Elastic behavior of vanadinite,Pb<Subscript>10</Subscript>(VO<Subscript>4</Subscript>)<Subscript>6</Subscript>Cl<Subscript>2</Subscript>, a microporous non-zeolitic mineral

The high-pressure behavior of a vanadinite (Pb₁₀(VO₄)₆Cl₂, a = b = 10.3254(5), c = 7.3450(4) Å, space group P6₃/m), a natural microporous mineral, has been investigated using in-situ HP-synchrotron X-ray powder diffraction up to 7.67 GPa with a diamond anvil cell under hydrostatic conditions. No phase transition has been observed within the pressure range investigated. Axial and volume isothermal Equations of State (EoS) of vanadinite were determined. Fitting the P–V data with a third-order Birch-Murnaghan (BM) EoS, using the data weighted by the uncertainties in P and V, we obtained: V ₀ = 681(1) Å³, K ₀ = 41(5) GPa, and K′ = 12.5(2.5). The evolution of the lattice constants with P shows a strong anisotropic compression pattern. The axial bulk moduli were calculated with a third-order “linearized” BM-EoS. The EoS parameters are: a ₀ = 10.3302(2) Å, K ₀(a) = 35(2) GPa and K′(a) = 10(1) for the a-axis; c ₀ = 7.3520(3) Å, K ₀(c) = 98(4) GPa, and K′(c) = 9(2) for the c-axis (K ₀(a):K ₀(c) = 1:2.80). Axial and volume Eulerian-finite strain (fe) at different normalized stress (Fe) were calculated. The weighted linear regression through the data points yields the following intercept values: Fe _a (0) = 35(2) GPa for the a-axis, Fe _c (0) = 98(4) GPa for the c-axis and Fe _V (0) = 45(2) GPa for the unit-cell volume. The slope of the regression lines gives rise to K′ values of 10(1) for the a-axis, 9(2) for the c-axis and 11(1) for the unit cell-volume. A comparison between the HP-elastic response of vanadinite and the iso-structural apatite is carried out. The possible reasons of the elastic anisotropy are discussed.     

Argon retention properties of silicate glasses and implications for <Superscript>40</Superscript>Ar/<Superscript>39</Superscript>Ar age and noble gas diffusion studies

Sized aggregates of glasses (47–84 wt% SiO₂) were fused from igneous-derived cohesive fault rock and igneous rock, and step-heated from ~400 to >1,200 °C to obtain their ³⁹Ar diffusion properties (average E=33,400 cal mol^?1; D _o=4.63×10^?3 cm² s^?1). At T<~1,000 °C, glasses containing <~69 wt% SiO₂ and abundant network-forming cations (Ca, Fe, Mg) reveal moderate to strong non-linear increases in D and E, reflecting structural modifications as the solid transitions to melt. Extrapolation of these Arrhenius properties down to typical geologic T-t conditions could result in a 1.5 log₁₀ unit underestimation in the diffusion rate of Ar in similar materials. Numerical simulations based upon the diffusion results caution that some common geologic glasses will likely yield ⁴⁰Ar/³⁹Ar cooling ages rather than formation ages. However, if cooling rates are sufficiently high, ambient temperatures are sufficiently low (e.g., <65–175 °C), and coarse particles (e.g., radius (r) >~1 mm) are analyzed, glasses with compositions similar to ours may preserve their formation ages.     

Stability at high-pressure,elastic behaviour and pressure-induced structural evolution of CsAlSi<Subscript>5</Subscript>O<Subscript>12</Subscript>, a potential host for nuclear waste

The elastic and structural behaviour of the synthetic zeolite CsAlSi₅O₁₂ (a = 16.753(4), b = 13.797(3) and c = 5.0235(17) Å, space group Ama2, Z = 2) were investigated up to 8.5 GPa by in situ single-crystal X-ray diffraction with a diamond anvil cell under hydrostatic conditions. No phase-transition occurs within the P-range investigated. Fitting the volume data with a third-order Birch–Murnaghan equation-of-state gives: V ₀ = 1,155(4) ų, K _T0 = 20(1) GPa and K′ = 6.5(7). The “axial moduli” were calculated with a third-order “linearized” BM-EoS, substituting the cube of the individual lattice parameter (a ³, b ³, c ³) for the volume. The refined axial-EoS parameters are: a ₀ = 16.701(44) Å, K _T0a = 14(2) GPa (β_a = 0.024(3) GPa^?1), K′ _a = 6.2(8) for the a-axis; b ₀ = 13.778(20) Å, K _T0b = 21(3) GPa (β_b = 0.016(2) GPa^?1), K′ _b = 10(2) for the b-axis; c ₀ = 5.018(7) Å, K _T0c = 33(3) GPa (β_c = 0.010(1) GPa^?1), K′ _c = 3.2(8) for the c-axis (K _T0a:K _T0b:K _T0c = 1:1.50:2.36). The HP-crystal structure evolution was studied on the basis of several structural refinements at different pressures: 0.0001 GPa (with crystal in DAC without any pressure medium), 1.58(3), 1.75(4), 1.94(6), 3.25(4), 4.69(5), 7.36(6), 8.45(5) and 0.0001 GPa (after decompression). The main deformation mechanisms at high-pressure are basically driven by tetrahedral tilting, the tetrahedra behaving as rigid-units. A change in the compressional mechanisms was observed at P ≤ 2 GPa. The P-induced structural rearrangement up to 8.5 GPa is completely reversible. The high thermo-elastic stability of CsAlSi₅O_12, the immobility of Cs at HT/HP-conditions, the preservation of crystallinity at least up to 8.5 GPa and 1,000°C in elastic regime and the extremely low leaching rate of Cs from CsAlSi₅O₁₂ allow to consider this open-framework silicate as functional material potentially usable for fixation and deposition of Cs radioisotopes.     

Detailed comparison of nine intact rock failure criteria using polyaxial intact coal strength data obtained through PFC<Superscript>3D</Superscript> simulations

Study of intact rock failure criteria is an important topic in rock mechanics. In this study, applicability of nine different intact rock failure criteria is investigated for intact coal strength data. PFC^3D modeling was used to simulate the laboratory polyaxial tests for cubic intact coal blocks of side dimension 110 mm under different confining stress combinations. A modified grid search procedure is proposed and used to find the best-fitting parameter values and to calculate the coefficient of determination (R ²) values for each criterion. Detailed comparisons of the nine criteria are made using the following aspects: R ² values, σ ₁ ? σ ₂ plots for different σ ₃, shapes on the deviatoric plane, linearity or nonlinearity on the meridian planes. Through the comparisons of R ² values, σ ₁ ? σ ₂ plots and meridian lines, the modified Wiebols–Cook and modified Lade criteria were found to fit the intact coal strength data best. The nine failure criteria are categorized into three types based on the appearances on the deviatoric plane.     

The potential use of OH-defects in enstatite as geobarometer

In this study, single crystals of pure enstatite (Mg₂Si₂O₆) were synthesised under water-saturated conditions at 4 and 8 GPa and 1,150°C with variable silica activity, leading to phase assemblages enstatite + forsterite, enstatite or enstatite + coesite. Run products were investigated using an FTIR spectrometer equipped with a focal plane array detector enabling IR imaging with a lateral pixel resolution of 2.7 μm. IR spectra within the OH-absorption region show two different groups of absorption bands: group 1 (wavenumbers at 3,592 and 3,687 cm^?1) shows strongest absorptions for E||n _β, whereas group 2 (wavenumbers at 3,067 and 3,362 cm^?1) shows strongest absorptions for E||n _γ. The groups are related to different defect types, group 1 to tetrahedral defects (T-site vacancies) and group 2 to octahedral defects (M-site vacancies). The intensity ratio of the bands within one group (i.e. A ₃₀₆₇/A ₃₃₆₂ and A ₃₅₉₂/A ₃₆₈₇) and the intensity ratio of E||n _γ and E||n _α in group 2 bands remain constant within error. In contrast, the intensity ratio of group 2 to group 1 absorption bands [e.g. (A ₃₃₆₂)/(A ₃₆₈₇)] is sensitive to the SiO₂ activity and pressure. On the basis of the results of this and previous studies, a barometer for pure orthoenstatite coexisting with forsterite can be formulated:\( P\,[{\text{GPa}}] = 1.056 + \sqrt {{\frac{{1.025 - A_{{\left( {3362} \right)/\left[ {(3362) + (3687)} \right]}} }}{0.009}}} , \) where A ₍₃₃₆₂₎ and A ₍₃₆₈₇₎ are the integral absorbances of the component E||n _γ of the absorption bands at 3,362 cm^?1 and the component E||n _β of the absorption band at 3,687 cm^?1, respectively.     

The crystal structure and thermal expansion tensor of MgSO<Subscript>4</Subscript>–11D<Subscript>2</Subscript>O(meridianiite) determined by neutron powder diffraction

We have collected high-resolution neutron powder diffraction patterns from MgSO₄·11D₂O over the temperature range 4.2–250 K. The crystal is triclinic, space-group \( \text{P} \bar{1} \) (Z = 2) with a = 6.72746(6) Å, b = 6.78141(6) Å, c = 17.31803(13) Å, α = 88.2062(6)°, β = 89.4473(8)°, γ = 62.6075(5)°, and V = 701.140(6) ų at 4.2 K, and a = 6.75081(3) Å, b = 6.81463(3) Å, c = 17.29241(6) Å, α = 88.1183(3)°, β = 89.4808(3)°, γ = 62.6891(3)°, and V = 706.450(3) ų at 250 K. Structures were refined to wRp = 3.99 and 2.84% at 4.2 and 250 K, respectively. The temperature dependence of the lattice parameters over the intervening range have been fitted with a modified Einstein oscillator model which was used to obtain the coefficients of the thermal expansion tensor. The volume thermal expansion, α_V, is considerably smaller than ice Ih at all temperatures, and smaller even than MgSO₄·7D₂O (although ?α_V/?T is very similar for both sulfates); MgSO₄·11D₂O exhibits negative α_V below 55 K (compared to 70 K in D₂O ice Ih and 20 K in MgSO₄·7D₂O) The relationship between the magnitude and orientation of the principal axes of the expansion tensor and the main structural elements are discussed.     

Seismic source characteristics in Kachchh and Saurashtra regions of Western India: <Emphasis Type="Italic">b</Emphasis>-value and fractal dimension mapping of aftershock sequences

Seismic source characteristics in the Kachchh rift basin and Saurashtra horst tectonic blocks in the stable continental region (SCR) of western peninsular India are studied using the earthquake catalog data for the period 2006–2011 recorded by a 52-station broadband seismic network known as Gujarat State Network (GSNet) running by Institute of Seismological Research (ISR), Gujarat. These data are mainly the aftershock sequences of three mainshocks, the 2001 Bhuj earthquake (M _w 7.7) in the Kachchh rift basin, and the 2007 and 2011 Talala earthquakes (M _w ≥ 5.0) in the Saurashtra horst. Two important seismological parameters, the frequency–magnitude relation (b-value) and the fractal correlation dimension (D _c) of the hypocenters, are estimated. The b-value and the D _c maps indicate a difference in seismic characteristics of these two tectonic regions. The average b-value in Kachchh region is 1.2 ± 0.05 and that in the Saurashtra region 0.7 ± 0.04. The average D _c in Kachchh is 2.64 ± 0.01 and in Saurashtra 2.46 ± 0.01. The hypocenters in Kachchh rift basin cluster at a depth range 20–35 km and that in Saurashtra at 5–10 km. The b-value and D _c cross sections image the seismogenic structures that shed new light on seismotectonics of these two tectonic regions. The mainshock sources at depth are identified as lower b-value or stressed zones at the fault end. Crustal heterogeneities are well reflected in the maps as well as in the cross sections. We also find a positive correlation between b- and D _c-values in both the tectonic regions.     

Shear wave velocity as function of cone penetration resistance and grain size for Holocene-age uncemented soils: a new perspective

For feasibility studies and preliminary design estimates, field measurements of shear wave velocity, V _s, may not be economically adequate and empirical correlations between V _s and more available penetration measurements such as cone penetration test, CPT, data turn out to be potentially valuable at least for initial evaluation of the small-strain stiffness of soils. These types of correlations between geophysical (Vs) and geotechnical (N-SPT, q _c-CPT) measurements are also of utmost importance where a great precision in the calculation of the deposit response is required such as in liquefaction evaluation or earthquake ground response analyses. In this study, the stress-normalized shear wave velocity V _s1 (in m/s) is defined as statistical functions of the normalized dimensionless resistance, Q _tn-CPT, and the mean effective diameter, D ₅₀ (in mm), using a data set of different uncemented soils of Holocene age accumulated at various sites in North America, Europe, and Asia. The V _s1–Q _tn data exhibit different trends with respect to grain sizes. For soils with mean grain size (D ₅₀) < 0.2 mm, the V _s1/Q _tn ^0.25 ratio undergoes a significant reduction with the increase in D ₅₀ of the soil. This trend is completely reversed with further increase in D ₅₀ (D ₅₀ > 0.2 mm). These results corroborate earlier results that stressed the use of different CPT-based correlations with different soil types, and those emphasized the need to impose particle-size limits on the validity of the majority of available correlations.     

Compressibility of strontium orthophosphate Sr<Subscript>3</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript> at high pressure

High pressure in situ synchrotron X-ray diffraction experiment of strontium orthophosphate Sr₃(PO₄)₂ has been carried out to 20.0 GPa at room temperature using multianvil apparatus. Fitting a third-order Birch–Murnaghan equation of state to the P–V data yields a volume of V ₀ = 498.0 ± 0.1 Å³, an isothermal bulk modulus of K _T  = 89.5 ± 1.7 GPa, and first pressure derivative of K _T ′ = 6.57 ± 0.34. If K _T ′ is fixed at 4, K _T is obtained as 104.4 ± 1.2 GPa. Analysis of axial compressible modulus shows that the a-axis (K _a  = 79.6 ± 3.2 GPa) is more compressible than the c-axis (K _c  = 116.4 ± 4.3 GPa). Based on the high pressure Raman spectroscopic results, the mode Grüneisen parameters are determined and the average mode Grüneisen parameter of PO₄ vibrations of Sr₃(PO₄)₂ is calculated to be 0.30(2).     

High-pressure displacive phase transition of a natural Mg-rich pigeonite

A high-pressure single-crystal X-ray diffraction study has been carried out on a P2₁/c natural Mg-rich pigeonite sample with composition ca. Wo₆En₇₆Fs₁₈ using a diamond anvil-cell. The unit-cell parameters were determined at 14 different pressures to 7.14 GPa. The sudden disappearance of the b-type reflections (h + k = odd) and a strong discontinuity (about 2.8%) in the unit-cell volume indicated a first-order P2₁/c–C2/c phase transition between 4.66 and 4.88 GPa. The P(V) data of the P2₁/c phase were fitted to 4.66 GPa by a third-order Birch–Murnaghan equation of state (BM3 EoS), whereas the limited number of experimental data collected within the C2/c phase between 4.88 and 7.14 GPa were fitted using the same equation of state but with K′ constrained to the value obtained for the P2₁/c fitting. The equation of state coefficients are V ₀ = 424.66(6) ų, K _T0 = 104(2) GPa and K′ = 8(1) for the P2₁/c phase, and V ₀ = 423.6(1) ų, K _T0 = 112.4(8) GPa, and K′ fixed to 8(1) for the C2/c phase. The axial moduli for a, b, and c for the P2₁/c phase were obtained using also a BM3-EoS, while for the C2/c phase only a linear calculation could be performed, and therefore the same approach was applied for comparison also to the P2₁/c phase. In general the C2/c phase exhibits axial compressibilities (β _c > β _a >> β _b) lower than those of the P2₁/c phase (β _b > β _c ≈ β _a; similar to those found in previous studies in clinopyroxenes and orthopyroxenes). The lower compressibility of the C2/c phase compared with that of the P2₁/c could be ascribed to the greater stiffness along the b direction. A previously published relationship between P _c and M2 average cation radius (i.r.) has been updated using all the literature data on P2₁/c clinopyroxene containing large cations at M2 site and our new data. The following weighted regression was obtained: P _c (GPa) = 26(4) ? 28(5) ×  i.r (Å), R ² = 0.97. This improved equation can be used to predict the critical pressure of natural P2₁/c clinopyroxene samples just knowing the composition at M2 site.     

The compressibility of Fe- and Al-bearing phase D to 30 GPa

High-pressure in situ X-ray diffraction experiment of Fe- and Al-bearing phase D (Mg_0.89Fe_0.14Al_0.25Si_1.56H_2.93O₆) has been carried out to 30.5 GPa at room temperature using multianvil apparatus. Fitting a third-order Birch–Murnaghan equation of state to the P–V data yields values of V ₀ = 86.10 ± 0.05 ų; K ₀ = 136.5 ± 3.3 GPa and K′ = 6.32 ± 0.30. If K′ is fixed at 4.0 K ₀ = 157.0 ± 0.7 GPa, which is 6% smaller than Fe–Al free phase D reported previously. Analysis of axial compressibilities reveals that the c-axis is almost twice as compressible (K _c  = 93.6 ± 1.1 GPa) as the a-axis (K _a  = 173.8 ± 2.2 GPa). Above 25 GPa the c/a ratio becomes pressure independent. No compressibility anomalies related to the structural transitions of H-atoms were observed in the pressure range to 30 GPa. The density reduction of hydrated subducting slab would be significant if the modal amount of phase D exceeds 10%.     

The effect of silica activity on the diffusion of Ni and Co in olivine

The diffusion of Ni and Co was measured at atmospheric pressure in synthetic monocrystalline forsterite (Mg₂SiO₄) from 1,200 to 1,500 °C at the oxygen fugacity of air, along [100], with the activities of SiO₂ and MgO defined by either forsterite + periclase (fo + per buffer) or forsterite + protoenstatite (fo + en buffer). Diffusion profiles were measured by three methods: laser-ablation inductively-coupled-plasma mass-spectrometry, nano-scale secondary ion mass spectrometry and electron microprobe, with good agreement between the methods. For both Ni and Co, the diffusion rates in protoenstatite-buffered experiments are an order of magnitude faster than in the periclase-buffered experiments at a given temperature. The diffusion coefficients D _M (M = Ni or Co) for the combined data set can be fitted to the equation:

$$\log \,D_{\text{M}} \,\left( {{\text{in}}\,{\text{m}}^{2} \,{\text{s}}^{ - 1} } \right) = - 6.77( \pm 0.33) + \Delta E_{\text{a}} (M)/RT + 2/3\log a_{{SiO_{2} }}$$

with E_a(Ni) = ? 284.3 kJ mol^?1 and E_a(Co) = ? 275.9 kJ mol^?1, with an uncertainty of ±10.2 kJ mol^?1. This equation fits the data (24 experiments) to ±0.1 in log D _M. The dependence of diffusion on \(a_{{{\text{SiO}}_{2} }}\) is in agreement with a point-defect model in which Mg-site vacancies are charge-balanced by Si interstitials. Comparative experiments with San Carlos olivine of composition Mg_1.8Fe_0.2SiO₄ at 1,300 °C give a slightly small dependence on \(a_{{{\text{SiO}}_{2} }}\), with D \(\propto\) (\(a_{{{\text{SiO}}_{2} }}^{0.5}\)), presumably because the Mg-site vacancies increase with incorporation of Fe³⁺ in the Fe-bearing olivines. However, the dependence on fO₂ is small, with D \(\propto\) (fO₂)^0.12±0.12. These results show the necessity of constraining the chemical potentials of all the stoichiometric components of a phase when designing diffusion experiments. Similarly, the chemical potentials of the major-element components must be taken into account when applying experimental data to natural minerals to constrain the rates of geological processes. For example, the diffusion of divalent elements in olivine from low SiO₂ magmas, such as kimberlites or carbonatites, will be an order of magnitude slower than in olivine from high SiO₂ magmas, such as tholeiitic basalts, at equal temperatures and fO₂.

     

Electron paramagnetic resonance studies on clinochlore from Longitudinal Valley area,northeastern Taiwan

A natural sample of clinochlore from the Longitudinal Valley area of northeastern Taiwan has been characterized by using the powder X-ray diffraction (XRD), differential thermal analysis and electron paramagnetic resonance (EPR) spectroscopic techniques. The lattice parameters of the monoclinic (IIb) clinochlore with the composition (Mg_2.988 Al_1.196 Fe_1.6845 Mn_0.026)_5.8945 (Si_2.559 Al_1.441)₄ O₁₀ (OH)₈ have been calculated from the powder XRD data and are found to be a = 5.347 Å, b = 9.223 Å, c = 14.250 Å, β = 97.2° and Z = 2. The thermal behaviour of the sample showed the typical behaviour of clinochlore with a hydroxyl content of 12.5 wt%. The EPR spectrum at room temperature exhibits two resonance signals centred at g ≈ 2.0 and g ≈ 8.0. The signal at g ≈ 2.0 shows a six-line hyperfine structure which is a characteristic of Mn²⁺ ions in octahedral symmetry. The resonance signal at g ≈ 8.0 is a characteristic of Fe³⁺ ions. The EPR spectra have also been recorded at different temperatures (123–295 K). The population of spin levels (N) has been calculated for g ≈ 2.0 and g ≈ 8.0 resonance signals. It is observed that N increases with decreasing temperature. From EPR spectra, the spin-Hamiltonian parameters have been evaluated. The zero-field splitting parameter (D) is found to be temperature dependent. The peak-to-peak width of the g ≈ 8.0 resonance signal is found to increase with decrease in temperature.     

Thermal equation of state of natural tourmaline at high pressure and temperature

Synchrotron-based in situ angle-dispersive X-ray diffraction experiments were conducted on a natural uvite-dominated tourmaline sample by using an external-heating diamond anvil cell at simultaneously high pressures and temperatures up to 18 GPa and 723 K, respectively. The angle-dispersive X-ray diffraction data reveal no indication of a structural phase transition over the P–T range of the current experiment in this study. The pressure–volume–temperature data were fitted by the high-temperature Birch–Murnaghan equation of state. Isothermal bulk modulus of K ₀ = 96.6 (9) GPa, pressure derivative of the bulk modulus of \(K_{0}^{\prime } = 12.5 \;(4)\), thermal expansion coefficient of α ₀ = 4.39 (27) × 10^?5 K^?1 and temperature derivative of the bulk modulus (?K/?T) _P  = ?0.009 (6) GPa K^?1 were obtained. The axial thermoelastic properties were also obtained with K _a0 = 139 (2) GPa, \(K_{a0}^{\prime }\) = 11.5 (7) and α _a0 = 1.00 (11) × 10^?5 K^?1 for the a-axis, and K _c0 = 59 (1) GPa, \(K_{c0}^{\prime }\) = 11.4 (5) and α _c0 = 2.41 (24) × 10^?5 K^?1 for the c-axis. Both of axial compression and thermal expansion exhibit large anisotropic behavior. Thermoelastic parameters of tourmaline in this study were also compared with that of the other two ring silicates of beryl and cordierite.     

Estimation of excess lifetime cancer risk and radiation hazard indices in southern Iraq

Relatively high activity concentrations of some radionuclides (²²⁶Ra, ²³⁸U, ²³²Th, and ⁴⁰K) have been measured in surface and subsurface soils in areas (southern Iraq) where many warfare actions have taken place during the Iran–Iraq and Gulf wars. Such high activity concentrations might be related to the increase in cancerous injuries and birth defects recently reported. The study was aimed to estimate the activity concentrations of some nuclides and a comparison of results with international health hazard indices. In addition, the excess lifetime cancer risk (ELCR) was assessed. Soil samples were collected at three depths (0, 30, and 60 cm) in three locations in Abu Al Khasib and Ad Dayr in Basrah governorates. The average activity concentrations were estimated employing hyper-pure germanium HPGe gamma-ray detection technology. The values obtained in Abu Al Khasib were: 58.44 Bq/kg (²²⁶Ra), 43.56 Bq/kg (²³⁸U), 19.38 Bq/kg (²³²Th), and 321.76 Bq/kg (⁴⁰K) whereas in Ad Dayr 45.71 Bq/kg (²²⁶Ra), 35.53 Bq/kg (²³⁸U), 20.33 Bq/kg (²³²Th), and 337.02 Bq/kg (⁴⁰K). According to UNSCEAR (Sources and effects of ionizing radiations: a report on the effects of atomic radiation to the general assembly with scientific annexes, Annex B, United Nations, New York, 2000) report, higher levels of ²²⁶Ra, ²³⁸U concentrations than the world’s average values (35 Bq/kg) were observed in both locations. In addition, some radiation hazard indices were determined for both locations: average outdoor external dose (D _out), average indoor external dose (D _in), total average value of the external dose (D _tot), average annual outdoor effective dose (E _out), average annual indoor effective dose (E _in), and averaged total annual effective dose (E _tot). Values for D _tot and E _tot were higher than the worldwide median (143 nGy/h and 0.48 mSv/y, respectively) in both regions. The measured values of activity concentrations were also used to estimate the outdoor, indoor, and total ELCR. The ELCR values were higher than the worldwide averages. Further analyses and studies need to assess the real risks for human health and possible soil remediation.     

Diffusive fractionation of volatiles and their isotopes during bubble growth in magmas

Bubbles grow in decompressing magmas by simple expansion and by diffusive supply of volatiles to the bubble/melt interface. The latter phenomenon is of significant geochemical interest because diffusion can fractionate elements and isotopes (or isotopologues) of dissolved components. This raises the possibility that the character of volatile components in bubbles may not reflect that of volatiles dissolved in the host melt over the lifetime of a bubble—even in the absence of equilibrium vapor/melt isotopic fractionation. Recent experiments have confirmed the existence of an isotope mass effect on diffusion of the volatile element Cl in silicate melt [Fortin et al. (Isotopic fractionation of chlorine during chemical diffusion in a dacitic melt and its implications for isotope behavior during bubble growth (abstract), 2016 Fall AGU Meeting, 2016)], so there is a clear need to understand the efficacy of diffusive fractionation during bubble growth. In this study, numerical models of diffusion and mass redistribution during bubble growth were implemented for both “passive” volatiles—those whose concentrations are generally well below saturation levels—and “active” volatiles such as CO₂ and H₂O, whose elevated concentrations and limited solubilities are the cause of bubble nucleation and growth. Both diffusive and convective bubble-growth scenarios were explored. The magnitude of the isotope mass effect on passive volatiles partitioned into bubbles growing at a constant rate R in a static system depends upon R/D _L, K _d and D _H/D _L (K _d = bubble/melt partition coefficient; D _H/D _L = diffusivity ratio of the heavy and light isotopes). During convective bubble growth, the presence of a discrete (physical) melt boundary layer against the growing bubble (of width x _BL) simplifies outcomes because it leads to the quick onset of steady-state fractionation during growth, the magnitude of which depends mainly upon R?x _BL/D _L and D _H/D _L (bubble/melt fractionation is maximized at R?x _BL/D _L ≈0.1). Constant R is unrealistic for most real systems, so other scenarios were explored by including the solubility and EOS of an “active” volatile (e.g., CO₂) in the numerical simulations. For plausible decompression paths, R increases exponentially with time—leading, potentially, to larger isotopic fractionation of species partitioned into the growing bubble. For volatile species whose isotope mass effects on diffusion have been measured (Cl, Li), predicted isotope fractionation in the exsolved vapor can be as large as ?4‰ for Cl and ?25‰ for Li.     

High-pressure phase transitions of CaRhO<Subscript>3</Subscript> perovskite

High-pressure phase transitions of CaRhO₃ perovskite were examined at pressures of 6–27 GPa and temperatures of 1,000–1,930°C, using a multi-anvil apparatus. The results indicate that CaRhO₃ perovskite successively transforms to two new high-pressure phases with increasing pressure. Rietveld analysis of powder X-ray diffraction data indicated that, in the two new phases, the phase stable at higher pressure possesses the CaIrO₃-type post-perovskite structure (space group Cmcm) with lattice parameters: a = 3.1013(1) Å, b = 9.8555(2) Å, c = 7.2643(1) Å, V _m  = 33.43(1) cm³/mol. The Rietveld analysis also indicated that CaRhO₃ perovskite has the GdFeO₃-type structure (space group Pnma) with lattice parameters: a = 5.5631(1) Å, b = 7.6308(1) Å, c = 5.3267(1) Å, V _m  = 34.04(1) cm³/mol. The third phase stable in the intermediate P, T conditions between perovskite and post-perovskite has monoclinic symmetry with the cell parameters: a = 12.490(3) Å, b = 3.1233(3) Å, c = 8.8630(7) Å, β = 103.96(1)°, V _m  = 33.66(1) cm³/mol (Z = 6). Molar volume changes from perovskite to the intermediate phase and from the intermediate phase to post-perovskite are –1.1 and –0.7%, respectively. The equilibrium phase relations determined indicate that the boundary slopes are large positive values: 29 ± 2 MPa/K for the perovskite—intermediate phase transition and 62 ± 6 MPa/K for the intermediate phase—post-perovskite transition. The structural features of the CaRhO₃ intermediate phase suggest that the phase has edge-sharing RhO₆ octahedra and may have an intermediate structure between perovskite and post-perovskite.     

The thermal expansion and crystal structure of mirabilite (Na<Subscript>2</Subscript>SO<Subscript>4</Subscript>·10D<Subscript>2</Subscript>O) from 4.2 to 300 K,determined by time-of-flight neutron powder diffraction

We have collected high resolution neutron powder diffraction patterns from Na₂SO₄·10D₂O over the temperature range 4.2–300 K following rapid quenching in liquid nitrogen, and over a series of slow warming and cooling cycles. The crystal is monoclinic, space-group P2₁/c (Z = 4) with a = 11.44214(4) Å, b = 10.34276(4) Å, c = 12.75486(6) Å, β = 107.847(1)°, and V = 1436.794(8) Å³ at 4.2 K (slowly cooled), and a = 11.51472(6) Å, b = 10.36495(6) Å, c = 12.84651(7) Å, β = 107.7543(1)°, V = 1460.20(1) Å³ at 300 K. Structures were refined to R _P (Rietveld powder residual, \( R_{P} = {{\sum {\left| {I_{\text{obs}} - I_{\text{calc}} } \right|} } \mathord{\left/ {\vphantom {{\sum {\left| {I_{\text{obs}} - I_{\text{calc}} } \right|} } {\sum {I_{\text{obs}} } }}} \right. \kern-\nulldelimiterspace} {\sum {I_{\text{obs}} } }} \)) better than 2.5% at 4.2 K (quenched and slow cooled), 150 and 300 K. The sulfate disorder observed previously by Levy and Lisensky (Acta Cryst B34:3502–3510, 1978) was not present in our specimen, but we did observe changes with temperature in deuteron occupancies of the orientationally disordered water molecules coordinated to Na. The temperature dependence of the unit-cell volume from 4.2 to 300 K is well represented by a simple polynomial of the form V = ? 4.143(1) × 10^?7 T ³ + 0.00047(2) T² ? 0.027(2) T + 1437.0(1) Å³ (R ² = 99.98%). The coefficient of volume thermal expansion, α _V , is positive above 40 K, and displays a similar magnitude and temperature dependence to α _V in deuterated epsomite and meridianiite. The relationship between the magnitude and orientation of the principal axes of the thermal expansion tensor and the main structural elements are discussed; freezing in of deuteron disorder in the quenched specimen affects the thermal expansion, manifested most obviously as a change in the behaviour of the unit-cell parameter β.     

Early Eocene planktonic and benthic foraminifera from the Khangiran formation (northeast of Iran)

The Kopet-Dagh sedimentary basin is located in northeast of Iran and southeast of Turkmenistan in the Middle East. The Khangiran formation represents the last marine deposition in the Kopet-Dagh sedimentary basin. The early Eocene planktonic and benthic foraminifera from the Khangiran formation which belongs to the lower 376 m thickness of this formation are identified and biostratigraphically evaluated. Due to rarity of Morozovella species, planktonic foraminiferal zonation was difficult to determine in this formation. The determination of upper part of the late Paleocene for the lower 124 m of this formation is according to the lowest occurrence of Acarinina sibaiyaensis species. From E₅ to near middle of E₇ biozone, increasing trend of Acarinina frequency and a peak in Morozovella species and decreasing trend of frequency of Subbotina and Pseudohastigerina species indicate the warm and oligotrophic condition of the seawater during sedimentation of the studied interval. Toward the Ypresian-Lutetian boundary, the increasing trend of Pseudohastigerina and Subbotina species and decreasing in frequency of Acarinina species suggest the low-oxygen level, eutrophic and intermediate condition of the seawater. In this formation, the high abundance of the epifaunal taxa such as Anomalinoides spp., Cibicidoides spp., Gyroidinoides spp., and Lenticulina spp. from the base (late Paleocene sediments) up to E₆ biozone reflects oligotrophic and oxic shallow water conditions. The occurrence of several peaks in abundance of Bulimina and Uvigerina species at the Ypresian/Lutetian boundary suggests eutrophic condition. These paleoecological conditions could be correlated with fluctuations in the numbers of the planktonic foraminifera.