Search

Online-laser ablation of solids in liquid (online-LASIL) coupled with ICP-MS detection was used as a new sampling strategy for the analysis of complex metal oxide (CMO) thin films. The in-house built and optimized online-LASIL ablation cell provides the unique possibility to correlate the signal intensities with the spatial origin of the signal at the sample. For that purpose a particle transport with as little particle dispersion as possible is crucial. To demonstrate the 2D imaging capability of this technique, geometrically structured samples with varying composition were prepared by pulsed laser deposition (PLD) and ion beam etching procedures. These thin films with a thickness of 220 nm were spatially resolved analysed. As a result, 2D intensity maps obtained by online-LASIL can be reported for the first time. Additionally a new approach for simultaneous online quantification was developed by adopting the standard addition concept allowing to correct for instrumental drifts of long time measurements.

Rare earth elements (REE) concentrated on cation-exchange resin particles were measured with laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) to obtain chondrite-normalized REE plots. The sensitivity of REE increased in ascending order of the atomic number, according to the sensitivity trend in pneumatic nebulization ICP-MS (PN-ICP-MS). The signal intensities of REE were nearly proportional to the concentrations of REE in the immersion solution used for particle-preparation. Minimum measurable concentration calculated from the net signals of REE was approximately 1 ng/g corresponding to 0.1 ng in the particle-preparation solution. In LA analysis, formation of oxide and hydroxide of the light REE and Ba which causes spectral interferences in the heavy REE measurement was effectively attenuated due to the solvent-free measurement capability, compared to conventional PN-ICP-MS. To evaluate the applicability of the proposed method, the REE-adsorbed particles prepared by immersing them in a U-bearing solution (commercially available U standard solution) were measured with LA-ICP-MS. Aside from the LA analysis, each concentration of REE in the same U standard solution was determined with conventional PN-ICP-MS after separating REE by cation-exchange chromatography. The concentrations of REE were ranging from 0.04 (Pr) to 1.08 (Dy) μg/g-U. The chondrite-normalized plot obtained through LA-ICP-MS analysis of the U standard sample exhibited close agreement with that obtained through the PN-ICP-MS of the REE-separated solution within the uncertainties.

A novel sample pre-treatment method for multi trace element enrichment from environmental waters prior to optical emission spectrometry analysis with inductively coupled plasma (ICP-OES) is proposed, based on dispersed particle extraction (DPE). This method is based on the use of silica nanoparticles functionalized with strong cation exchange ligands. After separation from the investigated sample solution, the nanoparticles used for the extraction are directly introduced in the ICP for measurement of the adsorbed target analytes. A prerequisite for the successful application of the developed slurry approach is the use of sorbent particles with a mean size of 500 nm instead of commercially available μm sized beads. The proposed method offers the known advantages of common bead-injection (BI) techniques, and further circumvents the elution step required in conventional solid phase extraction procedures. With the use of 14.4 mL sample and addition of ammonium acetate buffer and particle slurry limits of detection (LODs) from 0.03 μg L(-1) for Be to 0.48 μg L(-1) for Fe, with relative standard deviations ranging from 1.7% for Fe and 5.5% for Cr and an average enrichment factor of 10.4 could be achieved. By implementing this method the possibility to access sorbent materials with irreversible bonding mechanisms for sample pre-treatment is established, thus improvements in the selectivity of sample pre-treatment procedures can be achieved. The presented procedure was tested for accuracy with NIST standard reference material 1643e (fresh water) and was applied to drinking water samples from the vicinity of Vienna.

This paper details an improved approach to environmental particle analysis for safeguards by means of a combination of an upgraded version of the so-called fission track method with state-of-the-art microscope and microprobe techniques. Improvements to the fission track method comprise a novel sample assembly, the automation of several of its steps and the extensive use of correlative microscopy. This is followed by an automated isolation of particles-of-interest by means of laser micro-dissection (LMD) and their collection onto a harvester for transfer to other micro-analytical instruments for further analysis. The samples examined in this contribution were analysed for their nuclear material signatures, in particular the presence of uranium isotopes. The length of a single analysis cycle herewith was reduced to 12 days.