Thermodynamics of neptunium(V) fluoride and sulfate at elevated temperatures

Complexation of neptunium(V) with fluoride and sulfate at elevated temperatures was studied by microcalorimetry. Thermodynamic parameters, including the equilibrium constants and enthalpy of protonation of fluoride and sulfate, and the enthalpy of complexation between Np(V) and fluoride and sulfate at 25 - 70 C were determined. Results show that the complexation of Np(V) with fluoride and sulfate is endothermic and that the complexation is enhanced by the increase in temperature - a three-fold increase in the stability constants of NpO{sub 2}F(aq) and NpO{sub 2}SO{sub 4}{sup -} as the temperature is increased from 25 to 70 C

Spectrophotometric and Calorimetric Studies of Np(V) Complexation with Sulfate at 10-70oC

Sulfate, one of the inorganic constituents in the groundwater of nuclear waste repository, could affect the migration of radioactive materials by forming complexes. Spectrophotometric and microcalorimetric titrations were performed to identify the Np(V)/sulfate complex and determine the equilibrium constants and enthalpy of complexation at 10-70 C. Results show that the complexation of Np(V) with sulfate is weak but slightly enhanced by the increase in temperature. The complexation is endothermic and becomes more endothermic with the increase in temperature. The enhanced complexation at elevated temperatures is due to the increasingly larger entropy of complexation that exceeds the increase in enthalpy, suggesting that the complexation of Np(V) with sulfate is entropy-driven

Actinide Thermodynamics at Elevated Temperatures

The postclosure chemical environment in the proposed Yucca Mountain repository is expected to experience elevated temperatures. Predicting migration of actinides is possible if sufficient, reliable thermodynamic data on hydrolysis and complexation are available for these temperatures. Data are scarce and scattered for 25 degrees C, and nonexistent for elevated temperatures. This collaborative project between LBNL and PNNL collects thermodynamic data at elevated temperatures on actinide complexes with inorganic ligands that may be present in Yucca Mountain. The ligands include hydroxide, fluoride, sulfate, phosphate and carbonate. Thermodynamic parameters of complexation, including stability constants, enthalpy, entropy and heat capacity of complexation, are measured with a variety of techniques including solvent extraction, potentiometry, spectrophotometry and calorimetr

Np Behavior in Synthesized Uranyl Phases: Results of Initial Tests

Initial tests were completed at Pacific Northwest National Laboratory for developing a potential mechanism to retard the mobility of neptunium at the Yucca Mountain repository. Neptunium is of concern because of its mobility in the environment and long half life, contributing a large percentage of the potential dose over extended times at the perimeter of the site. The mobility of neptunium could be retarded by associating with uranium mineral phases. The following four uranium mineral phases were examined and are potential secondary phases expected to form as a result of interactions of spent nuclear fuel with the local environment: meta-schoepite, studtite, uranophane, and sodium boltwoodite. The fate of the neptunium was examined in these synthetic experiments

Final Report for DHS FY10 Uranium Methodology Project Analyses of PTRM10 1.1, 1.2, 3.1, and 3.2

This report contains a description of activities performed in support of the FY10 Uranium Methodologies Project at PNNL, as well as the final data from the analyse

Methods to Collect, Compile, and Analyze Observed Short-lived Fission Product Gamma Data

A unique set of fission product gamma spectra was collected at short times (4 minutes to 1 week) on various fissionable materials. Gamma spectra were collected from the neutron-induced fission of uranium, neptunium, and plutonium isotopes at thermal, epithermal, fission spectrum, and 14-MeV neutron energies. This report describes the experimental methods used to produce and collect the gamma data, defines the experimental parameters for each method, and demonstrates the consistency of the measurements

A Discussion of Procedures and Equipment for the Comprehensive Test Ban Treaty On-Site Inspection Environmental Sampling and Analysis

This paper is intended to serve as a scientific basis to start discussions of the available environmental sampling techniques and equipment that have been used in the past that could be considered for use within the context of the Comprehensive Nuclear-Test-Ban Treaty (CTBT) on-site inspections (OSI). This work contains information on the techniques, equipment, costs, and some operational procedures associated with environmental sampling that have actually been used in the past by the United States for the detection of nuclear explosions. This paper also includes a discussion of issues, recommendations, and questions needing further study within the context of the sampling and analysis of aquatic materials, atmospheric gases, atmospheric particulates, vegetation, sediments and soils, fauna, and drill-back materials