Multielemental analysis of geological and biological samples using laser ablation ICP-SFMS
Abstract: The analytical performance of laser ablation (LA) for multielemental determination of geological and biological samples has been investigated. In the present study, LA has been used for sample introduction in inductively coupled plasma sector field mass spectrometry (ICP-SFMS). Although LA can provide semi-quantitative results rapidly and easily, the calibration process still remains the "Achilles heel" of the technique. The major goal of this study has been to investigate the capabilities of LA-ICP-SFMS for qualitative and quantitative analysis of various solid materials. LA was used for analyses of coal were calibration was performed by using coal powder doped with analyte elements. This was done by adding solution standards (including analyte and internal standard elements) to the coal, drying and finally homogenising, followed by pressing tablets. LA results were compared with data obtained by conventional solution nebulisation (SN) after preparation of coal samples using microwave (MW) digestion or fusion. In spite of a relatively poor agreement for elements such as As, Se, Sn, Re, Te, and Tl, accuracy obtained with LA in the present study is otherwise generally superior to previously reported data for LA and slurry nebulisation. For about 50 elements, results obtained with LA fall within 20% of those obtained by SN. The study shows the potential of LA quantification, based on solution-doped powders. However, the necessity of sample grinding and homogenising results in loss of spatial distribution information and makes the approach more vulnerable to sample contamination. The possibilities of sulphide minerals analysis by ICP-SFMS have been investigated. Seven elements (Co, Fe, Cd, Ag, Mn, Cu and S) have been quantitatively determined in sphalerite samples from the Zinkgruvan mine, using Zn as internal standard (IS). A straightforward calibration procedure allows on-line correction for possible Fe impurities at percent levels. Consequently, the use of complimentary techniques for determination of actual Zn content in the samples is avoided. The LA-ICP-SFMS results were compared with data from conventional SN introduction of sample solutions following acid digestion. Good agreement was found between the methods. For homogeneously distributed elements the overall precision for LA was found to be better than 10% RSD. A method for total mineral dissolution of five sulphides (sphalerite, pyrite, galena, pyrrhotite and chalcopyrite) has been developed, followed by multielemental analysis by ICP-SFMS. By performing this mineral characterisation the intention was to determine whether the analysed bulk mineral samples could be used as in-house LA calibration standards. The use of LA was focused towards elucidating whether the observed deviations in results obtained by ICP-SFMS for the two reference material powders used were caused by sample inhomogeneity or by inefficient matrix dissolution. It was found that the reference materials showed lack of accuracy in recommended concentrations for many trace and ultra trace elements, as well as possible inhomogeneity when using 50 mg sample amounts. The sulphide minerals studied appears to be suitable as matrix matched calibration standards for the determination of about 20 trace and ultra trace elements by LA. Laser ablation was also used for analysing element to sulphur ratios in washed human nails. The element ratios were then used to display the effectiveness of the applied washing method applied prior to MW digestion and analysis by ICP-SFMS. Based on the LA analysis, it was found that, even after the applied nail washing procedure, many elements are enriched in the surface of the nail.
CLICK HERE TO DOWNLOAD THE WHOLE DISSERTATION. (in PDF format)