Current developments in laser ablation-inductively coupled plasma-mass spectrometry for use in geology, forensics, and nuclear nonproliferation research

This dissertation focused on new applications of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The diverse fields that were investigated show the versatility of the technique. In Chapter 2, LA-ICP-MS was used to investigate the rare earth element (REE) profiles of garnets from the Broken Hill Deposit in New South Wales, Australia. The normalized REE profiles helped to shed new light on the formation of deposits of sulfide ores. This information may be helpful in identifying the location of sulfide ore deposits in other locations. New sources of metals such as Pg, Zn, and Ag, produced from these ores, are needed to sustain our current technological society. The application of LA-ICP-MS presented in Chapter 3 is the forensics analysis of automotive putty and caulking. The elemental analysis of these materials was combined with the use of Principal Components Analysis (PCA). The PCA comparison was able to differentiate the automotive putty samples by manufacturer and lot number. The analysis of caulk was able to show a differentiation based on manufacturer, but no clear differentiation was shown by lot number. This differentiation may allow matching of evidence in the future. This will require many more analyses and the construction of a database made up of many different samples. The 4th chapter was a study of the capabilities of LA-ICP-MS for fast and precise analysis of particle ensembles for nuclear nonproliferation applications. Laser ablation has the ability to spatially resolve particle ensembles which may contain uranium or other actinides from other particles present in a sample. This is of importance in samples obtained from air on filter media. The particle ensembles of interest may be mixed in amongst dust and other particulates. A problem arises when ablating these particle ensembles directly from the filter media. Dust particles other than ones of interest may be accidentally entrained in the aerosol of the ablated particle ensemble. This would cause the analysis to be skewed. The use of a gelatin substrate allows the ablation a particle ensemble without disturbing other particles or the gelatin surface. A method to trap and ablate particles on filter paper using collodion was also investigated. The laser was used to dig through the collodion layer and into the particle ensemble. Both of these methods fix particles to allow spatial resolution of the particle ensembles. The use of vanillic acid as a possible enhancement to ablation was also studied. A vanillic acid coating of the particles fixed on top of the gelatin substrate was not found to have any positive effect on either signal intensity or precision. The mixing of vanillic acid in the collodion solution used to coat the filter paper increased ablation signal intensity by a factor of 4 to 5. There was little effect on precision, though. The collodion on filter paper method and the gelatin method of resolving particles have shown themselves to be possible tools in fighting proliferation of nuclear weapons and material. Future applications of LA-ICP-MS are only limited by the imagination of the investigator. Any material that can be ablated and aerosolized is a potential material for analysis by LA-ICP-MS. Improvements in aerosol transport, ablation chamber design, and laser focusing can make possible the ablation and analysis of very small amounts of material. This may perhaps lead to more possible uses in forensics. A similar method to the one used in Chapter 3 could perhaps be used to match drug residue to the place of origin. Perhaps a link could be made based on the elements leached from the soil by plants used to make drugs. This may have a specific pattern based on where the plant was grown. Synthetic drugs are produced in clandestine laboratories that are often times very dirty. The dust, debris, and unique materials in the lab environment could create enough variance to perhaps match drugs produced there to samples obtained off the street. Even if the match was not strong enough to be evidence, the knowledge that many samples of a drug are being produced from a similar location could help law enforcement find and shut down the lab. Future nuclear nonproliferation research would also be helped by the ability to get more analyte signal from smaller and smaller amounts of material. One possible future line of research would be to find a way to make the collodion layer as thin as possible so less laser shots are needed to get to the particle of interest. Collodion and gelatin analysis could also be used for environmental applications where spatial resolution of particles is needed. Individual particles could give information about the contaminants present in a given location. The wide versatility of LA-ICP-MS makes it a useful tool for nearly nondestructive analysis of a variety of samples and matrices