ETD RECORD
Chemical warfare blister agent detection and uranium characterization via tandem mass spectrometry
Citation
Gresham, Garold Linn.. (2006). Chemical warfare blister agent detection and uranium characterization via tandem mass spectrometry. Theses and Dissertations Collection, University of Idaho Library Digital Collections. https://www.lib.uidaho.edu/digital/etd/items/etd_6.html
- Title:
- Chemical warfare blister agent detection and uranium characterization via tandem mass spectrometry
- Author:
- Gresham, Garold Linn.
- Date:
- 2006
- Keywords:
- Chemical agents (Munitions)--Analysis Chemical agents (Munitions)--Measurement Blister agents--Analysis Blister agents--Measurement
- Abstract:
- Tandem ion trap mass spectrometry (IT-MS) provided a robust analytical approach for the investigation of surface analytes and host-guest complexes. Polyatomic primary ion sources utilized in static IT secondary ion mass spectrometry (SIMS) provided significantly improved molecular secondary ion yields of analytically significant ions, allowing for the investigation of the top-most surface monolayers of solid materials. Static IT-SIMS has been applied to the detection and characterization of sulfur- (HD) and nitrogen- (HN) based mustards on environmental solid surfaces, as well as actinide metals from solid materials. Utilizing IT-SIMS, gas-phase uranium reactant ions sputtered from the surface of UO3 were isolated and reacted with gaseous water inherent in the IT to investigate uranyl hydration chemistry. ESI provided an alternative method of investigation of metal-ligand chemistries, and used in conjunction with tandem IT-MS, has provided a method for the intrinsic chemistry of gas-phase metal ion complexes to be easily probed in an ion selective manner.;Results of the vesicant research demonstrate that the nitrogen mustards (HN-2 and HN-3) and their exhaustive hydrolysis products, as well as adsorbed sulfur mustard (HD), can be easily characterized on soil surfaces using static IT-SIMS. The results emphasized the need for an analytical methodology capable of detecting a range of degradation and condensation products on environmental surfaces. The ability of the IT to isolate and accumulate ions, and then perform tandem MS analysis improves the limits of detection of low-abundance surface contaminants and the specificity of the analytical technique. The limits of detection for the blister agents and their degradation products was found to be in the sub-monolayer level (0.001 to 0.07), corresponding to the low ppm level (0.9 to 100 ppm mass/mass).;The first examination of the intrinsic hydration reactivity of U(IV), U(V), and U(VI) dioxo monocations was investigated using IT-SIMS and revealed the kinetics for the formation of the inner hydration sphere. Control of the time between ion generation and detection in the IT enabled reaction pathways and kinetics to be deduced. All three monocation species investigated, ([UO(OH)] +, [UO2]+ and [UO2(OH)] +), formed H2O adducts by termolecular association reactions, where the gas-phase uranium species added 3 to 4 water molecules. The research showed that the optimum extent of ligation increased with increasing oxidation state of the uranium metal. Kinetic models showed that in general, formation of the monohydrates was slow, but that hydration efficiency increased upon addition of the second H2O, with reduced hydration efficiency for the third and fourth H2O molecule. Reverse rate constants also typically decreased with increasing ligation by H2O. (Abstract shortened by UMI.).
- Description:
- Thesis (Ph. D.)--University of Idaho, May 2006.
- Major Professor:
- Peter R. Griffiths
- Defense Date:
- May 2006.
- Type:
- Text
- Format Original:
- xiv, 147 leaves :ome col.) ;29 cm.
- Format:
- record
Rights
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- In Copyright - Educational Use Permitted. For more information, please contact University of Idaho Library Special Collections and Archives Department at libspec@uidaho.edu.
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