CO<Subscript>2</Subscript>-assisted removal of nutrients from municipal wastewater by microalgae <Emphasis Type="Italic">Chlorella vulgaris</Emphasis> and <Emphasis Type="Italic">Scenedesmus obliquus</Emphasis>

Axenic culture of microalgae Chlorella vulgaris ATCC^® 13482 and Scenedesmus obliquus FACHB 417 was used for phycoremediation of primary municipal wastewater. The main aim of this study was to measure the effects of normal air and CO₂-augmented air on the removal efficacy of nutrients (ammonia N and phosphate P) from municipal wastewater by the two microalgae. Batch experiments were carried out in cylindrical glass bottles of 1 L working volume at 25 °C and cool fluorescent light of 6500 lux maintaining 14/10 h of light/dark cycle with normal air supplied at 0.2 L min^?1 per liter of the liquid for both algal strains for the experimental period. In the next set of experiments, the treatment process was enhanced by using 1, 2 and 5% CO₂/air (vol./vol.) supply into microalgal cultures. The enrichment of inlet air with CO₂ was found to be beneficial. The maximum removal of 76.3 and 76% COD, 94.2 and 92.6% ammonia, and 94.8 and 93.1% phosphate after a period of 10 days was reported for C. vulgaris and S. obliquus, respectively, with 5% CO₂/air supply. Comparing the two microalgae, maximum removal rates of ammonia and phosphate by C. vulgaris were 4.12 and 1.75 mg L^?1 day^?1, respectively, at 5% CO₂/air supply. From kinetic study data, it was found that the specific rates of phosphate utilization (q _phsophate) by C. vulgaris and S. obliquus at 5% CO₂/air supply were 1.98 and 2.11 day^?1, respectively. Scale-up estimation of a reactor removing phosphate (the criteria pollutant) from 50 MLD wastewater influent was also done.     

Sulfate Reduction and Sulfur Cycles at Two Seagrass Beds Inhabited by Cold Affinity <Emphasis Type="Italic">Zostera marina</Emphasis> and Warm Affinity <Emphasis Type="Italic">Halophila nipponica</Emphasis> in Temperate Coastal Waters

To evaluate the impact of invading seagrass on biogeochemical processes associated with sulfur cycles, we investigated the geochemical properties and sulfate reduction rates (SRRs) in sediments inhabited by invasive warm affinity Halophila nipponica and indigenous cold affinity Zostera marina. A more positive relationship between SRR and below-ground biomass (BGB) was observed at the H. nipponica bed (SRR = 0.6809 × BGB ? 4.3162, r ² = 0.9878, p = 0.0006) than at the Z. marina bed (SRR = 0.3470 × BGB ? 4.0341, r ² = 0.7082, p = 0.0357). These results suggested that SR was more stimulated by the dissolved organic carbon (DOC) exuded from the roots of H. nipponica than by the DOC released from the roots of Z. marina. Despite the enhanced SR in spring-summer, the relatively lower proportion (average, 20%) of acid-volatile sulfur (AVS) in total reduced sulfur and the strong correlation between total oxalate-extractable Fe (Fe_(oxal)) and chromium-reducible sulfur (CRS = 0.2321 × total Fe_(oxal) + 1.8180, r ² = 0.3344, p = 0.0076) in the sediments suggested the rapid re-oxidation of sulfide and precipitation of sulfide with Fe. The turnover rate of the AVS at the H. nipponica bed (0.13 day^?1) was 2.5 times lower than that at the Z. marina bed (0.33 day^?1). Together with lower AVS turnover, the stronger correlation of SRR to BGB in the H. nipponica bed suggests that the extension of H. nipponica resulting from the warming of seawater might provoke more sulfide accumulation in coastal sediments.     

Variability of Winter-Spring Bloom <Emphasis Type="Italic">Phaeocystis pouchetii</Emphasis> Abundance in Massachusetts Bay

Abundance of the prymnesiophyte Phaeocystis pouchetii was quantified via light microscopy at 2-week to monthly intervals in Massachusetts Bay (southern Gulf of Maine, NW Atlantic) during 1992–2012. Variability in the abundance and seasonal cycle of Phaeocystis are described and synoptic hydrographic, nutrient, and meteorological data were analyzed to identify factors that may influence Phaeocystis abundance. The maximum Phaeocystis abundance was 14?×?10⁶ cells L^?1 (10 Apr 2008). It was frequently (5 of 8 years) absent prior to year 2000, but not thereafter. Seasonally, it first appeared in February to early March, reached peak abundance in mid-April, and persisted until May or early June for a duration of 0–112 days (mean 34 days). A long-term alternation between Phaeocystis and centric diatom abundance was apparent, suggesting winter-spring selection of either Phaeocystis or centric diatoms. Phytoplankton community analysis suggested that blooms affected the rest of the phytoplankton community. Phaeocystis blooms were manifest as a substantial increase in particulate nutrients above normal levels. Phaeocystis blooms were preceded in February by a slightly elevated concentration of NO₃ (9.3 vs. 6.5 μM when absent) and PO₄ (0.99 vs. 0.79 μM when absent). Blooms were also preceded by elevated ratios of NO₃/PO₄, NO₃/Si, and PO₄/Si, and warmer, saltier waters reflecting reduced river discharge. The correlation with salinity and river discharge suggests that Phaeocystis bloom variability is partially determined by annually varying circulation processes that determine the degree of low nutrient, low salinity coastal water intrusion into Massachusetts Bay.     

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).     

Thermoelastic properties of chromium oxide Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> (eskolaite) at high pressures and temperatures

A new synchrotron X-ray diffraction study of chromium oxide Cr₂O₃ (eskolaite) with the corundum-type structure has been carried out in a Kawai-type multi-anvil apparatus to pressure of 15 GPa and temperatures of 1873 K. Fitting the Birch–Murnaghan equation of state (EoS) with the present data up to 15 GPa yielded: bulk modulus (K _0,T0), 206 ± 4 GPa; its pressure derivative K′_0,T , 4.4 ± 0.8; (?K _0,T /?T) = ?0.037 ± 0.006 GPa K^?1; a = 2.98 ± 0.14 × 10^?5 K^?1 and b = 0.47 ± 0.28 × 10^?8 K^?2, where α _0,T  = a + bT is the volumetric thermal expansion coefficient. The thermal expansion of Cr₂O₃ was additionally measured at the high-temperature powder diffraction experiment at ambient pressure and α _0,T0 was determined to be 2.95 × 10^?5 K^?1. The results indicate that coefficient of the thermal expansion calculated from the EoS appeared to be high-precision because it is consistent with the data obtained at 1 atm. However, our results contradict α ₀ value suggested by Rigby et al. (Brit Ceram Trans J 45:137–148, 1946) widely used in many physical and geological databases. Fitting the Mie–Grüneisen–Debye EoS with the present ambient and high-pressure data yielded the following parameters: K _0,T0 = 205 ± 3 GPa, K′_0,T  = 4.0, Grüneisen parameter (γ ₀) = 1.42 ± 0.80, q = 1.82 ± 0.56. The thermoelastic parameters indicate that Cr₂O₃ undergoes near isotropic compression at room and high temperatures up to 15 GPa. Cr₂O₃ is shown to be stable in this pressure range and adopts the corundum-type structure. Using obtained thermoelastic parameters, we calculated the reaction boundary of knorringite formation from enstatite and eskolaite. The Clapeyron slope (with \({\text{d}}P/{\text{d}}T = - 0.014\) GPa/K) was found to be consistent with experimental data.     

Comparative study of the absorptive potential of raw and activated carbon <Emphasis Type="Italic">Acacia nilotica</Emphasis> for Reactive Black 5 dye

Acacia nilotica was used for the adsorption of Reactive Black 5 (RB5) dye from an aqueous solution. Both the raw and activated (with H₃PO₄) carbon forms of Acacia nilotica (RAN and ANAC, respectively) were used for comparison. Various parameters (including dye concentration, contact time, temperature, and pH) were optimized to obtain the maximum adsorption capacity. RAN and ANAC were characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. The maximum experimental adsorption capacities for RAN and ANAC were 34.79 and 41.01 mg g^?1, respectively, which agreed with the maximum adsorption capacities predicted by the Langmuir, Freundlich, and Dubinin–Radushkevich equilibrium isotherm models. The adsorption data of ANAC showed a good fit to the isotherm models based on the coefficient of determination (R ²): Langmuir type II (R ² = 0.99) > Freundlich (R ² = 0.9853) > Dubinin–Radushkevich (R ² = 0.9659). This result suggested monolayer adsorption of RB5 dye. The adsorption of RB5 dye followed pseudo-second-order kinetics. The RAN adsorbent reflected an exothermic reaction (enthalpy change, ΔH = ?0.006 kJ mol^?1) and increased randomness (standard entropy change, ΔS = 0.038 kJ mol^?1) at the solid–solution interface. In contrast, ANAC reflected both exothermic [?0.011 kJ mol^?1 (303–313 K)] and endothermic [0.003 kJ mol^?1 (313–323 K)] reactions. However, the ΔS value of ANAC was lower when the RB5 adsorption increased from 313 to 323 K. The negative values for the Gibbs free energy change at all temperatures indicated that the adsorption of RB5 dye onto RAN and ANAC was spontaneous in the forward direction.     

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.     

Potential of <Emphasis Type="Italic">Micranthemum umbrosum</Emphasis> for phytofiltration of organic arsenic species from oxic water environment

Arsenic (As) is a toxic and carcinogenic metalloid that causes various hazards to human health. Phytofiltration is a more eco-friendly and green approach than chemoremediation, or other traditional technologies, for removing As from aquatic environments. Recently, Micranthemum umbrosum was shown as a promising candidate for phytofiltration of inorganic As species. This work examines the potential application of M. umbrosum to phytofiltration of organic As species, such as monomethylarsonic acid (MMAA, CH₅AsO₃) and dimethylarsinic acid (DMAA, C₂H₇AsO₂), from oxic water environments. M. umbrosum plants were grown in two test concentrations of MMAA and DMAA, or a control, in a hydroponic experiment. After seven days, leaves accumulated 90 ± 3.2 and 48 ± 1.6 µg As g^?1 (oven dry basis) from 1 µg As mL^?1 of water added from MMAA and DMAA, respectively. Bioconcentration factor values and translocation factor values were always greater than 1.0, indicating that M. umbrosum was a good As accumulator and that leaves accumulated significantly higher amounts of As than stems and roots. Analysis of macro- and micronutrient data showed that M. umbrosum had higher resistance to organic As treatments than the control. These results confirm the potential application of M. umbrosum for phytofiltration of organic As from contaminated oxic water environments.     

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.     

Behavior of 10-Å phase at low temperatures

The thermal evolution of 10-Å phase Mg₃Si₄O₁₀(OH)₂·H₂O, a phyllosilicate which may have an important role in the storage/release of water in subducting slabs, was studied by X-ray single-crystal diffraction in the temperature range 116–293 K. The lattice parameters were measured at several intervals both on cooling and heating. The structural model was refined with intensity data collected at 116 K and compared to the model refined at room temperature. As expected for a layer silicate on cooling in this temperature range, the a and b lattice parameters undergo a small linear decrease, α _a  = 1.7(4) 10^?6 K^?1 and α _b  = 1.9(4) 10^?6 K^?1, where α is the linear thermal expansion coefficient. The greater variation is along the c axis and can be modeled with the second order polynomial c _T  = c ₂₉₃(1 + 6.7(4)10^?5 K^?1ΔT + 9.5(2.5)10^?8 K^?2(ΔT)²) where ΔT = T ? 293 K; the monoclinic angle β slightly increased. The cell volume thermal expansion can be modeled with the polynomial V _T  = V ₂₉₃ (1 + 8.0 10^?5 K^?1 ΔT + 1.4 10^?7 K^?2 (ΔT)²) where ΔT = T ? 293 is in K and V in ų. These variations were similar to those expected for a pressure increase, indicating that T and P effects are approximately inverse. The least-squares refinement with intensity data measured at 116 K shows that the volume of the SiO₄ tetrahedra does not change significantly, whereas the volume of the Mg octahedra slightly decreases. To adjust for the increased misfit between the tetrahedral and octahedral sheets, the tetrahedral rotation angle α changes from 0.58° to 1.38°, increasing the ditrigonalization of the silicate sheet. This deformation has implications on the H-bonds between the water molecule and the basal oxygen atoms. Furthermore, the highly anisotropic thermal ellipsoid of the H₂O oxygen indicates positional disorder, similar to the disorder observed at room temperature. The low-temperature results support the hypothesis that the disorder is static. It can be modeled with a splitting of the interlayer oxygen site with a statistical distribution of the H₂O molecules into two positions, 0.6 Å apart. The resulting shortest O_bas–O_W distances are 2.97 Å, with a significant shortening with respect to the value at room temperature. The low-temperature behavior of the H-bond system is consistent with that hypothesized at high pressure on the basis of the Raman spectra evolution with P.     

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.     

Chemical treatment of teff straw by sodium hydroxide,phosphoric acid and zinc chloride: adsorptive removal of chromium

In this study, teff (Eragrostis tef) straw has been chemically treated and tested as an adsorbent for Cr(VI) removal. Chemically treatment of teff straw was done by NaOH, H₃PO₄ and ZnCl₂ solutions. Scanning electron micrograph and X-ray diffraction were used for anatomical characterization, whereas Fourier transform infrared spectroscopy was used for surface change characterization of adsorbents. Effects of different experimental parameters like pH (2–12), initial Cr(VI) concentration (100–900 mg/L), adsorbent dose (2.5–20 g/L), contact time (15–360 min) and temperature (288–318 K) were studied. Temperature increment was found to stimulate the adsorption process. Langmuir isotherm was found to give better representation over wide range of temperature for untreated, H₃PO₄- as well as ZnCl₂-treated teff straw, and Freundlich isotherm best represented the isotherm data for NaOH-treated teff straw. Maximum Cr(VI) adsorption capacity of untreated, NaOH-, H₃PO₄- and ZnCl₂-treated teff straw was found to be 86.1, 73.8, 89.3 and 88.9 mg/g, respectively. Respective values of average effective diffusion coefficient (D _e) were found to be 2.8 × 10^?13, 2.59 × 10^?14, 1.32 × 10^?13 and 1.14 × 10^?13 m²/s, respectively. The negative value of ΔG _o for all the adsorbents indicates Cr(VI) spontaneous adsorption. Isosteric heat of adsorption (ΔH _st,a) was found to vary with surface coverage (θ). ΔH _st,a increased for untreated, H₃PO₄- and ZnCl₂-treated teff straw, and decreased steadily with θ for NaOH-treated teff straw.     

The Influence of Benthic Macrofauna on the Erodibility of Intertidal Sediments with Varying mud Content in Three New Zealand Estuaries

Fine sediment inputs can alter estuarine ecosystem structure and function. However, natural variations in the processes that regulate sediment transport make it difficult to predict their fate. In this study, sediments were sampled at different times (2011–2012) from 45 points across intertidal sandflat transects in three New Zealand estuaries (Whitford, Whangamata, and Kawhia) encompassing a wide range in mud (≤63 μm) content (0–56 %) and macrofaunal community structure. Using a core-based erosion measurement device (EROMES), we calculated three distinct measures of sediment erosion potential: erosion threshold (? _c ; N m^?2), erosion rate (ER; g m^?2 s^?1), and change in erosion rate with increasing bed shear stress (m _e ; g N^?1 s^?1). Collectively, these measures characterized surface (? _c and ER) and sub-surface (m _e ) erosion. Benthic macrofauna were grouped by functional traits (size and motility) and data pooled across estuaries to determine relationships between abiotic (mud content, mean grain size) and biotic (benthic macrofauna, microbial biomass) variables and erosion measures. Results indicated that small bioturbating macrofauna (predominantly freely motile species <5 mm in size) destabilized surface sediments, explaining 23 % of the variation in ? _c (p ≤ 0.01) and 59 % of the variation in ER (p ≤ 0.01). Alternatively, mud content and mean grain size cumulatively explained 61 % of the variation in m _e (p ≤ 0.01), where increasing mud and grain size stabilized sub-surface sediments. These results highlight that the importance of biotic and abiotic predictors vary with erosion stage and that functional group classifications are a useful way to determine the impact of benthic macrofauna on sediment erodibility across communities with different species composition.     

On the crystal chemistry and elastic behavior of a phlogopite 3<Emphasis Type="Italic">T</Emphasis>

The crystal chemistry and the elastic behavior under isothermal conditions up to 9 GPa of a natural, and extremely rare, 3T-phlogopite from Traversella (Valchiusella, Turin, Western Alps) [(K_0.99Na_0.05Ba_0.01)(Mg_2.60Al_0.20Fe _0.21 ²⁺ )[Si_2.71Al_1.29O₁₀](OH)₂, space group P3₁12, with a = 5.3167(4), c = 30.440(2) Å, and V = 745.16(9) ų] have been investigated by electron microprobe analysis in wavelength dispersion mode, single-crystal X-ray diffraction at 100 K, and in situ high-pressure synchrotron radiation powder diffraction (at room temperature) with a diamond anvil cell. The single-crystal refinement confirms the general structure features expected for trioctahedral micas, with the inter-layer site partially occupied by potassium and sodium, iron almost homogeneously distributed over the three independent octahedral sites, and the average bond distances of the two unique tetrahedra suggesting a disordered Si/Al-distribution (i.e., 〈T1-O〉 ~ 1.658 and 〈T2-O〉 ~ 1.656 Å). The location of the H-site confirms the orientation of the O–H vector nearly perpendicular to (0001). The refinement converged with R ₁(F) = 0.0382, 846 unique reflections with F _O > 4σ(F _O) and 61 refined parameters, and not significant residuals in the final difference-Fourier map of the electron density (+0.77/?0.37 e ^?/ų). The high-pressure experiments showed no phase transition within the pressure range investigated. The P–V data were fitted with a Murnaghan (M-EoS) and a third-order Birch-Murnaghan equation of state (BM-EoS), yielding: (1) M-EoS, V ₀ = 747.0(3) ų, K _T0 = 44.5(24) GPa, and K′ = 8.0(9); (2) BM-EoS, V ₀ = 747.0(3) ų, K _T0 = 42.8(29) GPa, and K′ = 9.9(17). A comparison between the elastic behavior in response to pressure observed in 1M- and 3T-phlogopite is made.     

<Emphasis Type="Italic">P</Emphasis>–<Emphasis Type="Italic">V</Emphasis>–<Emphasis Type="Italic">T</Emphasis> equation of state of CaAl<Subscript>4</Subscript>Si<Subscript>2</Subscript>O<Subscript>11</Subscript> CAS phase

The thermoelastic parameters of the CAS phase (CaAl₄Si₂O₁₁) were examined by in situ high-pressure (up to 23.7 GPa) and high-temperature (up to 2,100 K) synchrotron X-ray diffraction, using a Kawai-type multi-anvil press. P–V data at room temperature fitted to a third-order Birch–Murnaghan equation of state (BM EOS) yielded: V _0,300 = 324.2 ± 0.2 Å³ and K _0,300 = 164 ± 6 GPa for K′ _0,300 = 6.2 ± 0.8. With K′ _0,300 fixed to 4.0, we obtained: V _0,300 = 324.0 ± 0.1 Å³ and K _0,300 = 180 ± 1 GPa. Fitting our P–V–T data with a modified high-temperature BM EOS, we obtained: V _0,300 = 324.2 ± 0.1 Å³, K _0,300 = 171 ± 5 GPa, K′ _0,300 = 5.1 ± 0.6 (?K _0,T /?T) _P  = ?0.023 ± 0.006 GPa K^?1, and α_0,T  = 3.09 ± 0.25 × 10^?5 K^?1. Using the equation of state parameters of the CAS phase determined in the present study, we calculated a density profile of a hypothetical continental crust that would contain ~10 vol% of CaAl₄Si₂O₁₁. Because of the higher density compared with the coexisting minerals, the CAS phase is expected to be a plunging agent for continental crust subducted in the transition zone. On the other hand, because of the lower density compared with lower mantle minerals, the CAS phase is expected to remain buoyant in the lowermost part of the transition zone.     

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.     

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.     

Synthesis,TEM characterization and thermal behaviour of LiNiSi<Subscript>2</Subscript>O<Subscript>6</Subscript> pyroxene

A pyroxene with composition LiNiSi₂O₆ was synthesized at T = 1,473 K and P = 2.0 GPa; the cell parameters at T = 298 K are a = 9.4169(6) Å, b = 8.4465(7) Å, c = 5.2464(3) Å, β = 110.534(6)°, V = 390.78(3) Å³. TEM examination of the LiNiSi₂O₆ pyroxene showed the presence of h + k odd reflections indicative of a primitive lattice, and of antiphase domains obtained by dark field imaging of the h + k odd reflections. A HT in situ investigation was performed by examining TEM selected area diffraction patterns collected at high temperature and synchrotron radiation powder diffraction. In HTTEM the LiNiSi₂O₆ was examined together with LiCrSi₂O₆ pyroxene. In LiCrSi₂O₆ the h + k odd critical reflections disappear at about 340 K; they are sharp up to the transition temperature and do not change their shape until they disappear. In LiNiSi₂O₆ the h + k odd reflections are present up to sample deterioration at 650 K. A high temperature synchrotron radiation powder diffraction investigation was performed on LiNiSi₂O₆ between 298 and 773 K. The analysis of critical reflections and of changes in cell parameters shows that the space group is P-centred up to the highest temperature. The comparative analysis of the thermal and spontaneous strain contributions in P2₁/c and C2/c pyroxenes indicates that the high temperature strain in P-LiNiSi₂O₆ is very similar to that due to thermal strain only in C2/c spodumene and that a spontaneous strain contribution related to pre-transition features is not apparent in LiNiSi₂O₆. A different high-temperature behaviour in LiNiSi₂O₆ with respect to other pyroxenes is suggested, possibly in relation with the presence of Jahn–Teller distortion of the M1 polyhedron centred by low-spin Ni³⁺.     

Structural investigations of (Ca,Sr)ZrO<Subscript>3</Subscript> and Ca(Sn,Zr)O<Subscript>3</Subscript> perovskite compounds

(Ca _x ,Sr_1?x )ZrO₃ and Ca(Sn _y ,Zr_1-y )O₃ solid solutions were synthesized by solid-state reaction at high temperature before to be studied by powder X-ray diffraction and Raman Spectroscopy. Diffraction data allow the distortion of the ABO₃ perovskite structure to be investigated according to cations substitution on A and B-sites. It is shown that distortion, characterized by Φ, the tilt angle of BO₆ octahedra, slightly increases with decreasing y content in Ca(Sn _y ,Zr_1?y )O₃ compounds and strongly decreases with decreasing x content in (Ca _x ,Sr_1?x )ZrO₃ compounds. Such results are discussed in view of the relative A and B cation sizes. Raman data show that vibrational spectra are strongly affected by the cation substitution on A-site; the frequencies of most vibrational modes increase with increasing x content in (Ca _x ,Sr_1?x )ZrO₃ compounds, i.e. with the decreasing mean size of the A-cation; the upper shift is observed for the 358 cm^?1 mode (?ν/?r = ?60.1 cm^?1/Å). On the other hand, the cation substitution on B-sites, slightly affect the spectra; it is shown that in most cases, the frequency of vibrational modes increases with increasing y content in Ca(Sn _y ,Zr_1?y )O₃ compounds, i.e. with the decreasing mean size of the B-cation, but that two modes (287 and 358 cm^?1) behave differently: their frequencies decrease with the decreasing mean size of the B-cation, with a shift respectively equal to +314 and +162 cm^?1/Å. Such results could be used to predict the location of different elements such as trivalent cations or radwaste elements on A- or B-site, in the perovskite structure.