Reevaluation of Neptunium-Nitric Acid Radiation Chemistry by Multiscale Modeling.

Multiscale modeling has been used to quantitatively reevaluate the radiation chemistry of neptunium in a range of aerated nitric acid solutions (0.1-6.0 mol dm-3). Exact calculation of initial radiolytic yields accounting for changes in radiation track chemistry was found to be crucial for reproducing experimental data. The γ irradiation induces changes in the Np(VI)/Np(V) oxidation-state distribution, predominantly driven by reactions involving HNO2, H2O2, NO2•, and NO3• from the radiolysis of aqueous nitric acid. Oxidation of Np(V) by NO3• (k = 8.1 × 108 dm3 mol-1 s-1) provides the initial increase in Np(VI) concentration, while also delaying net reduction of Np(VI) by consuming HNO2. Reduction of Np(VI) is dominated by thermal reactions with HNO2 (k = 0.7-73 dm3 mol-1 s-1) and H2O2 (k = 1.9 dm3 mol-1 s-1). A steady state is eventually established once the concentration of Np(V) is sufficiently high to be oxidized by NO2• (k = 2.4 × 102-3.1 × 104 dm3 mol-1 s-1). An additional thermal oxidation reaction between Np(V) and HNO3 (k = 2.0 × 103 dm3 mol-1 s-1) is required for nitric acid concentrations >4.0 mol dm-3. For 0.1 mol dm-3 HNO3, the rate of Np(VI) reduction is in excess of that which can be accounted for by radiolytic product mass balance, suggesting the existence of a catalytic-acid-dependent reduction process.

Isotope Dependence and Quantum Effects on Atomic Hydrogen Diffusion in Liquid Water.

Relative diffusion coefficients were determined in water for the D, H, and Mu isotopes of atomic hydrogen by measuring their diffusion-limited spin-exchange rate constants with Ni(2+) as a function of temperature. H and D atoms were generated by pulse radiolysis of water and measured by time-resolved pulsed EPR. Mu atoms are detected by muonium spin resonance. To isolate the atomic mass effect from solvent isotope effect, we measured all three spin-exchange rates in 90% D2O. The diffusion depends on the atomic mass, demonstrating breakdown of Stokes-Einstein behavior. The diffusion can be understood using a combination of water "cavity diffusion" and "hopping" mechanisms, as has been proposed in the literature. The H/D isotope effect agrees with previous modeling using ring polymer molecular dynamics. The "quantum swelling" effect on muonium due to its larger de Broglie wavelength does not seem to slow its "hopping" diffusion as much as predicted in previous work. Quantum effects of both the atom mass and the water librations have been modeled using RPMD and a qTIP4P/f quantized flexible water model. These results suggest that the muonium diffusion is very sensitive to the Mu versus water potential used.

Characterization of CMPO and its radiolysis products by direct infusion ESI-MS.

Direct infusion electrospray ionization mass spectrometry (ESI-MS) approaches were developed for rapid identification of impurity compounds formed from octylphenyl-(N,N-(diisobutyl)carbamoylmethyl) phosphine oxide (CMPO) during alpha and gamma irradiation experiments of this compound in dodecane. CMPO is an aggressive Lewis base, and produces extremely abundant metal complex ions in the ESI-MS analysis that make identification of low abundance compounds that are less nucleophilic challenging. Radiolysis products were identified using several approaches including restricting ion trapping so as to exclude the abundant natiated CMPO ions, extraction of acidic products using aqueous NaOH, and extraction of basic products using HNO(3). These approaches generated protonated, natiated and deprotonated species derived from CMPO degradation products formed via radiolytic cleavages of several different bonds. Cleavages of the amide and methylene-phosphoryl bonds appear to be favored by both alpha and gamma irradiation, while alpha irradiation also appears to induce cleavage of the methylene-carbonyl bond. The degradation products observed are formed from recombination of the initially formed radicals with hydrogen, methyl, isopropyl and hydroxyl radicals that are derived either from CMPO, contacted aqueous nitric acid, or the dodecane solvent.

Determination of the rate constant for the reaction of hydroxyl and oxide radicals with cysteine in aqueous solution.

The techniques of pulse radiolysis and absorption spectroscopy have been used to determine absolute rate constants for the reaction of hydroxyl and oxide radicals with cysteine (CysS) species in aqueous solution. Using measured equilibrium constants for radical disulfide anion formation, over the pH range 6.0-13.0, observed reaction rate constants were resolved into their constituent reactions .OH + CysSH-->H2O + CysS. and .O(-) + CysS-( + H2O)-->CysS. + 2OH- with calculated limiting rate constants of (5.35 +/- 0.82) x 10(9) and (3.28 +/- 0.49) x 10(8) dm3 mol-1 s-1, respectively. The rate constant for hydroxyl radical reaction with CysS- was found to be the same as that for CysSH.