Multi-element analysis of environmental samples using LA-ICP-MS method developments with emphasis on calibration strategies

Abstract: Analytical applications based on the use of laser ablation-inductively coupled plasma-sector field mass spectrometry (LA-ICP-SFMS) have shown great potential for both quantitative and qualitative determination of elements in a variety of materials, although the weak point is finding a suitable calibration approach. The major focus of this work has, therefore, been internal standardisation and calibration. Methods for quantitative and qualitative analysis of geological (coal, ferromanganese concretions, sulphide minerals) and biological (nail and hair) samples have been developed. For coal, two reference materials were analysed after microwave (MW) treatment with different combinations of HNO3, aqua regia, HF and H2O2. Lithium metaborate (LMB) fusion with and without ashing of samples, as well as LA solid sampling on pressed coal pellets were also evaluated. External calibration for LA-ICP-SFMS was conducted using matrix-matched standard dopeds with standard solutions. This approach resulted in good accuracy for 46 out of 47 elements tested in the coal fly ash reference material. The precision was assessed in this work by replicate analyses of coal samples and was found to be, as average values for all elements, 4-5% and 10-15% relative standard deviation (RSD) for procedures involving digestion and LA sampling, respectively. For ferromanganese concretions, improvement of existing sample preparation schemes was necessary in order to expand the element coverage. The optimised and validated (for about 60 elements) method has the potential to replace the multitude of sample preparation and instrumental analytical techniques previously used to determine specific groups of elements in ferromanganese nodules. By using this improved method, it was possible to successfully quantify more than 50 elements by LA-ICP-SFMS using external calibration against matrix-matched standards. The results also show how different LA parameters affect the isotopic response and RSD. For sulphide minerals, LA-ICP-SFMS analysis was performed directly on polished crystalline sections. In sphalerite, a number of major and trace elements were determined by a ‘single-standard’ method using Zn for internal standardisation, together with correction for FeS impurities in the mineral, allowing straightforward quantification without using external methods for the determination of the actual Zn content. Results obtained by this approach were in good agreement with those from using external calibration. In order to evaluate the possibility to use crystalline sections of sphalerite and four other sulphide minerals as in-house standards, an analytical method was developed for multi-elemental analysis of such samples after preparation based on both MW digestion using different acid mixtures and LMB fusion. The performance of the sample preparation and analysis stages was evaluated using powdered pyrite and galena reference materials. It was found possible to use the selected minerals as matrix-matched standards for the determination of about 20 trace and ultra-trace elements by LA-ICP-SFMS. The second group of matrices concerned in this work comprises hair and nail samples. The first part of this study was focused on method validation for the determination of 71 elements by conventional ICP-SFMS analysis after MW-assisted digestion, with special attention paid to the correction of spectral interferences and to accuracy assessment. In the follow up study, the main concern was to evaluate the capabilities of LA-ICP-SFMS for quantitative multi-elemental analysis of hair and nail samples, emphasising the collection of spatially resolved information. Quantification was performed by means of an in-house, multi-element, matrix-matched standard using 32S+ as internal standard. A major conclusion of this thesis is that each sample type is in many respects unique, and therefore demands careful selection of a suitable calibration protocol, in order to ensure that reliable analytical results are delivered. The developed methods will make it possible to quantitatively analyse samples such as geological thin-sections, single sulphide grains, ferromanganese concretions, fingernails and hair. The results also show that LA-ICP-SFMS potentially can be used for obtaining quantitative analyses with good spatial resolution in a variety of materials.