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Linfeng Rao Thandankorai G. Srinivasan PierLuigi Zanonato Arturo Bismondo 《Geochimica et cosmochimica acta》2004,68(23):4821-4830
Neptunium is one of the few radioactive elements that are of great concern in the disposal of nuclear wastes in the geological repository, due to its hazards and the long half-life of the isotope, 237Np (t1/2 = 2.14 × 106 years). To understand and predict the migration behavior of neptunium in the geological media, it is of importance to study its hydrolysis at elevated temperatures, because the temperature in the waste package and the vicinity of the repository could be high. Moreover, the chemical analogy between neptunium(V) and plutonium(V) adds even greater value to this investigation, because the latter could exist at tracer levels in neutral and slightly oxidizing waters but is difficult to study due to its rather labile redox behavior.In this work, the hydrolysis of neptunium(V) was studied at variable temperatures (10 to 85°C) in tetramethylammonium chloride (1.12 mol kg−1). Two hydrolyzed species of neptunium(V), NpO2OH(aq) and NpO2(OH)2−, were identified by potentiometry and Near-IR absorption spectroscopy. The hydrolysis constants (*βn) and enthalpy of hydrolysis (ΔHn) for the reaction NpO2+ + nH2O = NpO2(OH)n(1−n)+ + nH+ (n = 1 and 2) were determined by titration potentiometry and microcalorimetry. The hydrolysis constants, *β1 and *β2, increased by 0.8 and 3.4 orders of magnitude, respectively, as the temperature was increased from 10 to 85°C. The enhancement of hydrolysis at elevated temperatures is mainly due to the significant increase of the degree of ionization of water as the temperature is increased. The hydrolysis reactions are endothermic but become less endothermic as the temperature is increased. The heat capacities of hydrolysis, ΔCp1 and ΔCp2, are calculated to be −(71 ± 17) J K−1 mol−1 and −(127 ± 17) J K−1 mol−1, respectively. Approximation approaches to predict the effect of temperature, including the constant enthalpy approach, the constant heat capacity approach and the DQUANT equation, have been tested with the data. 相似文献
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Werner Smykatz-Kloss 《Chemie der Erde / Geochemistry》2007,67(2):175-176
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V. Neck 《Geochimica et cosmochimica acta》2006,70(17):4551-4555
In a recent study [Rao, L., Srinivasan, T.G., Garnov, A.Yu., Zanonato, P., Di Bernardo, P., Bismondo, A., 2004. Hydrolysis of neptunium(V) at variable temperatures (10-85 °C). Geochim. Cosmochim. Acta68, 4821-4830.] the hydrolysis of Np(V) was investigated at 10-85 °C by absorption spectroscopy, potentiometry, and microcalorimetry along the titration of Np(V) solutions with tetramethylammonium hydroxide up to pH 10. However, there is strong evidence that the precautions to avoid competing reactions with carbonate were not sufficient and that the measured effects are not caused by the formation of Np(V) hydroxide complexes but primarily by the formation of Np(V) carbonate complexes. The reported equilibrium constants, enthalpies, entropies, and heat capacities for the complexes NpO2OH(aq) and are severely in error and must not be used for the geochemical modeling of neptunium. If the hydrolysis constants reported by Rao et al. [Rao, L., Srinivasan, T.G., Garnov, A.Yu., Zanonato, P., Di Bernardo, P., Bismondo, A., 2004. Hydrolysis of neptunium(V) at variable temperatures (10-85 °C). Geochim. Cosmochim. Acta68, 4821-4830] are used to calculate neptunium solubilities in alkaline solutions relevant for nuclear waste repositories, the Np(V) concentrations are overestimated by orders of magnitude. 相似文献
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A thermodynamic model for the Gibbs free energy of igneous pyroxenes with the general formula [Na, Ca, Fe2+, Mg]M2[Fe2+, Mg, Ti, Al, Fe3+]M1[Al, Fe3+, Si]TetSiO6 is calibrated from experimentally determined compositions of coexisting pyroxene and silicate melt. The model is based upon the general formulation, and relies upon the calibration of the “quadrilateral” subsystem, previously published by the present authors. The calibration database of pyroxene-liquid equilibria spans a broad spectrum of temperature, pressure and oxygen fugacity conditions, ranging from 1000°–1600°C, 0.001–30 kbar and iron-wüstite to air. Chemical potentials of endmember pyroxene components as well as exchange potentials between pyroxenes and coexisting liquids are defined utilizing the present authors' thermodynamic melt model. Model parameters are extracted from these relations by regression analysis. The resulting model and derivative endmember properties are internally consistent with an existing standard state thermodynamic database. The success of the model and its applicability to igneous petrogenesis are demonstrated by comparing calculated and experimentally determined liquidus compositions, temperatures and symmetry states for pyroxenes crystallizing from a variety of silicate melts, ranging in composition from tholeiites and angrites through rhyolites to potash ankaratrites. 相似文献
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Celia Martín-Puertas Blas L. Valero-Garcés M. Pilar Mata Peter Dulski 《Quaternary Research》2009,71(2):108-120
The Iberian-Roman Humid Period (IRHP, 2600-1600 cal yr BP), is the most humid phase of the last 4000 yr in southern Spain as recorded in the sedimentary sequence of Zoñar Lake (37°29′00″N, 4°41′22″ W, 300 m a.s.l.). A varve chronology supported by several AMS 14C dates allows study of the lake evolution at annual scale in response to human impact and climate changes. There are four climate phases within this period: i) gradual transition (2600-2500 yr ago, 650-550 BC) from a previous arid period; ii) the most humid interval during the Iberian-Early Roman Epoch (2500-2140 yr ago, 550-190 BC); iii) an arid interval during the Roman Empire Epoch (2140-1800 yr ago, 190 BC AD 150); and iv) a humid period synchronous with the decline of the Roman Empire (1800-1600 yr ago, AD 150-350). Varve thickness and geochemical proxies show a multi-decadal cyclicity similar to modern North Atlantic Oscillation (NAO) (60, 20 years) and solar variability cycles (11 yr). The timing and the structure of this humid period is similar to that described in Eastern Mediterranean and northern European sites and supports the same large-scale climate control for northern latitudes and the Mediterranean region. 相似文献
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