aouad et al., C. R. Geoscience 337 (2005).     

Electronic absorption spectra of Fe2+ ions in oxygen-based rock-forming minerals at temperatures between 297 and 600 K

 Polarized electronic single crystal spectra of natural Fe²⁺ ion-bearing oxygen-based minerals, in which ferrous ions enter octahedral sites of different symmetry and distortion (olivine, cordierite, ortho- and clinopyroxene, amphibole), eightfold sites in garnet (almandine) and clinopyroxene (M2), and tetrahedral sites in spinel, were studied at temperatures from 300 to ca. 600 K. In the minerals studied, the spin-allowed bands of Fe²⁺ display rather variable temperature behaviour. In most cases, due to the thermal expansion of the Fe²⁺-bearing polyhedra, bands shift to lower energies upon increasing temperature, though there are some exceptions to this rule: in cases of other than sixfold octahedral or close to octahedral coordination, in almandine and spinel the bands shift to higher energies, which can be explained by an increase in distortions of the Fe²⁺-bearing polyhedra. Splitting of the excited ⁵ E _g-level of Fe²⁺ ions usually, but not always, increases with temperature, reflecting thermally induced increase in distortion of the Fe²⁺-bearing sites in the minerals studied. Integral intensities of the bands in question do not always obey the general rule, according to which intensity should increase with temperature, when the 3d ^N-centred site is centrosymmetric, or should remain unchanged when the 3d ^N site lacks an inversion centre. The experimental results show that the response of the characteristics of absorption bands such as width, intensity and energy caused by dd transitions of Fe²⁺ in oxygen-based minerals to increasing temperature is not always uniform and is at variance with expectation. This temperature dependence cannot be used directly to solve band assignment problems, as earlier proposed in the literature. Received: 22 December 1999 / Accepted: 30 October 2000     

Studies on the behaviour of nutrients in the Mandovi Estuary during premonsoon

Behaviour of silicate, nitrate and phosphate in the Mandovi Estuary was studied during the premonsoon season. The study shows that silicate is removed from the water column while nitrate showed an internal source. This nitrate source has been identified as the wash water from an iron ore screening plant which discharges the muddy waste directly into the river. Applying mixing relations, the distribution of this nitrate both up- and downstream of the outfall has been studied. Phosphate showed very low concentrations in the low salinity region; however, its concentration increased slightly towards the higher salinity region.     

Equilibrium thallium isotope fractionation and its constraint on Earth’s late veneer

Equilibrium isotope fractionation of thallium(Tl) includes the traditional mass-dependent isotope fractionation effect and the nuclear volume effect(NVE). The NVE dominates the overall isotope fractionation, especially at high temperatures. Heavy Tl isotopes tend to be enriched in oxidized Tl^3+-bearing species. Our NVE fractionation results of oxidizing Tl^+ to Tl^3+ can explain the positive enrichments observed in ferromanganese sediments. Experimental results indicate that there could be0.2–0.3 e-unit fractionation between sulfides and silicates at 1650 ℃. It is consistent with our calculation results,which are in the range of 0.17–0.38 e-unit. Importantly,Tl’s concentration in the bulk silicate Earth(BSE) can be used to constrain the amount of materials delivered to Earth during the late veneer accretion stage. Because the Tl concentration in BSE is very low and its Tl isotope composition is similar with that of chondrites, suggesting either no Tl isotope fractionation occurred during numerous evaporation events, or the Tl in current BSE was totally delivered by late veneer. If it is the latter, the Tl-contentbased estimation could challenge the magnitude of late veneer which had been constrained by the amount of highly siderophile elements in BSE. Our results show that the lateaccreted mass is at least five-times larger than the previously suggested magnitude, i.e., 0.5 wt% of current Earth’s mass. The slightly lighter 205 Tl composition of BSE relative to chondrites is probable a sign of occurrence of Tlbearing sulfides, which probably were removed from the mantle in the last accretion stage of the Earth.     

Authigenic potassic silicates in the Rathdowney Trend,southwest Ireland: New perspectives for ore genesis from petrography of gangue phases in Irish-type carbonate-hosted Zn-Pb deposits

Petrographic studies of Zn-Pb ore zones hosted by Lower Carboniferous dolomitized Waulsortian reef limestones in the Rathdowney Trend reveal a paragenetic association between sphalerite and potassium silicates: (Ba, K)-feldspar, adularia, and albite as well as rare quartz, illite and phengite. The dominant mineral assemblage is composed of 1) sphalerite ± (K,Ba) feldspar ± pengite/illite near the putative feeder conduit for the Lisheen Main Zone, and 2) a sphalerite ± pengite/illite assemblage distal to the major normal faults (NW of Main Zone, Island Zone and Rapla occurrence). In addition, clay minerals have been identified in fault gouges located at the interface between the Waulsortian reef and argillaceous limestone of the Ballysteen Formation. This mineral assemblage has provided additional constraints on the physico-chemical conditions of ore formation (eH, pH, sulfur and metal species). Another implication of the mineral assemblage, is a revision of fluid rock interaction processes, in which mineral solution-precipitation reactions are contributing to the development of hydrothermal breccias, with dolomitic black matrix breccias interpreted as a by-product of massive sulfide precipitation. Additionally, textural studies of the breccias through fractal dimension analysis of fragment geometry extracted from large scale scanning electron microscope element maps (1 cm² areas or more), indicates the prevalence of chemical brecciation-corrosion processes in the generation of the black matrix breccias. Integration of these new observations allows for comparison of ore forming processes across the Irish Midlands from the perspective of gangue mineralogy and may provide further links with classic Mississippi-type deposits from the mid-continent region of the United States of America.     

In Situ Determination of Au and Cu in Natural Pyrite by Near‐Infrared Femtosecond Laser Ablation‐Inductively Coupled Plasma‐Quadrupole Mass Spectrometry: No Evidence for Matrix Effects

Gold and copper concentrations were determined in natural pyrite by near‐infrared femtosecond LA‐ICP‐QMS, using both sulfide reference materials (pyrrhotite Po‐726 and in‐house natural chalcopyrite Cpy‐RM) and NIST SRM 610 as external calibrators. Firstly, using NIST SRM 610 as the external calibrator, we calculated the Au concentration in Po‐726 and the Cu concentration in Cpy‐RM. The calculated concentration averages for Au and Cu were similar to the values published for Po‐726 and Cpy‐RM, respectively. Secondly, we calculated Au and Cu concentrations taking NIST SRM 610 as an unknown sample and using Po‐726 and Cpy‐RM as external calibrators. Again, the average values obtained closely reflected the preferred concentrations for NIST SRM 610. Finally, we calculated Au and Cu concentrations in natural pyrite using sulfide and silicate reference materials as external calibrators. In both cases, calculated concentrations were very similar, independent of the external calibrator used. The aforementioned data, plus the fact that we obtained very small differences in relative sensitivity values (percentage differences are between 5% and 17% for ⁵⁷Fe, ⁶³Cu and ¹⁹⁷Au) on analyses of silicate and sulfide RMs, indicate that there were no matrix effects related to the differences in material composition. Thus, it is possible to determine Au and Cu in natural sulfides using NIST silicate glasses as an external calibrator.     

Crystal structure and compression of an iron-bearing Phase A to 33 GPa

Fe-bearing dense hydrous magnesium silicate Phase A, Mg_6.85Fe_0.14Si_2.00O₈(OH)₆ has been studied by single-crystal X-ray diffraction at ambient conditions and by high-pressure powder diffraction using synchrotron radiation to 33 GPa. Unit cell parameters at room temperature and pressure from single crystal diffraction are a=7.8678 (4) Å, c=9.5771 (5) Å, and V=513.43 (4) ų. Fitting of the P–V data to a third-order Birch-Murnaghan isothermal equation of state yields V ₀=512.3 (3) ų, K _T,0=102.9 (28) GPa and K′=6.4 (3). Compression is strongly anisotropic with the a-axes, which lie in the plane of the distorted close-packed layers, approximately 26% more compressible than the c-axis, which is normal to the plane. Structure refinement from single-crystal X-ray intensity data reveals expansion of the structure with Fe substitution, mainly by expansion of M-site octahedra. The short Si2–O6 distance becomes nearly 1% shorter with ~2% Fe substitution for Mg, possibly providing additional rigidity in the c-direction over the Mg end member. K _T obtained for the Fe-bearing sample is ~5.5% greater than reported previously for Fe-free Phase A, despite the larger unit cell volume. This study represents a direct comparison of structure and K _T–ρ relations between two compositions of a F-free dense hydrous magnesium silicate (DHMS) phase, and may help to characterize the effect of Fe substitution on the properties of other DHMS phases from studies of the Fe-free end-members.     

A crystal-chemical basis for Pb retention and fission-track annealing systematics in U-bearing minerals, with implications for geochronology

This study develops an empirical crystal-chemical framework for systematizing the kinetics of Pb loss and fission-track annealing in U-bearing minerals. Ionic porosity, Z (the fraction of a mineral's unit-cell volume not occupied by ions) potentially accounts for kinetic behavior by monitoring mean metal-oxygen bond length/strength. Various tests of a general kinetics-porosity relationship are presented, based upon diverse mineral data including: (1) Pb diffusion parameters; (2) measured closure temperatures (T_C) for fission-track annealing and (3) retentivities of both Pb and fission tracks, from apparent-age data. Every kinetic parameter (including T_C and mineral age for both the U/Pb and fission-track systems) is inversely correlated with Z within the sub-assemblage: zircon (Z ≈ 29%), titanite ( 34%) and apatite ( 38%). Assuming a diffusional closure model, Pb isotopic transport phenomena are described by a T_C-Z scale “calibrated” with field-based T_C data for titanite (≥ 680 ± 20°C) and apatite ( 500°C). Extrapolation of this scale yields T_C estimates for the following minerals: staurolite (T_C ≥ 1060°C, Z ≈ 25%); garnet (≥ 1010°C, 26.5%); zircon (≥900°C); monazite, xenotime, and epidote (≥ 750°C, 32%); and Ca-clinopyroxene (≥ 670 ± 30°C, 34 ± 1%, depending on composition). These empirical results imply that a (U/)Pb/Pb date for staurolite or garnet records the time of mineral growth, not post-growth isotopic closure, as also concluded in recent field studies. Because Z systematizes fission-track annealing, this recrystallization process, like volume-diffusion, must also be rate-limited by the strength of chemical bonds. The extent to which other recrystallization processes are likewise rate-limited is important to U/Pb geochronology because they potentially compete with diffusion as mechanisms for Pb-isotopic resetting in nature.