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⁺.     

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).     

Bioaccumulation of heavy metals in <Emphasis Type="Italic">Limnobium laevigatum</Emphasis> and <Emphasis Type="Italic">Ludwigia peploides</Emphasis>: their phytoremediation potential in water contaminated with heavy metals

Contamination with heavy metals in surface and groundwater is a threat to human health and ecosystems. Due to this, the need arises to remediate water polluted through ecological and profitable technologies, such as phytoremediation. The objective of the work was to evaluate the concentration of lead (Pb) and zinc (Zn) in the floating macrophytes Limnobium laevigatum and Ludwigia peploides, after being exposed to contaminated water experimentally. In this way to be able to determine if these plants have mechanisms that allow them to accumulate the metals in the roots and to perform the translocation of these to different vegetative organs, L. laevigatum and L. peploides were placed in solutions contaminated with Pb ([Pb]?=?5 mg/l) and Zn ([Zn]?=?20 mg/l). The concentrations of metals in water, root and leaf samples were evaluated as a function of time (0, 1, 2 and 4 days). The determination of the metals was performed by the atomic absorption spectrophotometry technique. After 4 days of exposure to Pb and Zn, the plants showed high metal removal efficiencies of water, more to 70% in all cases. Pb was accumulated fundamentally by roots, while Zn was accumulated more in the leaves. In addition, the bioconcentration and translocation factors for each metal were calculated.     

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.     

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.     

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.     

Dewatering Behaviour of a Uranium Ore Slurry Containing Clays

The main objective of this paper was to investigate the dewatering behaviour of a clayey uranium ore slurry. The slurry (containing 28% clay size) exhibited moderate water adsorption (w _l  = 83% and w _p  = 30%). Primarily composed of muscovite (46%) and quartz (30%), the clay minerals included illite (8%), chlorite (5%) and kaolinite (2%) alongside a CEC of 41 (cmol(+)/kg) with Ca²⁺ and Mg²⁺ as the dominant cations. Likewise, the high EC (17,600 μS/cm) and ionic strength (1.15 mol/L) indicated a flocculated microstructure due to the presence of SO₄ ^2? (22,600 mg/L) and Mg²⁺ (1340 mg/L) in the slurry water. Settling included sedimentation and consolidation at low initial solids condition (25–35%) whereas only consolidation was observed at high initial solids contents (40–50%). The average k reduced from 1.2 × 10^?6 m/s (initial s = 25%) to 5.3 × 10^?8 m/s (initial s = 50%) along with a void ratio reduction from 7.4 to 2.6. Due to thixotropic strength, volume compressibility during consolidation showed apparent pre-consolidation at low effective stress (0.3–2 kPa) with a reduction in void ratio from 2.6 to 2.5. The e _s was found to be 2.46 at σ′ = 2 kPa and was followed by a steeper slope with the void ratio reducing to 2.1 at σ′ = 31 kPa. Likewise, the hydraulic conductivity during consolidation decreased from 2.6 × 10^?9 m/s (at e = 2.6) to 2.0 × 10^?10 m/s (at e = 2.1).     

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.     

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.     

Optimization of ammonia removal by ion-exchange resin using response surface methodology

The ability of ion-exchange resin for ammonia removal from aqueous solution was studied. The results showed that Amberlite ion-exchange resin was effective in removing ammonia from aqueous solution. Factorial design and response surface methodology were applied to evaluate and optimize the effects of pH, resin dose, contact time, temperature and initial ammonia concentration. Low pH condition was preferred with the optimum pH found to be 6. High resin dose generated high removal rate and low exchange capacity. Results of factorial design and response surface methodology showed that temperature was not a significant parameter. The model prediction was in good agreement with observed data (R ² = 0.957). The optimum Q _e was 28.78 mg/g achieved at pH = 6 and initial TAN concentration of 3000 mg/L. The kinetics followed the pseudo-second-order kinetic model (R ² = 0.999). Equilibrium data were fitted to Langmuir and Freundlich isotherm models with Langmuir model providing a slightly better predication (R ² = 0.996). The resin was completely regenerated by 2 N H₂SO₄.     

Impacts of Varying Estuarine Temperature and Light Conditions on <Emphasis Type="Italic">Zostera marina</Emphasis> (Eelgrass) and its Interactions With <Emphasis Type="Italic">Ruppia maritima</Emphasis> (Widgeongrass)

Seagrass populations have been declining globally, with changes attributed to anthropogenic stresses and, more recently, negative effects of global climate change. We examined the distribution of Zostera marina (eelgrass) dominated beds in the York River, Chesapeake Bay, VA over an 8-year time period. Using a temperature-dependent light model, declines in upriver areas were associated with higher light attenuation, resulting in lower light availability relative to compensating light requirements of Z. marina compared with downriver areas. An inverse relationship was observed between SAV growth and temperature with a change between net bed cover increases and decreases for the period of 2004–2011 observed at approximately 23 °C. Z. marina-dominated beds in the lower river have been recovering from a die-off event in 2005 and experienced another near complete decline in 2010, losing an average of 97 % of coverage of Z. marina from June to October. These 2010 declines were attributed to an early summer heat event in which daily mean water temperatures increased from 25 to 30 °C over a 2-week time period, considerably higher than previous years when complete die-offs were not observed. Z. marina recovery from this event was minimal, while Ruppia maritima (widgeongrass) expanded its abundance. Water temperatures are projected to continue to increase in the Chesapeake Bay and elsewhere. These results suggest that short-term exposures to rapidly increasing temperatures by 4–5 °C above normal during summer months can result in widespread diebacks that may lead to Z. marina extirpation from historically vegetated areas, with the potential replacement by other species.     

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.     

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.     

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.     

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.     

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).     

Evaluation of the removal of heavy metals in a natural wetland impacted by mining activities in Mexico

This research is focused on evaluating heavy metals (Cd, Cu, Fe, Mn, Pb, and Zn) uptake and removal by Eleocharis ovata, Cyperus manimae, Typha dominguensis, and Pteridium aquilinum in a natural wetland impacted by mining activities. We analyzed heavy metals content and distribution in native plants, soils, and water of a semipermanent natural wetland in Taxco de Alarcón, Guerrero, and we also determined the physicochemical characteristics of the water. Translocation factor (TF) and bioconcentration factor (BCF) were evaluated. Results showed that physical and chemical conditions are favorable for plants development. Correlation analysis showed a good and positive relation (0.95) between Cu and Pb in soils and plants. In the analyzed matrices: Zn (0.62–2.20 mg/L) exceeded the permissible limits in water, high concentrations of Pb and Zn (26.57–525.67 and 266.67–983.33 mg/kg, respectively) were detected in the studied soils, and Pb exceeded the normal range for E. ovata and P. aquilinum in the analyzed plants. Uptake of heavy metals in the tissues of different species was found in the following order: root > leaf. Data of TF and BCF showed that E. ovata is a tolerant plant with respect to heavy metals exposure since TF value was greater than 1. This study showed that E. ovata could be considered as a bioaccumulator of heavy metals in contaminated soils.     

Thermal equation of state of CaIrO<Subscript>3</Subscript> post-perovskite

The pressure–volume–temperature (P–V–T) relation of CaIrO₃ post-perovskite (ppv) was measured at pressures and temperatures up to 8.6 GPa and 1,273 K, respectively, with energy-dispersive synchrotron X-ray diffraction using a DIA-type, cubic-anvil apparatus (SAM85). Unit-cell dimensions were derived from the Le Bail full profile refinement technique, and the results were fitted using the third-order Birth-Murnaghan equation of state. The derived bulk modulus \( K_{T0} \) at ambient pressure and temperature is 168.3 ± 7.1 GPa with a pressure derivative \( K_{T0}^{\prime } \) = 5.4 ± 0.7. All of the high temperature data, combined with previous experimental data, are fitted using the high-temperature Birch-Murnaghan equation of state, the thermal pressure approach, and the Mie-Grüneisen-Debye formalism. The refined thermoelastic parameters for CaIrO₃ ppv are: temperature derivative of bulk modulus \( (\partial K_{T} /\partial T)_{P} \) = ?0.038 ± 0.011 GPa K^?1, \( \alpha K_{T} \) = 0.0039 ± 0.0001 GPa K^?1, \( \left( {\partial K_{T} /\partial T} \right)_{V} \) = ?0.012 ± 0.002 GPa K^?1, and \( \left( {\partial^{2} P/\partial T^{2} } \right)_{V} \) = 1.9 ± 0.3 × 10^?6 GPa² K^?2. Using the Mie-Grüneisen-Debye formalism, we obtain Grüneisen parameter \( \gamma_{0} \) = 0.92 ± 0.01 and its volume dependence q = 3.4 ± 0.6. The systematic variation of bulk moduli for several oxide post-perovskites can be described approximately by the relationship K _T0  = 5406.0/V(molar) + 5.9 GPa.     

Accuracy assessment of near-shore bathymetry information retrieved from Landsat-8 imagery

The improvement in the capabilities of Landsat-8 imagery to retrieve bathymetric information in shallow coastal waters was examined. Landsat-8 images have an additional band named coastal/aerosol, Band 1: 435–451 nm in comparison with former generation of Landsat imagery. The selected Landsat-8 operational land image (OLI) was of Chabahar Bay, located in the southern part of Iran (acquired on February 22, 2014 in calm weather and relatively low turbidity). Accurate and high resolution bathymetric data from the study area, produced by field surveys using a single beam echo-sounder, were selected for calibrating the models and validating the results. Three methods, including traditional linear and ratio transform techniques, as well as a novel proposed integrated method, were used to determine depth values. All possible combinations of the three bands [coastal/aerosol (CB), blue (B), and green (G)] have been considered (11 options) using the traditional linear and ratio transform techniques, together with five model options for the integrated method. The accuracy of each model was assessed by comparing the determined bathymetric information with field measured values. The standard error of the estimates, correlation coefficients (R ² ) for both calibration and validation points, and root mean square errors (RMSE) were calculated for all cases. When compared with the ratio transform method, the method employing linear transformation with a combination of CB, B, and G bands yielded more accurate results (standard error = 1.712 m, R ² _calibration = 0.594, R ² _validation = 0.551, and RMSE =1.80 m). Adding the CB band to the ratio transform methodology also dramatically increased the accuracy of the estimated depths, whereas this increment was not statistically significant when using the linear transform methodology. The integrated transform method in form of Depth = b ₀  + b ₁ X _CB  + b ₂ X _B  + b ₅ ln(R _CB )/ln(R _G ) + b ₆ ln(R _B )/ln(R _G ) yielded the highest accuracy (standard error = 1.634 m, R ² _calibration = 0.634, R ² _validation = 0.595, and RMSE = 1.71 m), where R _i (i = CB, B, or G) refers to atmospherically corrected reflectance values in the i ^th band [X _i  = ln(R _i -R _{deep water})].