Rb–Sr and <Superscript>147</Superscript>Sm–<Superscript>143</Superscript>Nd systematics of gabbro and dolerites from fragments of ophiolite complexes of the Middle Urals

The Rb–Sr and ¹⁴⁷Sm–¹⁴³Nd age data obtained for sheeted dolerite dykes and rocks of the Platinum Belt of the Urals within the Tagil segment of the paleoceanic spreading structure (Middle Urals) are discussed. The study of the Rb–Sr isotope systematics of gabbro allowed us to reveal errochronous dependencies, which yielded ages of 415 and 345 Ma at (⁸⁷Sr/⁸⁶Sr)₀ = 0.70385 ± 0.00068 and 0.7029 ± 0.0010, correspondingly. The ¹⁴⁷Sm–¹⁴³Nd isotope age data demonstrate a specific coincidence of the chronometric ages of the sheeted dolerite dyke complex (426 ± 54, 426 ± 34, and 424 ± 19 Ma) and gabbro from the Revda gabbro–ultramafic massif (431 ± 27 Ma) and from screens between dolerite dykes in the sheeted dyke complex (427 ± 32 Ma, 429 ± 26 Ma). The proximity of the ¹⁴⁷Sm–¹⁴³Nd ages of gabbro and dolerite can be explained by the thermal effect of the basaltic melt, which is the protolith for the dyke complex, on the hosting gabbro.     

Competitiveness versus ‘clean and green’? The regulation and governance of GMOs in Australia and the UK

It is increasingly argued that we are entering into a “biotech century”, in which biotechnology promises major advances in agricultural productivity. The development of biotechnology is not a straightforward affair, however, and the advent of GMOs has led to public protest and consumer resistance. This paper draws upon a comparative Australian-UK project concerned with the role of regulation and governance in mediating the debates and managing the associated risks. Regulatory responses and the mediation of conflicts by the Australian and UK governments have been shaped by the institutional and policy environments in these two countries. The implications of these public debates and regulatory responses for the capture of competitive opportunities are considered. The fact that the two countries have broadly similar systems of governance and regulation reveals how alike the circumstances are in many respects. But at the same time there are important differences in both the style and the content of the policy debates. In both the UK and Australia, the respective central governments remain committed to a ‘biotechnology future’. Against this background, there is little doubt that the choices about biotechnology will play a defining role in shaping the future of rural places.     

Thermal behaviour of pyrope at 1000 and 1100 °C: mechanism of Fe<Superscript>2+</Superscript> oxidation and decomposition model

The mechanism of thermally induced oxidation of Fe²⁺ from natural pyrope has been studied at 1000 and 1100 °C using ⁵⁷Fe Mössbauer spectroscopy in conjunction with XRD, XRF, AFM, QELS, TG, DTA and electron microprobe analyses. At 1000 °C, the non-destructive oxidation of Fe²⁺ in air includes the partial stabilization of Fe³⁺ in the dodecahedral 24c position of the garnet structure and the simultaneous formation of hematite particles (15–20 nm). The incorporation of the magnesium ions to the hematite structure results in the suppression of the Morin transition temperature to below 20 K. The general garnet structure is preserved during the redox process at 1000 °C, in accordance with XRD and DTA data. At 1100 °C, however, oxidative conversion of pyrope to the mixed magnesium aluminium iron oxide, Fe-orthoenstatite and cristoballite was observed. During this destructive decomposition, Fe²⁺ is predominantly oxidized and incorporated into the spinel structure of Mg(Al,Fe)₂O₄ and partially stabilized in the structure of orthoenstatite, (Mg,Fe)SiO₃. The combination of XRD and Mössbauer data suggest the definite reaction mechanism prevailing, including the refinement of the chemical composition and quantification of the reaction products. The reaction mechanism indicates that the respective distribution of Fe²⁺and Fe³⁺ to the enstatite and spinel structures is determined by the total content of Fe²⁺ in pyrope.     

Conspicuous redemption? Reflections on the promises and perils of the ‘Celebritization’ of climate change

With rising public awareness of climate change, celebrities have become an increasingly important community of non nation-state ‘actors’ influencing discourse and action, thereby comprising an emergent climate science-policy-celebrity complex. Some feel that these amplified and prominent voices contribute to greater public understanding of climate change science, as well as potentially catalyze climate policy cooperation. However, critics posit that increased involvement from the entertainment industry has not served to influence substantive long-term advancements in these arenas; rather, it has instead reduced the politics of climate change to the domain of fashion and fad, devoid of political and public saliency. Through tracking media coverage in Australia, Canada, the United States, and United Kingdom, we map out the terrain of a ‘Politicized Celebrity System’ in attempts to cut through dualistic characterizations of celebrity involvement in politics. We develop a classification system of the various types of climate change celebrity activities, and situate movements in contemporary consumer- and spectacle-driven carbon-based society. Through these analyses, we place dynamic and contested interactions in a spatially and temporally-sensitive ‘Cultural Circuits of Climate Change Celebrities’ model. In so doing, first we explore how these newly ‘authorized’ speakers and ‘experts’ might open up spaces in the public sphere and the science/policy nexus through ‘celebritization’ effects. Second, we examine how the celebrity as the ‘heroic individual’ seeking ‘conspicuous redemption’ may focus climate change actions through individualist frames. Overall, this paper explores potential promises, pitfalls and contradictions of this increasingly entrenched set of ‘agents’ in the cultural politics of climate change. Thus, as a form of climate change action, we consider whether it is more effective to ‘plant’ celebrities instead of trees.     

Spectroscopic studies of synthetic and natural ringwoodite, γ-(Mg,Fe)<Subscript>2</Subscript>SiO<Subscript>4</Subscript>

Synthetic ringwoodite γ-(Mg_1?x Fe _x )₂SiO₄ of 0.4 ≤ x ≤ 1.0 compositions and variously colored micro-grains of natural ringwoodite in shock metamorphism veins of thin sections of two S6-type chondrites were studied by means of microprobe analysis, TEM and optical absorption spectroscopy. Three synthetic samples were studied in addition with Mössbauer spectroscopy. The Mössbauer spectra consist of two doublets caused by ^VIFe²⁺ and ^VIFe³⁺, with IS and QS parameters close to those established elsewhere (e.g., O’Neill et al. in Am Mineral 78:456–460, 1993). The Fe³⁺/Fe_total ratio evaluated by curve resolution of the spectra, ranges from 0.04 to 0.1. Optical absorption spectra of all synthetic samples studied are qualitatively very similar as they are directly related to the iron content. They differ mostly in the intensity of the observed absorption features. The spectra consist of a very strong high-energy absorption edge and a series of absorption bands of different width and intensity. The three strongest and broadest absorptions of them are attributed to splitting of electronic spin-allowed ⁵ T _2g → ⁵ E _g transitions of ^VIFe²⁺ and intervalence charge-transfer (IVCT) transition between ferrous and ferric ions in adjacent octahedral sites of the ringwoodite structure. The spin-allowed bands at ca. 8,000 and 11,500 cm^?1 weakly depend on temperature, whilst the Fe²⁺/Fe³⁺ IVCT band at ~16,400 cm^?1 displays very strong temperature dependence: i.e., with increasing temperature it decreases and practically disappears at about 497 K, a behavior typical for bands of this type. With increasing pressure the absorption edge shifts to lower energies while the spin-allowed bands shift to higher energy and strongly decreases in intensity. The IVCT band also strongly weakens and vanishes at about 9 GPa. We assigned this effect to pressure-induced reduction of Fe³⁺ in ringwoodite. By analogy with synthetic samples three broad bands in spectra of natural (meteoritic) blue ringwoodite are assigned to electronic spin-allowed transitions of ^VIFe²⁺ (the bands at ~8,600 and ~12,700 cm^?1) and Fe²⁺/Fe³⁺ IVCT transition (~18,100 cm^?1), respectively. Spectra of colorless ringwoodite of the same composition consist of a single broad band at ca. 12,000 cm^?1. It is assumed that such ringwoodite grains are inverse (Fe, Mg)₂SiO₄-spinels and that the single band is caused by the split spin-allowed ⁵ E → ⁵ T ₂ transition of ^IVFe²⁺. Ringwoodite of intermediate color variations between dark-blue and colorless are assumed to be partly inversed ringwoodite. No glassy material between the grain boundaries in the natural colored ringwoodite aggregates was found in our samples and disprove the cause of the coloration to be due to light scattering effect (Lingemann and Stöffler in Lunar Planet Sci 29(1308), 1998).     

Isotopic composition (δ<Superscript>13</Superscript>C and δ<Superscript>18</Superscript>O) and genesis of carbonates from the famennian manganiferous formation of Pai-Khoi

The results of isotope-geochemical studies of carbonates of different mineral types from manganese and host rocks of the Famennian manganiferous formation of Pai-Khoi are reported. Kutnahorite ores are characterized by δ¹³C values from–6.6 to 1.3‰ and δ¹⁸O from 20.0 to 27.4‰. Rhodonite–rhodochrosite rocks of the Silovayakha ore occurrence have δ¹³C from–5.2 to–2.9 and δ¹⁸O from 25.4 to 24.3‰. Mineralogically similar rocks of the Nadeiyakha ore occurrence show the lighter carbon and oxygen isotopic compositions: δ¹³C from–16.4 to–13.1 and δ¹⁸O from 24.8 to 22.5‰. Similar isotopic compositions were also obtained for rhodochrosite–kutnahorite rocks of this ore occurrence: δ¹³C from–13.0 to–10.4‰ and δ¹⁸O from 24.6 to 21.7‰. Siderorodochrosite ores differ in the lighter oxygen and carbon isotopic compositions: δ¹⁸O from 18.7 to 17.6‰ and δ¹³C from–10.2 to–9.3‰, respectively. In terms of the carbon and oxygen isotopic compositions, host rocks in general correspond to marine sedimentary carbonates. Geological-mineralogical and isotope data indicate that the formation of the manganese carbonates was related to the hydrothermal ore-bearing fluids with the light isotopic composition of oxygen and carbon dissolved in CO₂. The isotopic features indicate an authigenic formation of manganese carbonates under different isotopegeochemical conditions.     

Static compression of α-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>: linear incompressibility of lattice parameters and high-pressure transformations

The high-pressure behavior of -Fe₂O₃ has been studied under static compression up to 60 GPa, using a laser-heated diamond anvil cell. Synchrotron-based angular-dispersive X-ray diffraction shows that the sample remains in the corundum structure up to 50 GPa, but with the appearance of coexisting diffraction lines from a high-pressure phase at pressures above 45 GPa. A least-squares fit of low-pressure phase data to an Eulerian finite-strain equation of state yields linear incompressibilities of K _{a 0}=749.5 (± 18.4) GPa and K _{c 0}= 455.7 (± 21.4) GPa, differing by a factor of 1.6 along the two directions. The enhanced compressibility of the c axis may lead to breaking of vertex- or edge-sharing bonds between octahedra, inducing the high-pressure phase transformation at 50 GPa. Analysis of linear compressibilities suggests that the high-pressure phase above 50 GPa is of the Rh₂O₃ (II) structure. Continuous laser heating reveals a new structural phase transformation of -Fe₂O₃ at 22 GPa, to an orthorhombic structure with a=7.305(3) Å, b=7.850(3) Å, and c=12.877(14) Å, different from the Rh₂O₃ (II) structure.     

Experimental study of the dehydration of 10-Å phase,with implications for its H<Subscript>2</Subscript>O content and stability in subducted lithosphere

The 10-Å phase (TAP) is a hydrous magnesium silicate that forms from the reaction of talc with H₂O at high pressures. Its high-pressure, low-temperature stability means that it could be a storage site for H₂O in subduction zones. We have determined the position of the TAP dehydration reaction, TAP = enstatite + coesite + H₂O, in phase-equilibrium experiments from 5.0 to 7.1 GPa. Because previous studies had suggested that the composition of TAP is a function of synthesis duration, we used a TAP sample that was synthesised for 392 h. Over the pressure interval of our experiments, the dehydration reaction is isothermal, occurring at a temperature of ~690°C. It is coincident, within experimental uncertainty, with the position of the dehydration reaction of TAP synthesised in short experiments (up to 46 h). Above 7.5 GPa, TAP breaks down to enstatite + stishovite + H₂O. This reaction has a negative dP/dT and terminates at an invariant point involving the 3.65-Å phase at ~9.5 GPa, 500°C. The zero volume change implied by the isothermal reaction TAP = enstatite + coesite + H₂O was used to calculate the interlayer H₂O content of TAP along the reaction. A best-fit H₂O content of 1 H₂O pfu was obtained. This H₂O content is independent of TAP synthesis conditions, suggesting that variations in previously measured H₂O contents of TAP occur during quenching and decompression of the samples. The stability of TAP in the Earth is probably limited to cold subduction zones, but in these, it could persist to 300 km depth.     

Space group and hydrogen sites of δ-AlOOH and implications for a hypothetical high-pressure form of Mg(OH)<Subscript>2</Subscript>

The space group and hydrogen positions of -(Al_0.84Mg_0.07Si_0.09)OOH are investigated using a single crystal synthesized using a multi-anvil apparatus under conditions of 1000 °C and 21 GPa. The space group determined by single-crystal X-ray diffraction is to Pnn2, with unit-cell parameters of a=4.6975(8) Å, b= 4.2060(6) Å, c=2.8327(4) Å, and V=55.97(1) ų. Partial occupancy of the Al site by Mg and Si suggests the possibility of a limited solid solution between -AlOOH, stishovite, and a hypothetical CaCl₂-type Mg(OH)₂ that is 16% denser than brucite. Difference-Fourier maps reveal two small but significant Fourier peaks attributable to hydrogen atoms. Atomic distances and angles around the first peak indicate a hydrogen bond with O···O distances of 2.511 Å, while those around the second peak are suggestive of a bifurcated hydrogen bond with O···O distances of 2.743 and 2.743 Å.     

Simulation of molecular mass distributions and evaluation of O<Superscript>2−</Superscript> concentrations in polymerized silicate melts

A new statistical model is proposed for the molecular mass distributions (MMD) of polymerized anions in silicate melts. The model is based on the known distribution of Q ⁿ species in the MeO-Me₂O-SiO₂ system. In this model, chain and ring complexes are regarded as a random series of Q ⁿ structons with various concentrations of bridging bonds (1 ≤ n ≤ 4, Q ⁰ corresponds to SiO ₄ ^4? ). This approach makes it possible to estimate the probability of formation of various ensembles of polymer species corresponding to the general formula (Si _i O_3i+1?j )^2(i+1?j)?, where i is the size of the ion, and j is the cyclization number of intrachain bonds. The statistical model is utilized in the STRUCTON computer model, which makes use of the Monte Carlo method and is intended for the calculation of the composition and proportions of polyanions at a specified degree of polymerization of silicate melts (STRUCTON, version 1.2; 2007). Using this program, we simulated 1200 MMD for polyanions in the range of 0.52 ≤ p ≤98, where p is the fraction of nonbridging bonds in the silicon-oxygen matrix. The average number of types of anions in this range was determined to increase from three (SiO ₄ ^4? , Si₂O ₇ ^6? , and Si₃O ₁₀ ^8? ) to 153, and their average size increases from 1 to 7.2. A special option of the STRUCTON program combines MMD reconstructions in silicate melts with the formalism of the Toop-Samis model, which enables the calculation of the mole fraction of the O^2? ion relative to all anions in melts of specified composition. It is demonstrated that, with regard for the distribution and average size of anion complexes, the concentration of the O^2? ion in the MeO-SiO₂ system is characterized by two extrema: a minimum at 40–45 mol % SiO₂, which corresponds to the initial stages of the gelenization of the polycondensated silicate matrix, and a maximum, which is predicted for the range of 60–80 mol % SiO₂.     

Fluid–mineral reactions and melting of orthopyroxene–cordierite–biotite gneiss in the presence of H<Subscript>2</Subscript>O-CO<Subscript>2</Subscript>-NaCl and H<Subscript>2</Subscript>O-CO<Subscript>2</Subscript>-KCl fluids under parameters of granulite-facies metamorphism

Reactions and partial melting of peraluminous rocks in the presence of H₂O-CO₂–salt fluids under parameters of granulite-facies metamorphism were modeled in experiments on interaction between orthopyroxene–cordierite–biotite–plagioclase–quartz metapelite with H₂O, H₂O-CO₂, H₂O-CO₂-NaCl, and H₂O-CO₂-KCl fluids at 600 MPa and 850°C. Rock melting in the presence of H₂O and equimolar H₂O-CO₂ fluids generates peraluminous (A/CNK¹ > 1.1) melts whose composition corresponds to magnesian calcic or calc–alkaline S-type granitoids. The melts are associated with peritectic phases: magnesian spinel and orthopyroxene containing up to 9 wt % Al₂O₃. In the presence of H₂O-CO₂-NaCl fluid, cordierite and orthopyroxene are replaced by the association of K-Na biotite, Na-bearing gedrite, spinel, and albite. The Na₂O concentrations in the biotite and gedrite are functions of the NaCl concentrations in the starting fluid. Fluids of the composition H₂O-CO₂-KCl induce cordierite replacement by biotite with corundum and spinel and by these phases in association with potassium feldspar at X _KCl = 0.02 in the fluid. When replaced by these phases, cordierite is excluded from the melting reactions, and the overall melting of the metapelite is controlled by peritectic reactions of biotite and orthopyroxene with plagioclase and quartz. These reactions produce such minerals atypical of metapelites as Ca-Na amphibole and clinopyroxene. The compositions of melts derived in the presence of salt-bearing fluids are shifted toward the region with A/CNK < 1.1, as is typical of so-called peraluminous granites of type I. An increase in the concentrations of salts in the fluids leads to depletion of the melts in Al₂O₃ and CaO and enrichment in alkalis. These relations suggest that the protoliths of I-type peraluminous granites might have been metapelites that were melted when interacting with H₂O-CO₂-salt fluids. The compositions of the melts can evolve from those with A/CNK > 1.1 (typical of S-type granites) toward those with A/CNK = 1.0–1.1 in response to an increase in the concentrations of alkali salts in the fluids within a few mole percent. Our experiments demonstrate that the origin of new mineral assemblages in metapelite in equilibrium with H₂O-CO₂-salt fluids is controlled by the activities of alkaline components, while the H₂O and CO₂ activities play subordinate roles. This conclusion is consistent with the results obtained by simulating metapelite mineral assemblages by Gibbs free energy minimization (using the PERPE_X software), as shown in log(\({a_{{H_2}O}}\))–log(\({a_{N{a_2}O}}\)) and log(\({a_{{H_2}O}}\))–log(\({a_{{K_2}O}}\)) diagrams.     

Comparison of Mo/MgO and Mo/γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalysts: impact of support on the structure and dibenzothiophene hydrodesulfurization reaction pathways

The MgO and P₂O₅-promoted γ-Al₂O₃ supports with alkaline and acidic natures, respectively, were prepared, impregnated with Mo atoms, and compared for dibenzothiophene (DBT) hydrodesulfurization (HDS) reaction. Ultraviolet spectroscopy and the principal component analysis were used to identify the impact of the supports on the reaction pathways. The catalysts were characterized by BET surface analysis, X-ray diffraction, temperature-programmed reduction, Fourier transform infrared, and X-ray photoelectron spectroscopy. The γ-Al₂O₃-supported catalyst favors the hydrogenation pathway relative to the MgO-supported catalyst, which facilitates the direct desulfurization route. The different performance was attributed to the dissimilar Mo phases that emerged during the activation procedure. The activation under sulfo-reductive condition changed the Mo atoms on γ-Al₂O₃ support into the sulfide phase while extra oxidation took place for the MgO-supported catalyst. The migration and consumption of loosely bonded bulk oxygen atoms with under-coordinated Mo atoms on the MgO support were introduced as a possible reason for such extra oxidation. DFT calculations predicted an interaction between the Mo/MgO catalyst and DBT via the electron donation from the catalyst oxygen atoms to the aromatic rings, resulting in weakening and breaking of the C–S bonds. In spite of the higher resistance of the MgO-supported catalyst toward coking and its superior activity, its lower hydrogenation capability suggested using a dual-function catalyst. Accordingly, two catalysts were mixed and the synergism was observed in the HDS reaction of thiophene.     

Reconstruction of palaeohydrological conditions in a lagoon during the 2nd Zechstein cycle through simultaneous use of δD values of individual n-alkanes and δ<Superscript>18</Superscript>O and δ<Superscript>13</Superscript>C values of carbonates

For the first time ¹⁸O and ¹³C values from carbonates and D values of individual n-alkanes were used to reconstruct palaeohydrological conditions in a lagoon at the southern margin of the Central European Zechstein Basin (CEZB). A 12-m core covering the complete Ca2 interval and adjacent anhydrites (A1 and A2) was analyzed for ¹⁸O and ¹³C values of dolomitized carbonates and D values of individual n-alkanes. ¹⁸O_carb values (+2 to +5 vs. VPDB) were strongly influenced by evaporation and temporal freshwater input into the lagoon. The ¹³C_carb values (–1 to +4 vs. VPDB) were controlled mainly by changes in primary production. Both isotopic ratios show an inverse relationship throughout most of the core, contradicting diagenetic alteration, since ¹³C_carb values are not altered significantly during dolomitization. Assuming a temperature range of 35–40 °C in the lagoon, ¹⁸O_carb values of +2.5 to +8 (vs. VSMOW) for the lagoonal water can be reconstructed. The lagoon may have desiccated twice during the Ca2 interval, as indicated by very high ¹⁸O_carb and low ¹³C_carb values, coinciding with increasing amount of anhydrite in the analyzed sample. These events seem to reflect not just local but a regional intra-Ca2 cyclicity. Measured D values of the short-chain n-alkanes, namely n-C₁₆ and n-C₁₈ which are widely used as indicators for photosynthetic bacterial and algal input, reflect the isotopic composition of the lagoonal water. Assuming constant fractionation during incorporation of hydrogen into lipids of –160, an average D value of +70 (vs. VSMOW) can be reconstructed for the lagoonal water, accounting for very arid conditions. The long-chain n-alkanes n-C₂₇, n-C₂₈, n-C₂₉ and n-C₃₀, thought to be derived from the leaf waxes of terrestrial higher plants, were shown to be depleted in D relative to the short-chain alkanes, therefore indicating a different hydrogen source. Terrestrial plants in arid areas mainly use water supplied by precipitation. By using a smaller fractionation of –120 due to evaporation processes in the leaves, reconstructed values vary between –74 and –9 (vs. VSMOW). These values are not indicating extremely arid conditions, implying that the long-chain n-alkanes were transported trough wind and/or rivers into the lagoon at the Zechstein Sea coast. D_water values, reconstructed using the n-C₁₆ alkane and ¹⁸O _water values, independently reconstructed on the same sample using the temperature dependant fractionation for dolomites are good agreement and suggest high amounts of evaporation affecting the coastal lagoon. Altogether, our results indicate that hydrogen isotopic ratios of n-alkanes give information on their origin and are a useful proxy for palaeoclimatic reconstruction.     

Geochemistry of isotopes (δ<Superscript>13</Superscript>C and δ<Superscript>18</Superscript>O) and depositional environment of the upper Kazanian carbonate sediments in the Volga-Vyatka interfluve

This work reports the results of lithological and isotopic study of carbonate rocks from the Pechishchi stratotype section (Kazan) and three adjacent sections of Kazanian rocks of the Volga-Vyatka region at the eastern Russian Platform. These sections were recovered by the Kremeshki, Popovtsevo, and Chimbulat quarries (near the town of Sovetsk, southeastern Kirov district). Lithological features and wide variations of δ¹³C (from −6.0 to 6.8‰) and δ¹⁸ O (from 22.9 to 33.4 ‰) indicate that the rocks were formed in a shallow-marine basin with rapidly varying conditions of sedimentation which characterize different facies (and/or paleoecological) zones: lagoonal, supralittoral, littoral, shoal. They also suggest processes of postsedimentary alteration (mainly, under supergene conditions). Numerous short-term hiatuses are also recorded.     

Isotope (δ<Superscript>13</Superscript>C and δ<Superscript>18</Superscript>O) and genetic features of manganese carbonates of the Mazul deposit (Krasnoyarsk region)

New isotope and mineral data on manganese carbonates of the Mazul deposit (Krasnoyarsk region) in combination with morphology of ore bodies suggest that the ores were formed in several stages with the involvement of meteoric solutions through infiltration and, possibly, exfiltration mechanisms. Based on the geological–geochemical data, manganese carbonates of the Mazul deposit may be ascribed to a new genetic subtype of the catagenesis (epigenesis) zone.     

The solubility of Gd<Subscript>2</Subscript>Ti<Subscript>2</Subscript>O<Subscript>7</Subscript> and the hydrolysis of Gd<Superscript>3+</Superscript> in acidic solutions at 250°C and saturation vapor pressure

The solubility of Gd₂Ti₂O₇ ceramic in acidic solutions (HCl and HClO₄) was studied at 250°C and saturation vapor pressure within pH 2.5–5.2. The dissolution process occurs mainly via two reactions: 0.5 Gd₂Ti₂O_7(cr) + 3H⁺ = Gd³⁺ + TiO_2(cr) + 1.5 H₂O at pH < 3 and 0.5Gd₂Ti₂O₇(cr) + H⁺ + 0.5H₂O = Gd(OH) ₂ ⁺ TiO₂(cr) at pH 3–5. The thermodynamic equilibrium constants were calculated at the 0.95 confidence level as log K ₍₁₎ ^o = 4.12 ± 0.47; = ?0.97 ± 0.16 at 250°C. It was shown that Gd³⁺ undergoes hydrolysis in solutions with pH > 3, and the species Gd(OH) ₂ ⁺ dominates up to at least pH 5. At pH < 3, Gd occurs in solutions as Gd³⁺. The second constant of Gd³⁺ hydrolysis was determined at 250°C as K ^o = ?5.09 ± 0.5, and the thermodynamic characteristics of the initial Gd₂Ti₂O₇ solid phase were determined: S _298.15 ^o = 251.4 J/(mol K) and ΔfG _298.15 ^o = ?3630 ± 10 kJ/mol.     

Determination of geochemical background for environmental studies of soils via the use of HNO<Subscript>3</Subscript> extraction and Q–Q plots

The procedure proposed in this study is based on the extraction of elements in soils by analytical grade HNO₃, the distribution of the elemental data displayed on probability graphs (Q–Q plots) and the visualization of the results spatially by GIS software. The applicability of the procedure is demonstrated in an urban area and its surroundings (Kavala, northern Greece). A major (Ca) and a trace (Ag) element are used as examples in order to demonstrate the applicability of the proposed procedure. Normal probability and lognormal probability plots of Ca and Ag show that their concentrations are lognormally distributed and that their geochemical baseline and anomaly threshold values can be calculated with the aid of their geometric mean and geometric deviation. The advantages of the proposed procedure are simplicity, comprehensiveness, and low cost. It can be applied to environmental geochemical studies of soils in a variety of areas.     

Thermodynamic and magnetic properties of surface Fe<Superscript>3+</Superscript> species on quartz: effects of gamma-ray irradiation and implications for aerosol–radiation interactions

Samples of a natural amethyst, pulverized in air, and irradiated for gamma-ray doses from 0.14 to 70 kGy, have been investigated by powder electron paramagnetic resonance (EPR) spectroscopy from 90 to 294 K. The powder EPR spectra show that the surface Fe³⁺ species on the gamma-ray-irradiated quartz differ from its counterpart without irradiation in both the effective g value and the observed line shape, suggesting marked radiation effects. This suggestion is supported by quantitatively determined thermodynamic properties, magnetic susceptibility, relaxation times, and geometrical radius. In particular, the surface Fe³⁺ species on gamma-ray-irradiated quartz has larger Gibbs and activation energies than its non-irradiated counterpart, suggesting radiation-induced chemical reactions. The shorter phase-memory time (T _m) but longer spin–lattice relaxation time (T ₁) of the surface Fe³⁺ species on the gamma-ray-irradiated quartz than that without irradiation indicate stronger dipolar interactions in the former. Moreover, the calculated geometrical radius of the surface Fe³⁺ species on the gamma-ray-irradiated quartz is three orders of magnitude larger than that of its counterpart on the as-is sample. These results provide new insights into radiation-induced aerosol nucleation, with relevance to atmospheric cloud formation and global climate changes.     

Spatio-temporal variations of δ<Superscript>2</Superscript>H and δ<Superscript>18</Superscript>O in precipitation and shallow groundwater in the Hilly Loess Region of the Loess Plateau,China

Groundwater is of utmost significance to socio-economic development and ecological recovery for the Loess Plateau. However, studies regarding the mechanism governing groundwater recharge over this area appear to be inadequate. This study is to examine the spatio-temporal variations of δ²H and δ¹⁸O in precipitation and shallow groundwater. On the basis of this, the mechanisms governing shallow groundwater recharge were explored. Precipitation and groundwater were sampled monthly from May to October during the period 2004–2006 at 13 sites in the Chabagou Catchment (187 km²). In the Caopingxigou Experimental Watershed (0.1 km²), meteorological variables were observed and rainfall larger than 5 mm was sampled immediately after each rain event. Across the area, 90% of the precipitation occurred from May to September primarily in the form of heavy rains or rainstorms with great spatial variability. There were about 30 localized rains in each year. It was indicated that there existed notable seasonality and pronounced spatial variability in precipitation isotopic compositions. Contributing factors and indications of isotopic compositions, as well as their climatic indications such as monsoon intensities and mixing processes of water vapor, were investigated. The δ²H–δ¹⁸O relation of groundwater was found to be δ²H = 3.22 × δ¹⁸O − 38.1, deviating from the local meteoric water line δ²H = 7.57 × δ¹⁸O + 3.9. The range of δ values in groundwater is shrunken to be 15–21% of that in individual precipitations, and groundwater in the middle reaches shows a wider range of δ values. Isotopic results showed that groundwater originates from precipitation with hydrogen and oxygen isotopic compositions being −69 and −9.7‰, respectively, and most groundwater experiences serious evaporation and adequate mixing with old water during infiltration or percolation in the aerated zone. It was also founded that obvious fluctuations of isotopic compositions in groundwater mainly appear in the middle reaches especially at sites that are close to valleys, suggesting varying sources of groundwater from precipitation, precipitation runoff, isotopically enriched surface water and/or lateral recharge of adjacent groundwater.