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.     

Soil bacterial strains with heavy metal resistance and high potential in degrading diesel oil and <Emphasis Type="Italic">n</Emphasis>-alkanes

Four bacterial strains, capable of degrading diesel oil, n-alkanes or hexadecane, were isolated from soils contaminated with petroleum oil and identified. Strains of Pseudomonas sp., Pseudomonas putida TPHK-1 and Pseudomonas aeruginosa TPHK-4, were more efficient in degrading high concentrations of the hydrocarbons than the other two strains, Stenotrophomonas maltophilia TPHK-2 and Acenitobacter sp. TPHK-3. P. putida TPHK-1 exhibited tolerance to very high concentrations of heavy metals such as cadmium, lead, zinc and copper. The innate ability of P. putida TPHK-1, as evidenced by the amplified genes alkB1 and alkB2 that encode alkane hydroxylases, and cat12o and cat23o coding for catechol dioxygenase, in degrading diesel oil in the presence of heavy metals is far greater than that of the strains reported in the literature. Heavy metal tolerance coupled with rapid degradation of hydrocarbons, even at high concentrations, suggests that P. putida TPHK-1 has a great potential in remediating soils contaminated with mixtures of hydrocarbons and heavy metals.     

Enzymatic degradation of polyhydroxyalkanoate using lipase from <Emphasis Type="Italic">Bacillus subtilis</Emphasis>

Polyhydroxyalkanoates (PHAs) are an important class of biodegradable polymers synthesized by a few bacteria under nutrient-limiting conditions. In this study, the lipase-catalysed degradation of PHA synthesized by Enterobacter sp. was monitored. For this, the lipase-encoding gene from Bacillus subtilis DI2 was PCR-amplified, cloned into a T vector system and sequenced. It was expressed in Escherichia coli DH5α cells, the recombinant enzyme was purified 24.25-fold, and its molecular weight was determined to be around 28 kDa. When PHA biodegradation studies were carried out with this enzyme, gel permeation chromatography showed 21.3 and 28.3 % molecular weight decrease and weight loss, respectively. Further, scanning electron micrographs revealed alterations in polymer surface morphology. Changes in molecular vibrations were noticed in the FTIR spectra. When the chemical shifts in NMR spectra were studied, a steep reduction in area under the peak at 1.57 ppm was observed. In the heating range of 30–930 °C employed during thermogravimetry analysis, the degraded sample showed a total of 45.82 % weight loss, as against 18.89 % for the native sample. The melting temperature (T _m) of the polymer was also brought down from 126.22 to 118.18 °C, as inferred from differential scanning calorimetry. Lipase-catalysed chain scission reactions could thus be used to generate low molecular weight functional biopolymers with wide-ranging pharmaceutical applications, such as in sustained drug release.     

Sand-supported bio-adsorbent column of activated carbon for removal of coliform bacteria and <Emphasis Type="Italic">Escherichia coli</Emphasis> from water

New bio-adsorbent carbon materials were synthesized from the leaves and veins of Mucuna pruriens and Manihot esculenta plants, which are locally available in abundance. The synthesized carbons were activated using 0.01N HNO₃. Surface area of the activated carbons from M. pruriens and M. esculenta plants was found to be quite high, i.e., 918 and 865 m²/g, respectively. Scanning electron microscopy analysis of the carbons reflects complex disorganized surface structures of different open pore sizes, shapes and dimensions. These properties of the newly synthesized activated carbons led to the development of a sand-supported carbon column, for its possible use in the removal of coliform bacteria and Escherichia coli (E. Coli) from raw water samples. The removal percentage of E. coli was found to be 100% with both the types of carbon adsorbents, as confirmed from the McCardy most probable number table. Similarly, the removal percentage of coliform bacteria was found to be 99 and 98.7% by M. pruriens and M. esculenta carbon columns, respectively. These activated carbons synthesized from locally available plants possess the characteristics of good low-cost adsorbents which can be easily used for the removal of bacteria from water by adsorption method.     

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.     

Antimicrobial phenolic compounds from <Emphasis Type="Italic">Enterococcus faecium</Emphasis> S29 (EU 158188): characterization and production optimization

The present study aimed to investigate and optimize the promising antagonistic activity of the exogenous Enterococcus faecium S29 (EU 158188) isolated from the heavily polluted coastal waters of Alexandria, Egypt. Statistical designs, mutations and immobilization were used as optimization procedures. Cells grown in Luria-Bertani and/or UV-treated medium showed optimum activity compared to those grown under basal conditions or ethidium bromide treatment as well as wild-type variants. Immobilization decreased the antagonistic activity of E. faecium compared to their free cells. Ethyl acetate extract (12 organic compounds) exhibited the highest antimicrobial activity and was dominated by phenol (52.11%) and 1, 2 Benzenedicarboxylic acid, diisooctyl ester (29.44%) with molecular weights 94 and 390.28, respectively. Thin-layer chromatography (TLC) fractionation of the bioactive compounds showed two spots with RF: 0.32 and 0.61 with the latter exhibits a broad spectrum of antagonistic activity against six reference pathogens {Staphylococcus aureus (ATCC 6538), Streptococcus faecalis (ATCC 8043), Pseudomonas aeruginosa (ATCC 8739), Escherichia coli (ATCC 8739), Micrococcus luteus (ATCC 10240) and Candida albicans}. The yellow gelatinous purified compound was characterized by an aromatic odor; λ _{max =} 0.629 at 210 nm and IR spectrum [IR (K Br): 1750 ester].     

Antimicrobial resistance and prevalence of extended-spectrum beta-lactamase genes in <Emphasis Type="Italic">Escherichia coli</Emphasis> from major rivers in Podhale,southern Poland

The aim of this study was to assess the antimicrobial resistance and the prevalence of genes determining the presence of extended-spectrum beta-lactamase (ESBL) enzymes in Escherichia coli isolated from two major rivers of the Podhale region in southern Poland. In total, 196 E. coli isolates were analyzed—98 from each river—Bia?ka and Zakopianka, collected in 8 campaigns, over the period of two years. Antimicrobial resistance was assessed using disk diffusion method and PCR tests were conducted to detect the ESBL genes. In E. coli isolated from Bia?ka, the resistance to amoxicillin/clavulanic acid was detected most frequently (54.08%) and ESBL was detected in 14.29% of strains. In strains isolated from Zakopianka, most frequent resistance was observed toward ticarcillin (51.02%), while ESBL was observed in 16.33% of isolates. In the total pool of isolates, the resistance to amoxicillin/clavulanic acid was most frequent (48.98% of isolates) and ESBL producers comprised 15.30% of E. coli isolates derived from both rivers. Multidrug resistance was observed less frequently in strains derived from Bia?ka (4 isolates resistant to 10 and more antimicrobials) than from Zakopianka, where 10 isolates were resistant to 10 and more antibiotics. Out of the tested ESBL genes blaTEM was detected most frequently (45.4% of isolates), whereas blaCTX-M1 and blaCTX-M3 were recorded in one isolate.     

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⁺.     

Modified water treatment residual as flocculant for <Emphasis Type="Italic">Microcystis aeruginosa</Emphasis> removal and water purification

Based on previous research, muriatic modification parameters (including the volume of hydrochloric acid, modification temperature and reaction time) were optimized by L₉ (3³) orthogonal design using the removal efficiency of unicellular M. aeruginosa as an index. The results showed that the optimized modification conditions consisted of a hydrochloric acid volume of 4 mL, a modification temperature of 200 °C and a reaction time of 3 h. Under the above conditions, the removal rate for unicellular and colonial M. aeruginosa was 89.26 and 75.53%, respectively. In addition, the flocculation process caused no cell damage, and the cells remained intact after use of the modified water treatment residuals (WTRs) flocculant. TP and TN in water were reduced by 63.37 and 19.03%, respectively. Therefore, the modified WTR flocculant was a technically viable method to remove unicellular and colonial M. aeruginosa.     

The Bloom-Forming Macroalgae, <Emphasis Type="Italic">Ulva</Emphasis>, Outcompetes the Seagrass, <Emphasis Type="Italic">Zostera marina</Emphasis>, Under High CO<Subscript>2</Subscript> Conditions

While multiple species of macroalgae and seagrass can benefit from elevated CO₂ concentrations, competition between such organisms may influence their ultimate responses. This study reports on experiments performed with a Northwest Atlantic species of the macroalgae, Ulva, and the seagrass, Zostera marina, grown under ambient and elevated levels of pCO₂, and subjected to competition with each other. When grown individually, elevated pCO₂ significantly increased growth rates and productivity of Ulva and Zostera, respectively, beyond control treatments (by threefold and 27%, respectively). For both primary producers, significant declines in tissue δ¹³C signatures suggested that increased growth and productivity were associated with a shift from use of HCO₃^? toward CO₂ use. When grown under higher pCO₂, Zostera experienced significant increases in leaf and rhizome carbon content as well as significant increases in leaf carbon-to-nitrogen ratios, while sediments within which high CO₂ Zostera were grown had a significantly higher organic carbon content. When grown in the presence of Ulva; however, above- and below-ground productivity and tissue nitrogen content of Zostera were significantly lower, revealing an antagonistic interaction between elevated CO₂ and the presence of Ulva. The presence of Zostera had no significant effect on the growth of Ulva. Collectively, this study demonstrates that while Ulva and Zostera can each individually benefit from elevated pCO₂ levels, the ability of Ulva to grow more rapidly and inhibit seagrass productivity under elevated pCO₂, coupled with accumulation of organic C in sediments, may offset the potential benefits for Zostera within high CO₂ environments.     

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.     

Bioaugmentation for the enhancement of hydrocarbon phytoremediation by rhizobacteria consortium in pilot horizontal subsurface flow constructed wetlands

The development of the bioaugmentation during the phytoremediation of contaminated water with diesel in pilot horizontal subsurface flow constructed wetlands was investigated for 63 days. The objective of this study was to examine the enrichment of rhizobacteria in a pilot-scale system for efficient treatment of total petroleum hydrocarbon (TPH) effluent. A consortium of three rhizobacteria strains (Bacillus aquimaris, Bacillus anthracis and Bacillus cereus), which were able to utilize hydrocarbon compounds as sole carbon sources, was injected into the constructed wetlands (batchwise operation) planted with Scirpus grossus. The TPH removals from water, without or with the addition of rhizobacteria, were found to be 72 and 84%, while from sand was found to be 59 and 77%, for each treatment, respectively. These results showed that the rhizobacteria strains could enhance S. grossus growth by decreasing diesel stress and protecting S. grossus against diesel, with 12 and 18% additional TPH removal from water and sand, respectively. Our results demonstrate that S. grossus is potential to improve the phytoremediation of hydrocarbon contaminants through inoculation with effective rhizobacterial strains.     

Representatives of genera <Emphasis Type="Italic">Malbosiceras</Emphasis> and <Emphasis Type="Italic">Pomeliceras</Emphasis> (Neocomitidae,Ammonoidea) from the Berriasian of the Crimean Mountains

The revised representatives of ammonite genera Malbosiceras and Pomeliceras from the Berriasian of the Crimean Mountains are classed with seven species, four of the first genus [M. malbosi (Pictet), M. chaperi (Pictet), M. broussei (Mazenot), M. pictetiforme Tavera] and three of the second one [P. aff. boisseti Nikolov, P. breveti (Pomel), P. (?) funduklense Lysenko et Arkadiev sp. nov.]. The identified species are described. The genus Mazenoticeras is considered as synonym of Malbosiceras. The above species prove that all the Berriasian zones (jacobi, occitanica and boissieri) are characteristic of corresponding deposits in the Crimean Mountains.     

<Emphasis Type="Italic">Salpingoporella</Emphasis> (dasycladalean algae) species from the Lower Cretaceous carbonate facies of Kopet Dagh basin (NE Iran)

Salpingoporella species from algal bearing of Barremian-Aptian limestones in the Kopet Dagh basin (NE of Iran) are described. Different species (S. cemi, S. hasi, S. heraldica, S. hispanica, S. milovanovici, S. muehlmbergi, S. parapiriniae, S. piriniae, S. cf. biokovensis, S. steinhauseri, S. polygonalis) are investigated from different biometrical aspects such as depositional environments and biogeographical distribution as well as their systematic palaeontology from two formations (the Tirgan and Sarcheshmeh formations) in nine stratigraphic sections.     

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.     

Systematic paleontology,biostratigraphy, paleobiogeography of <Emphasis Type="Italic">Loftusia</Emphasis> (foraminifera) and <Emphasis Type="Italic">Rudist</Emphasis> assemblages in a regressive sequence in the Hekimhan-Malatya area (Eastern Anatolia) Turkey

The Maastrichtian regressive sequence of the Hekimhan-Malatya area in Eastern Turkey consists of dolomitic limestones, limestones and calcareous mudstones which are dominated by rudists and Loftusia (foraminifera) assemblages. Several Loftusia species indicating middle to late Maastrichtian age such as Loftusia anatolica Meriç, L. baykali Meriç, L. coxi Henson, L. harrisoni Cox, L. minor Cox and L. morgani Douvillé have been recorded. Other benthic foraminifers present include Orbitoides medius d’ Archiac, Omphalocyclus macroporus (Lamarck), Laffitteina conica Drooger, Laffitteina mengaudi (Astre) and Laffitteina oeztuerki Inan. The rudists are abundant in the dolomitic limestones in the study area. The genus Miseia Patrulius is dominant and represented by Miseia bilacunosa Özer and Miseia hekimhanensis Karacabey-Öztemür. The Loftusia species and the Rudists assemblage indicates middle to late Maastrichtian age for the formation. The paleobiogeographic distribution of the assemblage has been discussed taking this find into account.     

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.     

Single-crystal structure and Raman spectroscopy of synthetic titanite analog CaAlSiO<Subscript>4</Subscript>F

Synthetic CaAlSiO₄F, the Al-F analog of titanite, has been investigated using single-crystal synchrotron diffraction experiments at Beamline X06DA (Swiss Light Source, Paul Scherrer Institute, Villigen, Switzerland) and Raman spectroscopy. The presented structural model with 40 parameters was refined against 506 unique reflections to a final R _{o b s} of 0.026 (space group A2/a, a = 6.9120(11), b = 8.5010(10), c = 6.435(2) Å, β = 114.670(11)°, and Z = 4) and exhibits less distorted coordination polyhedra than earlier models from powder data. Vibrational spectra were calculated in harmonic approximation at the Γ point from fully relaxed energy optimisations of the crystal structure, using 3D-periodic density functional theory with Gaussian basis sets and the software CRYSTAL06. The lattice parameters of the fully relaxed structure were in good agreement with the experimental values, with the calculated values 0.8 ± 0.4 % too large; the monoclinic angle was calculated 0.4° too large. The agreement of the calculated Raman frequencies with the observed ones was very good, with standard deviation ±3 cm^?1 and maximum deviations of ±7 cm^?1. Furthermore, a detailed discussion of the atomic displacements associated with each Raman mode is given.     

Laboratory parallel-beam transmission X-ray powder diffraction investigation of the thermal behavior of nitratine NaNO<Subscript>3</Subscript>: spontaneous strain and structure evolution

Present work provides in-situ structural data at a fine temperature scale from RT to the melting point of nitratine, NaNO₃. From the analysis of log e ₃₃ versus log t plots, it is possible to prove that an univocal indication on the R \( \overline{3} \) c (low temperature, LT) → R \( \overline{3} \) m (high temperature, HT) transition mechanism cannot be obtained because of the relevant role played by the arbitrary assumptions required for defining the c ₀ dependence from temperature of the HT phase. This is due to the occurrence of excess thermal expansion for the HT phase. A significantly better fit for an Ising-spin structural model over a non-Ising rigid-body one has been obtained for the LT phase. Moreover, the Ising model led to a smooth variation of the oxygen site x fractional coordinate throughout the transition. The structure of the HT polymorph has been successfully refined considering an oxygen site at x, 0, ½, with 50% occupancy. Such model was the only acceptable one from the crystal chemical point of view as the alternative model (oxygen site at x, y, z with 25% occupancy) led to unrealistically aplanar \( {\text{NO}}_{3}^{ - } \) groups.     

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.