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.     

Biosorption optimization and equilibrium isotherm of industrial dye compounds in novel strains of microscopic fungi

The aim of this study was to evaluate the biosorption capacity of selected strains of microscopic fungi. We optimized the biosorption process and used the Freundlich isotherm for three strains: H. haematococca BwIII43, K37 and T. harzianum BsIII33 to describe the biosorption equilibrium of anthraquinone dye, Alizarin Blue Black B (ABBB) and alkali lignin (AL). In optimal conditions (1 g of mycelium biomass, pH = 7.0, 28 °C) for ABBB and AL sorption, the live biomass of H. haematococca BwIII43 was characterized by a higher sorption capacity, amounting to 247.47 and 161.00 mg g^?1, respectively. The highest sorption properties toward anthraquinone dye (K _F = 19.96 mg g^?1) were shown for the biomass of H. haematococca K37. In the presence of alkali lignin, the highest sorption capacity and bond strength exhibited the biomass of H. haematococca BwIII43 (K _F = 28.20 mg g^?1, n = 3.46). Effective decolorization of ABBB and AL by the selected strains of microscopic fungi indicated that the biosorption process additionally enhanced the removal of color compounds from the solution.     

Efficient removal of Evans blue dye by Zn–Al–NO<Subscript>3</Subscript> layered double hydroxide

Evans blue (EB) dye has been successfully removed from aqueous solution through chemisorption process with synthetic layered double hydroxides (LDH) [Zn_1?x Al _x (OH)₂NO₃·nH₂O, x = 0.2–0.33]. Detailed evaluation of dye adsorption characteristics in aqueous medium has been studied for different layer charged hydroxides. The objective of the study was efficient removal of a dye by LDH and understanding the structure–property relationship of the LDH on its adsorption behaviour. Highest Langmuir monolayer adsorption capacity (Qt) of 113.64 mg g^?1 was observed for highest layer charge x = 0.33, and it is higher than previously reported values for the LDH-EB dye system. Under optimized condition, 99% of EB dye is removed from aqueous solution within 60 min at 313 K. The monotonous increase in Qt value with increasing layer charge is correlated with layer charge density (LCD) and lower particle size of the synthetic LDH. The variation in Qt among different layer charged materials is marginal (3.46–4.17%) with respect to the respective anion exchange capacity (AEC) of LDH NO₃. The limited contribution of AEC surmises the occurrence of surface-only adsorption and absence of intercalation as validated by the XRD analysis. The spontaneity of the EB dye removal increases with increasing temperature and LCD. The chemisorption nature of the adsorption reaction is well supported by the thermodynamics values.     

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.     

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).     

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.     

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.     

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.     

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.     

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⁺.     

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.     

Data-driven nonlinear modeling studies on removal of Acid Yellow 59 using Si-doped multi-walled carbon nanotubes

Data-driven modeling of removal of color index name of Acid Yellow 59 from aqueous solutions using multi-walled carbon nanotubes by multiple (non)linear regression and artificial neural networks (ANN) models based on leave-one-out cross-validation to predict the adsorbed dye amount per unit mass of adsorbent (mg g^?1) and performance evaluation of the proposed multiple (non)linear regression and ANN models is the main novel contributor of the present study. Initial dye concentration, adsorbent concentration, reaction time, and temperature were determined as explanatory variables and input neurons for multiple (non)linear regression and ANN models, respectively. The total number of experiments was determined as 1280 statistically. The results showed that multilayer perception ANN model (\(R^{2}_{\text{training}}\) = 0.9997, \(R^{2}_{\text{testing}}\) = 0.9993, RMSE = 0.7678, MAE of 0.0007) predicted q _t better than multiple (non)linear regression model (\(R^{2}_{\text{adj}}\) = 0.9645, \(R^{2}_{\text{pred}}\) = 0.9633, SE = 9.55) and MLR (R ² = 0.9543, SE = 10.87) models. The results justified the accuracy of ANN in prediction of q _t , significantly.     

Biodegradation of ortho-dimethyl phthalate by a binary culture of <Emphasis Type="Italic">Variovorax</Emphasis> sp. BS1 and <Emphasis Type="Italic">Achromobacter denitrificans</Emphasis>

Binary mixture of Variovorax sp. BS1 and Achromobacter denitrificans degraded >99 % of 300 mg l^?1 of ortho-dimethyl phthalate (DMP) within 24 h of incubation at 30 °C. Rate of degradation of DMP followed the order: A. denitrificans > binary mixture > Variovorax sp. BS1. Transient intermediate metabolites were not detected using HPLC analyses at any time points using Variovorax sp. BS1 and binary mixture. However, using pure culture of A. denitrificans, monomethyl phthalate was accumulated during the course of DMP biodegradation which disappeared with time of incubation. Binary mixture of Variovorax sp. BS1 and A. denitrificans exhibited better efficiency in terms of biodegradation of DMP as compared to either individual bacterial strain. In addition, fluorescence in situ hybridization technique was used to estimate the population dynamics of Variovorax sp. BS1 in binary mixture. A. denitrificans in mixed culture were estimated by subtracting total number of cells of Variovorax sp. BS1 from the total counts of microbial cells using an epifluorescence microscope after staining with 4′,6-diamidino-2-phenylindole. Results obtained at mid-exponential growth phase suggested the abundance of both bacterial strains as primary degraders.     

The use of ultrasonic frequencies to control the bloom formation,regrowth, and eco-toxicity in <Emphasis Type="Italic">Microcystis aeruginosa</Emphasis>

This study is focused on the use of ultrasound to disrupt Microcystis aeruginosa growth, with consideration for the gap between laboratory-scale experiment and field application. Laboratory-scale sonication systems with different frequencies (i.e., 20, 584, 869, and 1137 kHz) for 30 min at 10-min intervals were conducted to investigate their effectiveness at disrupting M. aeruginosa growth. The toxicological effect of sonicated M. aeruginosa including microcystin-LR was also evaluated using a Daphnia magna acute toxicity test. High frequencies, 869 and 1137 kHz, resulted in more than a 60% reduction of cells after 30 min of sonication. Low to middle frequencies, 20 and 584 kHz, only showed a 30% reduction of cells after 30 min of sonication. High frequencies also led to the inactivation of cell proliferation during M. aeruginosa regrowth, due to cellular destruction and finally cell death. However, the concentration of microcystin-LR and the potential adverse effects of M. aeruginosa on D. magna could not be controlled using ultrasonic frequencies. Therefore, our results suggest that ultrasonic frequencies between 869 and 1137 kHz are effective at controlling bloom formation in M. aeruginosa and the regrowth of M. aeruginosa after sonication, but not at controlling microcystin-LR concentrations and its adverse effects on D. magna. Consequently, a combined purification technology to reduce the cyanotoxins such as microcystin-LR, rather than ultrasonic frequency alone, will be needed to control M. aeruginosa growth and its toxicity levels in the aquatic environment.     

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.     

New insights on pressure,temperature, and chemical stability of CsAlSi<Subscript>5</Subscript>O<Subscript>12</Subscript>, a potential host for nuclear waste

A Cs-bearing polyphase aggregate with composition (in wt%): 76(1)_CsAlSi5O12 + 7(1)_CsAlSi2O6 + 17(1)_amorphous, was obtained from a clinoptilolite-rich epiclastic rock after a beneficiation process of the starting material (aimed to increase the fraction of zeolite to 90 wt%), cation exchange and then thermal treatment. CsAlSi₅O₁₂ is an open-framework compound with CAS topology; CsAlSi₂O₆ is a pollucite-like material with ANA topology. The thermal stability of this polyphase material was investigated by in situ high-T X-ray powder diffraction, the combined P–T effects by a series of runs with a single-stage piston cylinder apparatus, and its chemical stability following the “availability test” (“AVA test”) protocol. A series of additional investigations were performed by WDS–electron microprobe analysis in order to describe the P–T-induced modification of the material texture, and to chemically characterize the starting material and the run products. The “AVA tests” of the polyphase aggregate show an extremely modest release of Cs⁺: 0.05 mg/g. In response to applied temperature and at room P, CsAlSi₅O₁₂ experiences an unquenchable and displacive Ama2-to-Amam phase transition at about 770 K, and the Amam polymorph is stable in its crystalline form up to 1600 K; a crystalline-to-amorphous phase transition occurs between 1600 and 1650 K. In response to the applied P = 0.5 GPa, the crystalline-to-amorphous transition of CsAlSi₅O₁₂ occurs between 1670 and 1770 K. This leads to a positive Clapeyron slope (i.e., dP/dT > 0) of the crystalline-to-amorphous transition. When the polyphase aggregate is subjected at P = 0.5 GPa and T > 1770 K, CsAlSi₅O₁₂ melts and only CsAlSi₂O₆ (pollucite-like; dominant) and Cs-rich glass (subordinate) are observed in the quenched sample. Based on its thermo-elastic behavior, P–T phase stability fields, and Cs⁺ retention capacity, CsAlSi₅O₁₂ is a possible candidate for use in the immobilization of radioactive isotopes of Cs, or as potential solid hosts for ¹³⁷Cs γ-radiation source in sterilization applications. More in general, even the CsAlSi₅O₁₂-rich aggregate obtained by a clinoptilolite-rich epiclastic rock appears to be suitable for this type of utilizations.     

Toxinogenicity and cytotoxicity of <Emphasis Type="Italic">Alternaria,Aspergillus</Emphasis> and <Emphasis Type="Italic">Penicillium</Emphasis> moulds isolated from working environments

There is currently limited research available on the secondary metabolites of moulds in workplaces. The aim of this study was to determine the mould contamination in museums (N = 4), composting plants (N = 4) and tanneries (N = 4) and the secondary metabolite profiles of Alternaria, Aspergillus and Penicillium isolates from these workplaces. Alternaria, Aspergillus and Penicillium species were identified using the ITS1/2 sequence of the rDNA region. Mould metabolites were quantitatively analysed on standard laboratory medium and mineral medium containing materials specific to each workplace using liquid chromatography-mass spectrometry. We also examined the cytotoxicity of the moulds using MTT (3-(4,5-dimethylthiazolyl-2)-2,5-diphenyltetrazolium bromide) assays. Air microbiological contamination analyses showed a number of microorganisms, ranging from 2.4 × 10³ CFU m^?3 (composting plants) to 6.8 × 10⁴ CFU m^?3 (tanneries). We identified high percentages of Alternaria, Aspergillus and Penicillium moulds (air 57–59%, surfaces 10–65%) in all workplaces. The following moulds were the most cytotoxic (>90%): Alternaria alternata, A. limoniasperae, Aspergillus flavus, Penicillium biourgeianum, P. commune and P. spinulosum. The same mould species isolated from different working environments exhibited varying toxigenic and cytotoxic properties. Modifying the culture medium to simulate environmental conditions most often resulted in the inhibition of secondary metabolite production. Moulds isolated from the working environments produced the following mycotoxins (ng g^?1): chanoclavines (0.28–204), cyclopiazonic acid (27.1–1045), fumigaclavines (0.33–10,640,000), meleagrin (0.57–13,393), roquefortins (0.01–16,660), rugulovasines (112–220), viridicatin (0.12–957), viridicatol (4.23–2753) and quinocitrinines (0.07–1104), which may have a negative impact on human health.     

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.     

Pressure induced phase transition in Pb<Subscript>6</Subscript>Bi<Subscript>2</Subscript>S<Subscript>9</Subscript>

The crystal structure of Pb₆Bi₂S₉ is investigated at pressures between 0 and 5.6 GPa with X-ray diffraction on single-crystals. The pressure is applied using diamond anvil cells. Heyrovskyite (Bbmm, a = 13.719(4) Å, b = 31.393(9) Å, c = 4.1319(10) Å, Z = 4) is the stable phase of Pb₆Bi₂S₉ at ambient conditions and is built from distorted moduli of PbS-archetype structure with a low stereochemical activity of the Pb²⁺ and Bi³⁺ lone electron pairs. Heyrovskyite is stable until at least 3.9 GPa and a first-order phase transition occurs between 3.9 and 4.8 GPa. A single-crystal is retained after the reversible phase transition despite an anisotropic contraction of the unit cell and a volume decrease of 4.2%. The crystal structure of the high pressure phase, β-Pb₆Bi₂S₉, is solved in Pna2 ₁ (a = 25.302(7) Å, b = 30.819(9) Å, c = 4.0640(13) Å, Z = 8) from synchrotron data at 5.06 GPa. This structure consists of two types of moduli with SnS/TlI-archetype structure in which the Pb and Bi lone pairs are strongly expressed. The mechanism of the phase transition is described in detail and the results are compared to the closely related phase transition in Pb₃Bi₂S₆ (lillianite).