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Mechanisms and Kinetics of Organic Aging in High-Level Nuclear Waste (PNNL Scope #29531)

EMSL Project ID


Examine the aging of organic chemicals in high-level nuclear wastes stored in tanks at Hanford and develop a mechanistic model describing the reactions and kinetics.

The part of the work involving EMSL is the research on Thermochemical Property Measurements of Hydrogen Peroxide and the Hydroxyl Radical in
Aqueous Solution:

Photo-induced decomposition of hydrogen peroxide leads to the prompt formation of reactive hydroxyl radicals. The
photoacoustic signal generated by pulsed irradiation of an aqueous hydrogen peroxide solution is proportional to the
combined photo-induced volume changes from both the enthalpy and the molecular transformation of the
dissociation reaction. The magnitude of the photoacoustic signal arising from enthalpy of the reaction is due to local
heating of the solution and is dependent on the thermoelastic properties of the solution. One the other hand, the
magnitude of the photoacoustic signal arising from the molecular volume change is independent of the thermoelastic
properties of the solution since no heat is evolved in molecular transformations. Because the thermoelastic
properties of aqueous solutions change substantially over a narrow temperature range variable temperature
photoacoustic calorimetry provides an experimental approach to measure these two thermodynamic properties
simultaneously. This presentation will demonstrate how the thermochemical properties of a short-lived transient
hydroxyl radical can be measured by a variation of the thermoelastic properties of an aqueous solution as a function
of temperature.

Project Details

Project type
Exploratory Research
Start Date
End Date


Principal Investigator

Thomas Autrey
Pacific Northwest National Laboratory

Team Members

Donald Camaioni
Pacific Northwest National Laboratory

Related Publications

Autrey T, AK Brown, DM Camaioni, M Dupuis, NS Foster, and AD Getty. 2004. "Thermochemistry of Aqueous Hydroxyl Radical from Advances in Photoacoustic Calorimetry and ab Initio Continum Solvation Theory." Journal of the American Chemical Society 126(12):3680-3681.
Beck KM, AG Joly, O Diwald, S Stankic, PE Trevisanutto, PV Sushko, AL Shluger, and WP Hess. 2008. "Energy and Site Selectivity in O-Atom Photodesorption from Nanostructured MgO." Surface Science 602(11):1968-1973. doi:10.1016/j.susc.2008.03.046
Beck KM, M Henyk, CM Wang, PE Trevisanutto, P Sushko, WP Hess, and AL Shluger. 2006. "Site-Specific Laser Modification of MgO nanoclusters: Towards Atomic-Scale Surface Structuring." Physical Review. B, Condensed Matter 74:045404 (5 pages).
Joly AG, KM Beck, and WP Hess. 2008. "Electronic Energy Transfer on CaO Surfaces." Journal of Chemical Physics 129(12):124704. doi:10.1063/1.2980049
Joly AG, M Henyk, KM Beck, PE Trevisanutto, PV Sushko, WP Hess, and AL Shluger.  2006.  "Probing Electron Transfer Dynamics at MgO Surfaces by Mg-Atom Desorption."  Journal of Physical Chemistry B 110(37):18093-18096.  doi:10.1021/jp064092b
Knopf DA, PA Alpert, B Wang, RE O'Brien, ST Kelly, A Laskin, MK Gilles, and RC Moffet. 2014. "Micro-Spectroscopic Imaging and Characterization of Individually Identified Ice Nucleating Particles from a Case Field Study." Journal of Geophysical Research. D. (Atmospheres).
O'Brien RE, A Laskin, J Laskin, CL Rubitschun, JD Surratt, and AH Goldstein. 2014. "Molecular characterization of S- and N-containing organic constituents in ambient aerosols by negative ion mode high-resolution Nanospray Desorption Electrospray Ionization Mass Spectrometry: CalNex 2010 field study." Journal of Geophysical Research-Atmospheres 119:12706-12720. doi:10.1002/2014jd021955
O'Brien RE, A Neu, SA Epstein, A MacMillan, B Wang, ST Kelly, S Nizkorodov, A Laskin, RC Moffet, and MK Gilles. 2014. "Phase State and Physical Properties of Ambient and Laboratory Generated Secondary Organic Aerosol ." Geophysical Research Letters [epub ahead of print]:, doi:10.1002/2014GL060219
Trevisanutto PE, PV Sushko, KM Beck, AG Joly, WP Hess, and AL Shluger. 2009. "Excitation, Ionization, and Desorption: How Sub-band-gap Photons Modify the Structure of Oxide Nanoparticles." Journal of Physical Chemistry C 113(4):1274-1279.