Enhanced analysis of stratified climate archives through upgrade of Laser Ablation Inductively Coupled Plasma Quadrupole to Time of Flight Mass Spectrometry?

• Main Author: Wilhelms-Dick, Dorothee
• Other Authors: Miller, Heinrich, Kasten, Sabine
• Format: Doctoral or Postdoctoral Thesis
• Language: English
• Published: Universität Bremen 2008
• Subjects: ICP-MS; Time of Flight; laser ablation; solid and liquid samples; ice cores; Antarctica; mineral dust; trace element analysis; 550; 550 Earth sciences and geology; ddc:550; Frozen Lake; Antarc*; ice core
• Online Access: https://media.suub.uni-bremen.de/handle/elib/2526; https://nbn-resolving.org/urn:nbn:de:gbv:46-diss000110802

The analysis of the inorganic composition of climatic archives provides proxies for climate reconstruction. For many applications commercially available inductively coupled plasma quadrupole mass spectrometry (ICP-Q-MS) systems are used for investigations. One aim of this thesis was to test the laser ablation (LA)-ICP-Q-MS method for the analysis of different sample matrices (polar ice cores, bivalves, frozen lake sediment cores). The main limitation of LA-ICP-Q-MS measurements is the number of analysed isotopes, especially for point scan analysis of embedded particles in the ice matrix and the analysis of growth bands of bivalve shells. Analysing as many isotopes as possible is of interest to deduce e.g. the corresponding source region of embedded particles in the ice matrix. The quasi-simultaneous detection of several isotopes of transient signals is realised in ICP-Time of Flight-MS (ICP-TOF-MS) systems. The applicability of the newly developed ICP-TOF-MS system for ice core analysis in climatic research was explored in this thesis. With the present experimental setup the analysis of trace elements in ice core samples is only possible for liquid samples. The accuracy and precision compares to well established ICP-Q-MS systems. Using the Aridus II as sample introduction system the signal sensitivity was 2-10 times lower for the ICP-TOF-MS compared to ICP-Q-MS systems. Calibration studies and investigation of reference materials showed that the calibration range is limited to an order of magnitude of about 10exp4 to 10exp5 except for m/z ratios between 23 amu and 72 amu where it is even lower. The observed minor formation of oxides (0.3%) and high signal sensitivities for rare earth elements (16000-32000 cps and ug L-1; background: 20-80 cps) permits the characterisation of mineral dust in ice core samples at the low ng L-1 concentration range.