Plutonium reactive transport in fractured granite: Multi-species experiments and simulations.

Plutonium (Pu) in the subsurface environment can transport in different oxidation states as an aqueous solute or as colloidal particles. The transport behavior of Pu is affected by the relative abundances of these species and can be difficult to predict when they simultaneously exist. This study investigates the concurrent transport of Pu intrinsic colloids, Pu(IV)(aq) and Pu(V-VI)(aq) through a combination of controlled experiments and semi-analytical dual-porosity transport modeling. Pu transport experiments were conducted in a fractured granite at high and low flow rates to elucidate sorption processes and their scaling behavior. In the experiments, Pu(IV)(aq) was the least mobile of the Pu species, Pu(V-VI)(aq) had intermediate mobility, and the colloidal Pu, which consisted mainly of precipitated and/or hydrolyzed Pu(IV), was the most mobile. The semi-analytical modeling revealed that the sorption of each Pu species was rate-limited, as the sorption could not be described by assuming local equilibrium in the experiments. The model was able to describe the sorption of the different Pu species that occurring either on fracture surfaces, in the pores of the rock matrix, or simultaneously in both locations. While equally good fits to the data could be achieved using any of these assumptions, a fracture-dominated process was considered to be the most plausible because it provided the most reasonable estimates of sorption rate constants. Importantly, a key result of this work is that the sorption rate constant of all Pu species tends to decrease with increasing time scales, which implies that Pu will tend to be more mobile at longer time scales than observations at shorter time scales suggest. This result has important implications for predicting the environmental impacts of Pu in the safety assessments of geologic repositories for radioactive waste disposal, and we explore potential mechanistic bases for upscaling the sorption rate constants to time and distance scales that cannot be practically evaluated in experiments.

Sorption and desorption of Sr onto a rough single fractured granite.

To investigate the migration behavior of Sr (strontium) in granite, a rough-walled single fracture of granite was prepared with the self-built rock splitting apparatus. Surface roughness angle and hydraulic aperture of the fracture were measured by 3D laser scanning and fluid flow experiment, respectively. The sorption and desorption breakthrough experiments of Sr in the single fracture were conducted at different flow rates and initial concentrates of Sr, and the important transport parameters were derived by fitting the BTCs and DPCs. The results suggested that the sorption of Sr onto the fracture surface was a linear and reversible ion-exchange process, unaffected by the variation of flow rate and initial concentrate of Sr.

Note: Observation of a new electronically excited state of cobalt monoxide.

The laser-induced fluorescence excitation spectra of jet-cooled CoO molecules have been recorded in the energy region of 21,800-25,000 cm(-1). Apart from the seven vibronic bands assigned to the known G(4)Φ(9∕2)(υ(')) - X(4)Δ(7∕2)(υ(") = 0) progression [M. Barnes, D. J. Clouthier, P. G. Hajigeorgiou, G. Huang, C. T. Kingston, A. J. Merer, G. F. Metha, J. R. D. Peers, and S. J. Rixon, J. Mol. Spectrosc. 186, 374 (1997)], we observed a new band system assignable to the [22.95](4)Δ(7∕2)(υ(') = 0 - 4) - X(4)Δ(7∕2)(υ(") = 0) progression. Extensive perturbations among these vibronic bands have been revealed by means of reduced energy plots. The new electronically excited (4)Δ state has been determined to be most likely of an electronic configuration (2pπ)(3)(4sσ)(2)(3dδ)(3)(3dπ)(3) based on the charge-transferred promotion model.

Multiphoton dissociative ionization of tert-pentyl bromide near 265 nm.

We report on the photodissociation dynamics of tert-pentyl bromide near 265 nm investigated by time-sliced velocity map imaging. The speed and angular distributions have been analyzed for both the ground-state Br((2)P(3∕2)) atom (denoted Br) and the spin-orbit excited-state Br((2)P(1∕2)) atom (denoted Br*). The speed distributions of Br and Br* atoms are all found to consist of three Gaussian components, which correlate to three independent dissociation pathways on the excited potential energy surfaces: (1) the high translational energy (E(T)) component from the prompt dissociation along the C-Br stretching mode, (2) the middle E(T) component from the repulsive mode along the C-Br stretching coupled with some bending motions, and (3) the low E(T) component from the repulsive mode along the C-Br stretching coupled with more bending motions. More interestingly, we have also observed the tert-C(5)H(11)(+) ions in 263-267 nm. The near-zero kinetic energy distributions extracted from the three tert-C(5)H(11)(+) images near 265 nm show the typical characteristics that are attributable to multiphoton dissociative ionization, suggesting the existence of a neutral superexcited state of the parent tert-pentyl bromide molecule. The contribution of bromine atoms formed in this dissociative ionization channel adds in the total relative distribution of low E(T) component in the Br*(Br) formation channel, which reasonably explains the abnormal distributions observed in between the middle and low E(T) components in the Br*(Br) formation channel.