Enhanced analysis of stratified climate archives through upgrade of laser ablation inductively coupled plasma quadrupole to time of flight mass spectrometry? [Elektronische Ressource] / vorgelegt von Dorothee Wilhelms-Dick

Dorothee Dick

Informations

• Publié par: universitat_bremen
• Publié le: 01 janvier 2008
• Nombre de lectures: 25
• Langue: English
• Poids de l'ouvrage: 5 Mo

Extrait

Enhanced analysis of stratified climate archives through
upgrade of Laser Ablation Inductively Coupled Plasma
Quadrupole to Time of Flight Mass Spectrometry?
Dissertation zur Erlangung des Grades
Dr. rer. nat.



vorgelegt dem
Fachbereich Geowissenschaften (FB5)
der Universität Bremen



vorgelegt von
Dorothee Wilhelms-Dick


Bremen, Mai 2008

Gutachter
Prof. Dr. H. Miller
PD Dr. S. Kasten







Prüfer
Prof. Dr. W. Bach
Dr. M. Kriews







Promotionslolloquium
Am 24.07.2008
Preface
This work is submitted as a dissertation, instructed by Dr. Michael Kriews and
supervisor Prof. Dr. Heinrich Miller.
The cumulative thesis includes five manuscripts (2 published, 1 in press, 1
submitted and 1 in preparation for submission) to which a general introduction is
prefixed in Chapter 1. There, the thesis is linked to the overarching scientific
background, a general overview of related analytical methods in the Geosciences is
given, which concludes with a focus on inorganic mass-spectrometric methods,
particularly on time of flight-mass spectrometers (TOF-MS). The thesis’s objectives are
summarized in Chapter 1.1. In Chapter 2, a short summary of my own contributions is
given for each of the five manuscripts. Chapter 3 describes the recently developed
inductively coupled plasma (ICP)-TOF-MS, which I assessed within this study for the
analysis of frozen and liquid ice core samples. In Chapter 4 and 5 performance studies
of the ICP-TOF-MS system are presented and discussed. Conclusions and scientific
perspectives follow in Chapter 6. Chapter 7 compiles the references for Chapters 1–6. I
lead-author the Publications I, III and IV on the application of the analytical method
developed by Reinhardt (2002) to different sample matrices. Finally, in future our
studies aim for improved matching of different ice cores and climatic archives, which
refines on the basis for studies on couplings in the global climate system, as e.g.
undertaken in Publication II. Three different mass spectrometer systems, including the
ICP-TOF-MS system, are compared in Publication V with respect to the analysis of low
concentrated rare earth elements (REE) in Antarctic ice core samples. References in the
manuscripts are respectively included.
i
Contents
Preface i
Tables iv
Figures vi
Abbreviations ix
Summary 1
Zusammenfassung 4
1 Introduction 7
1.1 Objectives....................................................................................................12
2 List of Publication submitted for the thesis 13
3 Materials, Instrumentations and Methods 15
3.1 Inductively Coupled Plasma Mass Spectrometry........................................15
3.1.1 ICP-TOF-MS...................................................................................16
3.1.2 a............................................................17
3.1.3 Interface...........................................................................................20
3.1.4 Ion optic20
3.1.5 Ion repeller and mass analyzer ........................................................21
3.1.6 Detection system.............................................................................23
3.1.7 Interferences....................................................................................24
3.1.8 Sample introduction systems for liquid samples.............................26
3.2 Laser ablation as sample introduction system for solid samples ................28
3.2.1 Absorption characteristics of ice .....................................................29
3.3 Calibration standards...................................................................................30
3.3.1 Multi-element solutions for calibration standards...........................
3.3.2 Preparation of multi-element calibration standards.........................31
3.3.3 Particulate matter for calibration standards with embedded
particles............................................................................................32
3.3.4 Improvement of the preparation of calibration standards with
embedded particles ..........................................................................33
4 Performance study of the ICP-TOF-MS system for the analysis of liquid
samples 37
4.1 Comparison of different sample introduction systems................................37
4.2 Parameter study: Aridus II-ICP-TOF-MS...................................................40
4.2.1 ICP parameter..................................................................................41
4.2.2 Aridus II parameter..........................................................................43
4.2.3 Day to day signal variations ............................................................43
4.3 Interference studies.....................................................................................44
4.4 Instrumental detection limits, spectral resolution and the dynamic
range of the ICP-TOF-MS system ..............................................................44
4.5 Analysis of reference materials...................................................................47
ii
5 Performance study of the LA-ICP-TOF-MS system for the analysis of
solid samples 49
5.1 Parameter study: LA-ICP-TOF-MS............................................................50
5.1.1 Plasma jittering during the LA process ...........................................52
5.2 Parameter study: LA-Aridus II-ICP-TOF-MS ............................................52
5.2.1 ICP parameter..................................................................................53
5.2.2 Aridus II parameter..........................................................................53
5.3 Influence of helium as transport gas ...........................................................56
5.4 Internal standardisation for ice core analysis ..............................................57
5.5 Reasons for low ICP-TOF-MS signals .......................................................59
5.5.1 Duty cycle........................................................................................59
5.5.2 Components of the ion optics..........................................................59
5.5.3 Radio-frequency generator..............................................................60
5.5.4 Shielding of the plasma ...................................................................61
5.5.5 Polymers close to the plasma torch .................................................62
5.5.6 Pulsed aerosol introduction .............................................................63
5.5.7 Laser shot frequency........................................................................63
5.5.8 Size of the sample chamber64
6 Conclusions and Outlook 65
7 References 68
Publications
Publication I ............................................................................................................79
Publication II.........................................................................................................103
Publication III .......................................................................................................109
Publication IV119
Publication V129
Acknowledgement 151
Appendix 153
A1 Utility Model.............................................................................................153
A2 Publication Bunsen Magazin.....................................................................163
A3 Element concentrations along EDML meter 270......................................171
A4 Element concentrations of subsections of EDML meter 270 obtained
by LA-ICP-Q-MS and ICP-Q-MS analysis of acidified and digested
samples......................................................................................................175
A5 Relative element intensities in bivalves obtained by LA-ICP-Q-MS
analysis176
A6 Program (IDL®) for the evaluation of ICP-TOF-MS data .......................177
A7 Concentration data of reference materials analysed by Aridus II-ICP-
TOF-MS ....................................................................................................182
A8 Concentration data of Intercomparison samples analysed by
Aridus II-ICP-TOF-MS.............................................................................184
iii Tables
Tables
Table 1: Preparation of calibration standards for Quadrupole (Q) and Time of
Flight (TOF) ICP-MS systems using solutions A-C and F –H (see text,
chapter 3.3.1). ...............................................................................................32
Table 2: Preparation of calibration ice standards with defined amounts of
particulate matter (standard reference material NIST 1648) for laser
ablation ICP-MS analysis. Moreover, the concentration of each
certified and noncertified (grey shaded) element in each standard is
calculated......................................................................................................33
Table 3: LA-ICP-Q-MS calibration data of ice standards with embedded
particles (standard reference material NIST 1648). The