Thermodynamics of feldspathoid solutions

We have developed models for the thermody-namic properties of nephelines, kalsilites, and leucites in the simple system NaAlSiO₄?KAlSiO₄?Ca_0.5AlSiO₄?SiO₂?H₂O that are consistent with all known constraints on subsolidus equilibria and thermodynamic properties, and have integrated them into the existing MELTS software package. The model for nepheline is formulated for the simplifying assumptions that (1) a molecular mixing-type approximation describes changes in the configurational entropy associated with the coupled exchange substitutions □Si?NaAl and □Ca? Na₂ and that (2) Na⁺ and K⁺ display long–range non-convergent ordering between a large cation and the three small cation sites in the Na₄Al₄Si₄O₁₆ formula unit. Notable features of the model include the prediction that the mineral tetrakalsilite (“panunzite”, sensu stricto) results from anti-ordering of Na and K between the large cation and the three small cation sites in the nepheline structure at high temperatures, an average dT/dP slope of about 55^°/kbar for the reaction over the temperature and pressure ranges 800–1050 ^°C and 500–5000 bars, roughly symmetric (i.e. quadratic) solution behavior of the K–Na substitution along joins between fully ordered components in nepheline, and large positive Gibbs energies for the nepheline reciprocal reactions and and for the leucite reciprocal reaction      

Ree minerals of alkaline metasomatic rocks in the Main Sayan Fault

The composition of accessory REE minerals (allanite, chevkinite, fergusonite, and REE carbonates) in alkaline metasomatic rocks of the Main Sayan Fault (quartz-albite-microcline-riebeckite-aegirine, quartzalbite-microcline-magnetite, and clinopyroxene-albite) was studied using back-scattered scanning electron microscopy. Chevkinite occurs only in quartz-albite-microline metasomatic rock. The paragenesis of allanite and titanite is stable in clinopyroxene-albite metasomatic rocks. Allanite and fergusonite are typical of all zones of the metasomatic column. Chevkinite and allanite are often altered due to interaction with hydrothermal fluid and lose some amount of LREE. Secondary bastnaesite, synchysite, and ancylite are formed after allanite, while secondary monazite is developed after chevkinite. Presumably, the low-temperature alteration of allanite and chevkinite under effect of F^?, CO ₃ ^2? , and P ₄ ^3? -bearing fluids had not any significant manifestation in the total REE content in metasomatic rocks.     

Interaction of B(OH)_3^0 and HCO_3^ - in Seawater: Formation of B(OH)_2 CO_3^ -

Boron is known to interact with a wide variety of protonated ligands(HL) creating complexes of the form B(OH)₂L^-.Investigation of the interaction of boric acid and bicarbonate in aqueoussolution can be interpreted in terms of the equilibrium $B(OH)_3^0 + HCO_3^ - \rightleftharpoons B(OH)_2 CO_3^ - + H_2 O$ The formation constant for this reaction at 25 °C and 0.7 molkg^-1 ionic strength is $K_{BC} = \left[ {B(OH)_2 CO_3^ - } \right]\left[ {B(OH)_3^0 } \right]^{ - 1} \left[ {HCO_3^ - } \right]^{ - 1} = 2.6 \pm 1.7$ where brackets represent the total concentration of each indicatedspecies. This formation constant indicates that theB(OH)₂ $CO_3^ - $ concentration inseawater at 25 °C is on the order of 2 μmol kg^-1. Dueto the presence of B(OH)₂ $CO_3^ - $ , theboric acid dissociation constant ( $K\prime _B $ ) in natural seawaterdiffers from $K\prime _B $ determined in the absence of bicarbonate byapproximately 0.5%. Similarly, the dissociation constants of carbonicacid and bicarbonate in natural seawater differ from dissociation constantsdetermined in the absence of boric acid by about 0.1%. Thesedifferences, although small, are systematic and exert observable influenceson equilibrium predictions relating CO₂ fugacity, pH, totalcarbon and alkalinity in seawater.     

Talc paragenesis in some siliceous dolomitic rocks,and its sedimentologic significance

Thin (0.5–4 mm), contorted stringers of talc, associated with apatite and minor pyrite, are containdy Formation in eastern Alabama. The form, position and lithologic distribed within generally saccharoidal dolomite-quartz marbles of the Cambrian Shaution of the stringers strongly suggest an algalstromatolitic origin, with interlaminar trapped dolomitic muds. Metamorphic formation of talc plus apatite proceeded only within the stringers, whereas surrounding marble remained as unreacted dolomite plus quartz. Talc generation is best explained by the reaction $${\text{dolomite}} + {\text{silica}} + {\text{water}} + {\text{P}}_{\text{2}} {\text{O}}_{\text{5}} = {\text{talc}} + {\text{apatite}} + {\text{CO}}_{\text{2}}$$ in which the phosphate was supplied to the reaction from organic matter contained within the stromatolitic layers. The system was probably open to CO₂ during metamorphism, and \(P_{{\text{CO}}_{\text{2}} }\) remained relatively low.     

On the nonstoichiometry and point defects of olivine

This paper presents the point-defect thermodynamics for fayalite and olivine solid solutions (Fe _x Mg_1?x )₂SiO₄. By means of thermogravimetry, the metal-to-oxygen ratio of these silicates has been determined as a function of oxygen potential, compositionx and temperature. Experiments were performed in the range of 1,000° C≦T≦1,280° C and 0.2≦x≦1.0. It is found that V _Me ^″ , Fe _Me ^· and the associate {Fe′ _Si ^′ Fe _Me ^· } are the majority defects. With this knowledge it is possible to calculate the nonstoichiometry at given temperature as a function of \(p_{O_2 } \) and \(a_{SiO_2 } \) . The cation vacancy concentration shows a \(p_{O_2 }^{1/5} \) -dependence (forx≧0.2) and increases at givenT and \(p_{O_2 } \) almost exponentially with compositionx. In the composition range studied here, the silicates show an oxygen excess, and FeO is more soluble in the olivine than SiO₂.     

Crystallographic preferred orientation in wüstite (FeO) through the cubic-to-rhombohedral phase transition

Magnesiowüstite, (Mg_0.08Fe_0.88)O, and wüstite, Fe_0.94O, were compressed to ~36?GPa at ambient temperature in the diamond anvil cell (DAC) at the Advanced Light Source. X-ray diffraction patterns were taken in situ in radial geometry in order to study the evolution of crystallographic preferred orientation through the cubic-to-rhombohedral phase transition. Under uniaxial stress in the DAC, {100}_c planes aligned perpendicular to the compression direction. The {100}_c in cubic became { $\left\{ {10\bar 14} \right\}$ }_r in rhombohedral and remained aligned perpendicular to the compression direction. However, the {101}_c and {111}_c planes in the cubic phase split into { ${10{\bar{1}}4}$ }_r and { ${11{\bar{2}}0}$ }_r, and (0001)_r and { ${10{\bar{1}}1}$ }_r, respectively, in the rhombohedral phase. The { ${11{\bar{2}}0}$ }_r planes preferentially aligned perpendicular to the compression direction while { ${10{\bar{1}}4}$ }_r oriented at a low angle to the compression direction. Similarly, { ${10{\bar{1}}1}$ }_r showed a slight preference to align more closely perpendicular to the compression direction than (0001)_r. This variant selection may occur because the 〈 ${10{\bar{1}}4}$ 〉_r and [0001]_r directions are the softer of the two sets of directions. The rhombohedral texture distortion may also be due to subsequent deformation. Indeed, polycrystal plasticity simulations indicate that for preferred { ${10{\bar{1}}4}$ }〈 ${1{\bar{2}}10}$ 〉_r and { ${11{\bar{2}}0}$ }〈 ${{\bar{1}}101}$ 〉_r slip and slightly less active { ${10{\bar{1}}1}$ }〈 ${{\bar{1}}2{\bar{1}}0}$ 〉_r slip, the observed texture pattern can be obtained.     

Flow rule in a high-cycle accumulation model backed by cyclic test data of 22 sands

The flow rule used in the high-cycle accumulation (HCA) model proposed by Niemunis et al. (Comput Geotech 32: 245, 2005) is examined on the basis of the data from approximately 350 drained long-term cyclic triaxial tests (N = 10⁵ cycles) performed on 22 different grain-size distribution curves of a clean quartz sand. In accordance with (Wichtmann et al. in Acta Geotechnica 1: 59, 2006), for all tested materials, the “high-cyclic flow rule (HCFR)”, i.e., the ratio of the volumetric and deviatoric strain accumulation rates \(\dot{\varepsilon}_{\rm{v}}^{{\rm acc}}/\dot{\varepsilon}_{\rm{q}}^{{\rm acc}}\) , was found dependent primarily on the average stress ratio η ^av = q ^av/p ^av and independent of amplitude, soil density and average mean pressure. The experimental HCFR can be fairly well approximated by the flow rule of the modified Cam-clay (MCC) model. Instead of the critical friction angle \(\varphi_{\rm{c}}\) which enters the flow rule for monotonic loading, the HCA model uses the MCC flow rule expression with a slightly different parameter \(\varphi_{\rm{cc}}\) . It should be determined from cyclic tests. \(\varphi_{\rm{cc}}\) and \(\varphi_{\rm{c}}\) are of similar magnitude but not always identical, because they are calibrated from different types of tests. For a simplified calibration in the absence of cyclic test data, \(\varphi_{\rm{cc}}\) may be estimated from the angle of repose \(\varphi_{\rm{r}}\) determined from a pluviated cone of sand (Wichtmann et al. in Acta Geotechnica 1: 59, 2006). However, the paper demonstrates that the MCC flow rule with \(\varphi_{\rm{r}}\) does not fit well the experimentally observed HCFR in the case of coarse or well-graded sands. For an improved simplified calibration procedure, correlations between \(\varphi_{\rm{cc}}\) and parameters of the grain-size distribution curve (d ₅₀,   C _u) have been developed on the basis of the present data set. The approximation of the experimental HCFR by the generalized flow rule equations proposed in (Wichtmann et al. in J Geotech Geoenviron Eng ASCE 136: 728, 2010), considering anisotropy, is also discussed in the paper.     

The R{\overline{3}} c \to R{\overline{3}} m transition in nitratine, NaNO3, and implications for calcite, CaCO3

The temperature dependences of the crystal structure and superstructure intensities in sodium nitrate, mineral name nitratine, NaNO₃, were studied using Rietveld structure refinements based on synchrotron powder X-ray diffraction. Nitratine transforms from $R{\overline{3}} c\;\hbox{to}\;R{\overline{3}} m$ at T _c = 552(1) K. A NO₃ group occupies, statistically, two positions with equal frequency in the disordered $R{\overline{3}} m$ phase, but with unequal frequency in the partially ordered $R{\overline{3}} c$ phase. One position for the NO₃ group is rotated by 60° or 180° with respect to the other. The occupancy of the two orientations in the $R{\overline{3}} c$ phase is obtained from the occupancy factor, x, for the O1 site and gives rise to the order parameter, S = 2x ? 1, where S is 0 at T _c and 1 at 0 K. The NO₃ groups rotate in a rapid process from about 541 to T _c, where the a axis contracts. Using a modified Bragg–Williams model, a good fit was obtained for the normalized intensities (that is, normalized, NI^1/2) for the (113) and (211) reflections in $R{\overline{3}} c\hbox {\,NaNO}_{3},$ and indicates a second-order transition. Using the same model, a reasonable fit was obtained for the order parameter, S, and also supports a second-order transition.     

Standing stock and estimated production rates of phytoplankton and zooplankton in Narragansett Bay,Rhode Island

Seasonal changes in phytoplankton biomass and production, total zooplankton biomass, and biomass and potential production rates of the two dominant copepods, Acartia hudsonica (formerly called Acartia clausi) and Acartia tonsa are described for several stations in Narragansett Bay, R.I. Plankton in the bay behaved as a single population with simultaneous changes occurring at the upper bay (Station 5) and the lower bay (Station 1). Phytoplankton biomass was higher in the upper bay ( \(\bar x\) =16.95 mg chl a·m^?3) than in the lower bay ( \(\bar x\) =6.37 mg chl a·m^?3) and these 0269 0101 V differences in biomass were reflected in the phytoplankton production rates. The zooplankton, which was dominated by A. hudsonica in the spring and early summer and A. tonsa during summer and fall, showed no such consistent differences between the stations. Mean A. hudsonica biomass (St 1, \(\bar x\) ;=82.7 mg dry wt·m^?3; St 5, _ \(\bar x\) ;=95.2 mg dry wt·m^?3) exceeded that of A. tonsa (St 1, \(\bar x\) ;=56.7 mg dry wt·m^?3; St 5, \(\bar x\) ;=60.0 mg dry wt·m^?3). Potential production rates of the two Acartia 0269 0101 V spp. were strongly temperature dependent. Despite the higher biomass levels of A. hudsonica, low temperatures resulted in lower potential production rates ( \(\bar x\) ; St 1=7.25 mg C·m^?3 day^?1; \(\bar x\) ; St 5=10.77mg C·m^?3 day^?1) and biomass doubling times of up to 9.6 days. Potential production rates of A. tonsa at summer temperatures were high ( \(\bar x\) ; St 1=19.0 mg C·m^?3 day^?1; \(\bar x\) ; St 5=22.9 mg C·m^?3 day^?1) and biomass doubling times were generally less than one day.     

Crystal chemistry of perovskite-type compounds in the tausonite-loparite series, (Sr1−2 x Na x La x )TiO3

Perovskite-type compounds in the series tausonite-loparite, (Sr_{1?2 x} Na _x La _x )TiO₃, were synthesized by solid-state reaction (final heating at 1200–1300?°C), and studied using “conventional” and synchrotron X-ray powder diffractometry. The structures of intermediate compositions were determined using the Rietveld profile refinement method. In the compositional range 0?≤x?≤ 0.1, the series comprises perovskites characterized by an undistorted cubic structure (space group Pm3¯m, a?≈ 3.905–3.902?Å, Z?=?1). Intermediate compounds in the range 0.15?≤?x?≤?0.35 crystallize with tetragonal symmetry (I4/mcm, a?≈? , c?≈? , Z?=?4) derived from the cubic aristotype by antiphase rotation of the TiO₆ octahedra about a fourfold axis. The angle of rotation estimated from the positional parameters of oxygen atoms ranges from 2.5(7)° to 5.5(4)°. The cubic-to-tetragonal transition arises from substitution of Sr²⁺ by the comparatively smaller Na¹⁺ and La³⁺ cations. A further transition from the tetragonal to rhombohedral symmetry (R3¯c, a?≈? , c?≈?2 , Z?=?6) occurs between x?=?0.35 and 0.40, and apparently does not involve formation of perovskite with an intermediate two-tilt structure (Imma). The rhombohedral structure is characterized by a multicomponent octahedral tilt about a threefold axis ranging in magnitude from 6.5(2)° to 7.7(2)°. In the series (Sr_{1?2 x} Na _x La _x )TiO₃, the unit-cell dimensions decrease, and the degree of structural distortion increases with x.     

Experimental investigation of the mechanism of the reaction: 1 tremolite+11 dolomite ⇌ 8 forsterite+13 calcite+9 CO2+1H2O

Stoichiometric mixtures of tremolite and dolomite were heated to 50° C above equilibrium temperatures to form forsterite and calcite. The pressure of the CO₂-H₂O fluid was 5 Kb and \(X_{{\text{CO}}_{\text{2}} }\) varied from 0.1 to 0.6. The extent of the conversion was determined by the amount of CO₂ produced. The resulting mixtures of unreacted tremolite and dolomite and of newly-formed forsterite and calcite were examined with a scanning electron microscope. All tremolite and dolomite grains showed obvious signs of dissolution. At fluid compositions with \(X_{{\text{CO}}_{\text{2}} }\) less than about 0.4, the forsterite and calcite crystals are randomly distributed throughout the charges, indicating that surfaces of the reactants are not a controlling factor with respect to the sites of nucleation of the products. A change is observed when \(X_{{\text{CO}}_{\text{2}} }\) is greater than about 0.4; the forsterite and calcite crystals now nucleate and grow at the surface of the dolomite grains, thus indicating a change in mechanism at medium CO₂ concentrations. As the reaction progresses, the dolomite grains become more and more surrounded by forsterite and calcite, finally forming armoured relics of dolomite. Under experimental conditions this characteristic texture can only be formed if the CO₂-concentration is greater than about 40 mole %. These findings make it possible to estimate the CO₂-concentration from the texture of the dolomite+tremolite+forsterite+calcite assemblage. The results suggest a dissolution-precipitation mechanism for the reaction investigated. In a simplified form it consists of the following 4 steps:

1. Dissolution of the reactants tremolite and dolomite.
2. Diffusion of the dissolved constituents in the fluid.
3. Heterogeneous nucleation of the product minerals.
4. Growth of forsterite and calcite from the fluid.

Two possible explanations are discussed for the development of the amoured texture at \(X_{{\text{CO}}_{\text{2}} }\) above 0.4. The first is based upon the assumption that dolomite has a lower rate of dissolution than tremolite at high \(X_{{\text{CO}}_{\text{2}} }\) values resulting in preferential calcite and forsterite nucleation and growth on the dolomite surface. An alternative explanation is the formation of a raised CO₂ concentration around the dolomite grains at high \(X_{{\text{CO}}_{\text{2}} }\) values, leading to product precipitation on the dolomite crystals.     

Gehlenite stability in the system CaO-Al2O3-SiO2-H2O-CO2

P, T, \(X_{{\text{CO}}_{\text{2}} }\) relations of gehlenite, anorthite, grossularite, wollastonite, corundum and calcite have been determined experimentally at P _f =1 and 4 kb. Using synthetic starting minerals the following reactions have been demonstrated reversibly

1. 2 anorthite+3 calcite=gehlenite+grossularite+3 CO₂.
2. anorthite+corundum+3 calcite=2 gehlenite+3 CO₂.
3. 3anorthite+3 calcite=2 grossularite+corundum+3CO₂.
4. grossularite+2 corundum+3 calcite=3 gehlenite+3 CO₂.
5. anorthite+2 calcite=gehlenite+wollastonite+2CO₂.
6. anorthite+wollastonite+calcite=grossularite+CO₂.
7. grossularite+calcite=gehlenite+2 wollastonite+CO₂.

In the T, \(X_{{\text{CO}}_{\text{2}} }\) diagram at P _f =1 kb two isobaric invariant points have been located at 770±10°C, \(X_{{\text{CO}}_{\text{2}} }\) =0.27 and at 840±10°C, \(X_{{\text{CO}}_{\text{2}} }\) =0.55. Formation of gehlenite from low temperature assemblages according to (4) and (2) takes place at 1 kb and 715–855° C, \(X_{{\text{CO}}_{\text{2}} }\) =0.1–1.0. In agreement with experimental results the formation of gehlenite in natural metamorphic rocks is restricted to shallow, high temperature contact aureoles.     

Bimetasomatic zoning in the CaO-MgO-SiO2-H2O-CO2 system: Experiments with the use of natural rock samples

Experiments reproducing the development of bimetasomatic zoning in the CaO-MgO-SiO₂-H₂O-CO₂ system were conducted at elevated P-T parameters with the use of samples of naturally occurring quartzdolomite and calcite-serpentinite rocks. In order to maintain mass transfer exclusively via the diffusion-controlled mechanism, we used the method of the ensured compaction of the cylindrical sample surface with a thin-walled gold tube. In the course of the experiments, a single diopside zone ～2.5 × 10^?5 m thick was obtained at the quartz-dolomite interface at T = 600°C, $P_{H_2 O + CO_2 } $ = 200 MPa, and $X_{CO_2 } $ = 0.5 for 25–40 days and a succession of metasomatic zones at T = 750°C, $P_{H_2 O + CO_2 } $ = 300 MPa, and $X_{CO_2 } $ = 0.4 for 48 days. The metasomatic zones were as follows (listed in order from quartz to dolomite): wollastonite ‖ diopside ‖ tremolite ‖ calcite + forsterite; with the average width of the diopside zone equal to ～1.3 × 10^?5 m and the analogous part of the wollastonite zone equal to ～2.6 × 10^?5 m. Two zones (listed in order from calcite to serpentine) diopside and diopside-forsterite (the average widths of these zones were ～6 × 10^?4 and ～8 × 10^?4 m, respectively) were determined to develop at contact between serpentine and calcite during experiments that lasted 124 days at T = 500°C, $P_{H_2 O + CO_2 } $ = 200 MPa, and $X_{CO_2 } $ = 0.2–0.4. In the former and latter situations, the growth rate of the zoning ranged between 3.1 × 10^?12 and 1.2 × 10^?11 m/s and between 5.6 × 10^?11 and 7.5 × 10^?11 m/s, respectively. The higher growth rate in the latter case can be explained by the higher water mole fraction in the fluid, with this water released during serpentinite decomposition in the experiments. The development of the only diopside zone in the experiments modeling the interaction of quartz and dolomite at T = 600–650°C and $P_{H_2 O + CO_2 } $ = 200 MPa is in conflict with theoretical considerations underlain by the Korzhinskii-Fisher-Joesten model. The interaction of quartz and dolomite in the CaO-MgO-SiO₂-CO₂-H₂O system at the P-T- $X_{CO_2 } $ parameters specified above should be attended by the origin of a number of reaction zones consisting of various proportions of talc, forsterite, tremolite, diopside, and calcite. The saturation of the fluid with respect to these minerals was likely not reached, and this resulted in the degeneration of the respective stability fields in the succession of zones. Conceivably, this was related to the insufficient rates of quartz and dolomite dissolution and the relatively low diffusion rates of the dissolved species in the low-permeable medium. In the experiments with interacting calcite and serpentine, the zoning calcite ‖ diopside ‖ diopside + forsterite ‖ serpentine developed in its complete form, in agreement with the theory. Equilibrium was likely achieved in these experiments due to the higher diffusion coefficients.     

Natural Cr(VI) contamination of groundwater in the Cecina coastal area and its inner sectors (Tuscany,Italy)

A detailed hydrogeochemical study of groundwater in the Cecina coastal plain (Livorno province, Italy) and its inner sectors was undertaken in 2008, as chemical analyses carried out on groundwater since 2006 have revealed Cr(VI) concentrations of up to 49 μg/L (well above the permissible limit of 5 μg/L). Ophiolite outcrops are present throughout the study area, and their fragments likely represent a significant portion of the existing multilayered aquifer skeleton. Waters delivered by the serpentinite outcrops have a typically Mg–HCO₃ composition, whereas those of the coastal plain are prevailingly of the Ca/Mg–HCO₃ type with significant Mg contents. Significant NO₃ contamination characterises the studied coastal plain, and an interesting negative correlation exists between Cr(VI) and both NO₃ and SO₄ deriving from the widespread use of (NH₄)₂SO₄ as a farm fertilizer. Chromium speciation calculations carried out using the EQ3NR code reveal that the prevailing Cr(VI) species in solution is CrO₄ ^2?; however, CaCrO₄° and MgCrO₄° neutral complexes represent significant percentages (up to 42 %). These findings suggest that the mobility and consequently the bioavailability of Cr(VI) can be significantly enhanced by these neutral complexes, which are not considered to be affected by adsorption/desorption processes. The Cr(VI) source, investigated by means of the Mg/SiO₂ molar ratio, seems to be represented mainly by Mg-bearing minerals of the chlorite group. Petrographic observations confirm the occurrence of this mineral group. The interaction between rainwater and the local serpentinite rock was simulated at different $P_{{{\text{CO}}_{ 2} }}$ and $P_{{{\text{O}}_{ 2} }}$ conditions by reaction path modelling using the EQ3/6 software package. $P_{{{\text{O}}_{ 2} }}$ was varied in accordance with the assumption that redox conditions are determined in part by NO₃. Results are in good agreement with experimental data on spring waters and subordinately with data on some coastal plain groundwater, which plot in a rather wide $P_{{{\text{CO}}_{ 2} }}$ and $P_{{{\text{O}}_{ 2} }}$ field. Although the dissolved Cr content is mostly of natural origin, fertilization may affect its fate.     

Bootstrap determination of the reliability of b-values: an assessment of statistical estimators with synthetic magnitude series

We consider some practical issues of the determination of the b-value of sequences of magnitudes with the bootstrap method for short series of length L and various quantization levels $\Updelta m$ of the magnitude. Preliminary Monte Carlo tests performed with $\Updelta m = 0$ demonstrate the superiority of the maximum likelihood estimator b _MLE, and the inconsistency of the, yet often used, b _LR estimator defined as the least-squares slope of the experimental Gutenberg?CRichter curve. The Monte Carlo tests are also applied to an estimator, b _KS, which minimizes the Kolmogorov?CSmirnov distance between the cumulative distribution of magnitudes and a power-law model. Monte Carlo tests of discrete versions of the b _MLE and b _KS estimators are done for $\Updelta m = \{0.1, 0.2, 0.3 \}$ and used as reference to evaluate the performance of the bootstrap determination of b. We show that all estimators provide b estimates within 10?% error for L????100 and if a large number, n?=?2?×?10⁵, of bootstrapped sample series is used. A resolution test done with $\Updelta m = 0.1$ reveals that a clear distinction between b?=?0.8, 1.0, and 1.2 is obtained if L????200.     

The dilatant behaviour of sand–pile interface subjected to loading and stress relief

Property and behaviour of sand–pile interface are crucial to shaft resistance of piles. Dilation or contraction of the interface soil induces change in normal stress, which in turn influences the shear stress mobilised at the interface. Although previous studies have demonstrated this mechanism by laboratory tests and numerical simulations, the interface responses are not analysed systematically in terms of soil state (i.e. density and stress level). The objective of this study is to understand and quantify any increase in normal stress of different pile–soil interfaces when they are subjected to loading and stress relief. Distinct element modelling was carried out. Input parameters and modelling procedure were verified by experimental data from laboratory element tests. Parametric simulations of shearbox tests were conducted under the constant normal stiffness, constant normal load and constant volume boundary conditions. Key parameters including initial normal stress ( $ \sigma_{{{\text{n}}0}}^{\prime } $ ), initial void ratio (e ₀), normal stiffness constraining the interface and loading–unloading stress history were investigated. It is shown that mobilised stress ratio ( $ \tau /\sigma_{\text{n}}^{\prime } $ ) and normal stress increment ( $ \Updelta \sigma_{\text{n}}^{\prime } $ ) on a given interface are governed by $ \sigma_{{{\text{n}}0}}^{\prime } $ and e ₀. An increase in $ \sigma_{{{\text{n}}0}}^{\prime } $ from 100 to 400 kPa leads to a 30 % reduction in $ \Updelta \sigma_{\text{n}}^{\prime } $ . An increase in e ₀ from 0.18 to 0.30 reduces $ \Updelta \sigma_{\text{n}}^{\prime } $ by more than 90 %, and therefore, shaft resistance is much lower for piles in loose sands. A unique relationship between $ \Updelta \sigma_{\text{n}}^{\prime } $ and normal stiffness is established for different soil states. It can be applied to assess the shaft resistance of piles in soils with different densities and subjected to loading and stress relief. Fairly good agreement is obtained between the calculated shaft resistance based on the proposed relationship and the measured results in centrifuge model tests.     

Raman spectra of gypsum under pressure

Raman sprectra of a gypsum crystal were made at pressures between 0.001 and 7 kbar using He gas as the pressure medium. \(\frac{{{\text{d}}v}}{{dP}}\) values for bands in the range 3,600–100 cm^?1 were obtained. Comparison of results with \(\frac{{{\text{d}}v}}{{{\text{d}}T}}\) from the literature for temperatures of 77 and 300° K. shows that the internal modes of the SO₄ units are more sensitive to pressure than to temperature. The effect is small. Coupled H₂O-SO₄ translational modes are greatly affected by both pressure and temperature while coupled Ca-SO₄ mode are less so. It was found that stretching vibrations of water molecules were affected differently under pressure. The band at 3,500 cm^?1 is more greatly displaced by pressure \(\left( {\frac{{{\text{d}}v}}{{{\text{d}}P}} = {\text{2}}{\text{.11cm}}^{{\text{ - 1}}} /{\text{kbar}}} \right)\) than the band at 3,400 cm^?1 \(\left( {\frac{{{\text{d}}v}}{{{\text{d}}P}} \simeq {\text{2}}{\text{.11cm}}^{{\text{ - 1}}} /{\text{kbar}}} \right)\) . Assuming two different hydrogen bond intensities for the water molecules, one can attribute this difference in behavior of stretching modes to and increase in hydrogen bonding of one of the hydrogens which is exterior to the double H₂O planes in the gypsum structure. The great variety of pressure derivatives for the different types of vibrational modes observed indicates that each molecular unit readjusts internally to pressure induced volume changes and the some of the chemical bonds between the units are significantly affected.     

Impact of Data Density and Geostatistical Simulation Technique on the Estimation of Residence Times in a Synthetic Two-dimensional Aquifer

Connectivity patterns of heterogeneous porous media are important in the estimation of groundwater residence time distributions (RTDs). Understanding the connectivity patterns of a hydraulic conductivity ( \(K\) ) field often requires knowledge of the entire aquifer, which is not practical. As such, the method used to estimate unknown \(K\) values using known \(K\) values is important. This study investigates how varying levels of conditioning data and four simulation techniques, one multi-Gaussian and three multi-point, are able to recreate key \(K\) field features and connectivity patterns of a synthetic two-dimensional bimodal distributed ln( \(K\) ) field with highly connected high \(K\) features. These techniques are then assessed in the context of RTD estimation. It was found that the multi-Gaussian technique presented a bias towards earlier travel times with increased conditioning data. This was due to the inability of the method to recreate multiple scales of connecting features. Of the multi-point methods investigated, the facies method was unable to predict early arrival times. The use of a continuous variable training image produced good fits to the observed residence time distribution with a high number of conditioning points. The ability of the methods to predict the shape of residence time distributions appears to be related to their ability to reproduce the connection patterns of higher \(K\) features.     

Vigrishinite, Zn2Ti4 − x Si4O14(OH,H2O,□)8, a new mineral from the Lovozero alkaline complex, Kola Peninsula, Russia

A new mineral vigrishinite, epistolite-group member and first layer titanosilicate with species-defining Zn, was found at Mt. Malyi Punkaruaiv, in the Lovozero alkaline complex, Kola Peninsula, Russia. It occurs in a hydrothermally altered peralkaline pegmatite and is associated with microcline, ussingite, aegirine, analcime, gmelinite-Na, and chabazite-Ca. Vigrishinite forms rectangular or irregularly shaped lamellae up to 0.05 × 2 × 3 cm flattened on [001]. They are typically slightly split and show blocky character. The mineral is translucent to transparent and pale pink, yellowish-pinkish or colorless. The luster is vitreous. The Mohs’ hardness is 2.5–3. Vigrishinite is brittle. Cleavage is {001} perfect. D _meas = 3.03(2), D _calc = 2.97 g/cm³. The mineral is optically biaxial (?), α = 1.755(5), β = 1.82(1), γ = 1.835(8), 2V _meas = 45(10)°, 2V _calc = 50°. IR spectrum is given. The chemical composition (wt %; average of 9 point analyses, H₂O is determined by modified Penfield method) is as follows: 0.98 Na₂O, 0.30 K₂O, 0.56 CaO, 0.05 SrO, 0.44 BaO, 0.36 MgO, 2.09 MnO, 14.39 ZnO, 2.00 Fe₂O₃, 0.36 Al₂O₃, 32.29 SiO₂, 29.14 TiO₂, 2.08 ZrO₂, 7.34 Nb₂O₅, 0.46 F, 9.1 H₂O, ?0.19 O=F₂, total is 101.75. The empirical formula calculated on the basis of Si + Al = 4 is: H_7.42(Zn_1.30Na_0.23Mn_0.22Ca_0.07Mg_0.07K_0.05Ba_0.02)_Σ1.96(Ti_2.68Nb_0.41Fe _0.18 ³⁺ Zr_0.12)_Σ3.39(Si_3.95Al_0.05)_{Σ4 20.31}F_0.18. The simplified formula is: Zn₂Ti_4?x Si₄O₁₄(OH,H₂O,□)₈ (x < 1). Vigrishinite is triclinic, space group P $\bar 1$ , a = 8.743(9), b = 8.698(9), c = 11.581(11)Å, α = 91.54(8)°, β = 98.29(8)°, γ = 105.65(8)°, V = 837.2(1.5) ų, Z = 2. The strongest reflections in the X-ray powder pattern (d, Å, ?I[hkl]) are: 11.7-67[001], 8.27-50[100], 6.94-43[0 $\bar 1$ 1, $\bar 1$ 10], 5.73–54[1 $\bar 1$ 1, 002], 4.17-65[020, $\bar 1$ $\bar 1$ 2, 200], and 2.861-100[3 $\bar 1$ 0, 2 $\bar 2$ 2, 004, 1 $\bar 3$ 1]. The crystal structure model was obtained on a single crystal, R = 0.171. Vigrishinite and murmanite are close in the structure of the TiSiO motif, but strongly differ from each other in part of large cations and H-bearing groups. Vigrishinite is named in honor of Viktor G. Grishin (b. 1953), a Russian amateur mineralogist and mineral collector, to pay tribute to his contribution to the mineralogy of the Lovozero Complex. The type specimen is deposited in the Fersman Mineralogical Museum of Russian Academy of Sciences, Moscow.     

Oxygen potential of diamond formation in the lower mantle

Thermodynamic calculations have shown that when a metallic phase arising due to ferroan ion disproportionation is contained in lower-mantle rocks, carbon occurs as iron carbide and the oxygen fugacity corresponds to the equilibrium of ferropericlase with Fe-Ni alloy. The typical values of oxygen fugacity in zones of diamond formation in the lower mantle lie between the iron-wüstite buffer and six logarithmic units above this level. The processes that proceed in the lower mantle give rise to variation of $f_{O_2 }$ within several orders of magnitude above the elevated $f_{O_2 }$ values, which are necessary for the formation of diamond, as compared with a common level typical of the lower mantle. The mechanisms responsible for redox differentiation in the lower mantle comprise the subduction of oxidized crustal material, mechanical separation of metallic phase and silicate-oxide mineral assemblage enriched in ferric ions, as well as transfer of fused silicate material presumably enriched in Fe³⁺ through the mantle.