Heat capacity,entropy, and phase equilibria of dmitryivanovite

The heat capacity (C _p ) of dmitryivanovite synthesized with a cubic press was measured in the temperature range of 5–664 K using the heat capacity option of a physical properties measurement system and a differential scanning calorimeter. The entropy of dmitryivanovite at standard temperature and pressure (STP) was calculated to be 110.1 ± 1.6 J mol⁻¹ K⁻¹ from the measured C _p data. With the help of new phase equilibrium experiments done at 1.5 GPa, the phase transition boundary between krotite and dmitryivanovite was best represented by the equation: P (GPa) = −2.1825 + 0.0025 T (K). From the temperature intercept of this phase boundary and other available thermodynamic data for krotite and dmitryivanovite, the enthalpy of formation and Gibbs free energy of formation of dmitryivanovite at STP were calculated to be −2326.7 ± 2.1 and −2,208.1 ± 2.1 kJ mol⁻¹, respectively. It is also inferred that dmitryivanovite is the stable CaAl₂O₄ phase at STP and has a wide stability field at high pressures whereas the stability field of krotite is located at high temperatures and relatively low pressures. This conclusion is consistent with natural occurrences (in Ca–Al-rich inclusions) of dmitryivanovite and krotite, where the former is interpreted as the shock metamorphic product of originally present krotite.     

Heat capacity,entropy and phase equilibria of stishovite

The low-temperature heat capacity (C _P) of stishovite (SiO₂) synthesized with a multi-anvil device was measured over the range of 5–303 K using the heat capacity option of a physical properties measurement system (PPMS) and around ambient temperature using a differential scanning calorimeter (DSC). The entropy of stishovite at standard temperature and pressure calculated from DSC-corrected PPMS data is 24.94 J mol⁻¹ K⁻¹, which is considerably smaller (by 2.86 J mol⁻¹ K⁻¹) than that determined from adiabatic calorimetry (Holm et al. in Geochimica et Cosmochimica Acta 31:2289–2307, 1967) and about 4% larger than the recently reported value (Akaogi et al. in Am Mineral 96:1325–1330, 2011). The coesite–stishovite phase transition boundary calculated using the newly determined entropy value of stishovite agrees reasonably well with the previous experimental results by Zhang et al. (Phys Chem Miner 23:1–10, 1996). The calculated phase boundary of kyanite decomposition reaction is most comparable with the experimental study by Irifune et al. (Earth Planet Sci Lett 77:245–256, 1995) at low temperatures around 1,400 K, and the calculated slope in this temperature range is mostly consistent with that determined by in situ X-ray diffraction experiments (Ono et al. in Am Mineral 92:1624–1629, 2007).     

On some aspects of peaks-over-threshold modeling of floods under nonstationarity using climate covariates

This paper discusses some aspects of flood frequency analysis using the peaks-over-threshold model with Poisson arrivals and generalized Pareto (GP) distributed peak magnitudes under nonstationarity, using climate covariates. The discussion topics were motivated by a case study on the influence of El Niño–Southern Oscillation on the flood regime in the Itajaí river basin, in Southern Brazil. The Niño3.4 (DJF) index is used as a covariate in nonstationary estimates of the Poisson and GP distributions scale parameters. Prior to the positing of parametric dependence functions, a preliminary data-driven analysis was carried out using nonparametric regression models to estimate the dependence of the parameters on the covariate. Model fits were evaluated using asymptotic likelihood ratio tests, AIC, and Q–Q plots. Results show statistically significant and complex dependence relationships with the covariate on both nonstationary parameters. The nonstationary flood hazard measure design life level (DLL) was used to compare the relative performances of stationary and nonstationary models in quantifying flood hazard over the period of records. Uncertainty analyses were carried out in every step of the application using the delta method.     

U–Pb zircon and 40Ar–39Ar K-feldspar dating of syn-sedimentary volcanism of the Neoproterozoic Maricá Formation: constraining the age of foreland basin inception and inversion in the Camaquã Basin of southern Brazil

New U–Pb zircon and ⁴⁰Ar–³⁹Ar K-feldspar data are presented for syn-sedimentary volcanogenic rocks from the Neoproterozoic Maricá Formation, located in the southern Brazilian shield. Seven (of nine) U–Pb sensitive high-resolution ion microprobe analyses of zircons from pyroclastic cobbles yield an age of 630.2±3.4 Ma (2σ), interpreted as the age of syn-sedimentary volcanism, and thus of the deposition itself. This result indicates that the Maricá Formation was deposited during the main collisional phase (640–620 Ma) of the Brasiliano II orogenic system, probably as a forebulge or back-bulge, craton-derived foreland succession. Thus, this unit is possibly correlative of younger portions of the Porongos, Brusque, Passo Feio, Abapã (Itaiacoca) and Lavalleja (Fuente del Puma) metamorphic complexes. Well-defined, step-heating ⁴⁰Ar–³⁹Ar K-feldspar plateau ages obtained from volcanogenic beds and pyroclastic cobbles of the lower and upper successions of the Maricá Formation yielded 507.3±1.8 Ma and 506.7±1.4 Ma (2σ), respectively. These data are interpreted to reflect total isotopic resetting during deep burial and thermal effects related to magmatic events. Late Middle Cambrian cooling below ca . 200 °C, probably related to uplift, is tentatively associated with intraplate effects of the Rio Doce and/or Pampean orogenies (Brasiliano III system). In the southern Brazilian shield, these intraplate stresses are possibly related to the dominantly extensional opening of a rift or a pull-apart basin, where sedimentary rocks of the Camaquã Group (Santa Bárbara and Guaritas Formations) accumulated.     

Zur geomorphologischen und geologischen Entwicklungsgeschichte der Ostabdachung der Zentralalpen in der Miozänzeit

Ohne Zusammenfassung     

Der Unmittelbare Nachweis des Vindelizischen Rückens unter der Süddeutschen Molasse

Ohne Zusammenfassung     

Comparison of the quantitative determination of soil organic carbon in coastal wetlands containing reduced forms of Fe and S

The performance of the Walkley–Black wet oxidation chemical method for soil organic carbon (SOC) determination in coastal wetland soils (mangroves, coastal lagoons, and hypersaline tidal flats) was evaluated in the state of Ceará along the semiarid coast of Brazil, assessing pyrite oxidation and its effects on soil C stock (SCS) quantification. SOC determined by the chemical oxidation method (C_WB) was compared to that assessed by means of a standard elemental analyzer (C_EA) for surficial samples (<30 cm depth) from the three wetland settings. The pyrite fraction was quantified in various steps of the chemical oxidation method, evaluating the effects of pyrite oxidation. Regardless of the method used, and consistent with site-specific physicochemical conditions, higher pyrite and SOC contents were recorded in the mangroves, whereas lower values were found in the other settings. C_WB values were higher than C_EA values. Significant differences in SCS calculations based on C_WB and C_EA were recorded for the coastal lagoons and hypersaline tidal flats. Nevertheless, the C_WB and C_EA values were strongly correlated, indicating that the wet oxidation chemical method can be used in such settings. In contrast, the absence of correlation for the mangroves provides evidence of the inadequacy of this method for these soils. Air drying and oxidation decrease the pyrite content, with larger effects rooted in oxidation. Thus, the wet oxidation chemical method is not recommended for mangrove soils, but seems appropriate for SOC/SCS quantification in hypersaline tidal flat and coastal lagoon soils characterized by lower pyrite contents.     

Stable sulfur and oxygen isotope ratios of the Świętokrzyski National Park spring waters generated by natural and anthropogenic factors (south-central Poland)

This paper presents the results of an isotopic study of spring waters in ?wi?tokrzyski (Holy Cross Mountain) National Park (?NP), south-central Poland. The δ³⁴S_V-CDT and δ¹⁸O_V-SMOW of soluble sulfates (n = 40) varied from 0.5‰ to 18.1‰ and from 3.5‰ to 12.2‰, respectively. The average δ³⁴S values are closely similar to those of rainwater, soils and rocks (comprising scattered pyrite). This suggests that soluble sulfates in the springs originated from mixing of recent and historic deposition, sulfates derived from pyrite oxidation, and CS-mineralization in soils and debris. An additional anthropogenic sulfur input (inorganic fertilizer) occurs in the water of spring S-61 located in the ?wi?tokrzyski National Park buffer zone. The δ¹⁸O_V-SMOW of spring waters (n = 4) were in the range of −10.6‰ to −10.2‰ indicating that they are derived from vadose groundwater in ?NP. This was the first isotope study of spring waters in the national parks of Poland. It enabled the determination of sulfur pathways and discrimination between natural and anthropogenic sources of this element in a relatively pristine area.     

Adsorption of Sr and Ba at the cleaved mica-water interface: Free energy profiles and interfacial structure

Monte Carlo simulations show that the adsorption position of the Sr²⁺ or Ba²⁺ ion on the cleaved muscovite surface is determined by the radius of the ion’s first hydration shell, hydrogen bonding of the first shell water molecules with the basal oxygens of muscovite as well as a requirement of minimization of the number of muscovite’s lattice cations in the ion’s first coordination shell. Accordingly, Sr²⁺ or Ba²⁺ adsorbs in ditrigonal cavities at a distance of 1.12 Å or 1.35 Å, respectively, from the basal surface on dehydrated mica and above tetrahedral substitutions at a height of 1.93 ± 0.02 Å or 2.15 ± 0.03 Å, respectively, at the highest simulated water coverage of 28 H₂O per ion. The ion’s displacement from a ditrigonal cavity occurs upon adsorption of 2 H₂O per ion for Sr²⁺ and 3 H₂O per ion for Ba²⁺. At a coverage of 28 H₂O per ion, outer-sphere adsorption of Sr²⁺ or Ba²⁺ at a height of 3.9 ± 0.2 Å or 4.17 ± 0.07 Å, respectively, is possible albeit unfavorable on the free energy scale by 107 ± 7 kJ/mol or 89 ± 13 kJ/mol, respectively, as compared to inner-sphere adsorption. Activation energies for the transformation between inner-sphere and outer-sphere adsorptions are calculated to be 121 ± 3 kJ/mol for Sr²⁺ and 99 ± 10 kJ/mol for Ba²⁺. A comparison of these values with those reported recently for Mg²⁺ and Ca²⁺ results in an adsorption affinity sequence Mg²⁺ > Ca²⁺ > Sr²⁺ > Ba²⁺ in agreement with the sequence predicted recently for low dielectric constant solids (which include mica) (Sverjensky, 2006). A recent resonant anomalous X-ray reflectivity study of Sr²⁺ adsorption on muscovite (Park et al., 2006) has questioned the common assumption (Stumm, 1992), which is supported by the present simulation results, that inner-sphere adsorption is stronger than outer-sphere adsorption. A modification of the cleaved muscovite surface as a result of Sr²⁺ adsorption in muscovite’s ditrigonal cavities and related destabilization of muscovite’s hydroxyl groups is proposed as a possible reason for this controversy.