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PCA Principle Components Analysis PLS Partial Least Squares PM Phase Modulation PMT Photo Multiplier Tube PVT Pressure Volume Temperature RET Resonance Energy Transfer RF Radio Frequency RI Refractive Index SARA Saturates Aromatics Resins Asphaltenes SFS Synchronous Fluorescence Spectra SLI Structured Light Illumination SPA N-(3-sulfopropyl) acridinium salt TAC Time to Amplitude Convertor TCSPC Time Correlated Single Photon Counting TRES Time Resolved Emission Spectra TSFS Total Synchronous Fluorescence Spectra UV Ultra-Violet XRF X-Ray Fluorescence xi Abbreviations
Chapter 1 Introduction For many years chemists, physicists and geologists have strived to characterise the physical and chemical nature of crude oils. The main impetus for this development has been the oil industry but techniques developed in this area also have environ- mental applications such as determination of oil spill type and petroleum in waste water systems and soils [1]. Crude oil can be separated into subfractions by Liquid Chromatography and High Pressure Liquid Chromatography (HPLC) [2] and sub- sequent analysis of these fractions can be performed by Gas Chromatography (GC). Mass Spectrometry can also be used to give a detailed chemical fingerprint of the oil [3]. However these methods are destructive and time consuming, requiring sep- aration of heavy crude oil constituents before analysis. Non-destructive analytical methods may provide an welcome alternative to these methods where fast analysis is required. For example, in the case of the oil industry, the pursuit of a real-time and in-situ analytical techniques for the determination of oil composition has been a major goal [4]. Knowledge of oil composition can be used to aid resource optimisation and exploitation, i.e., crude oils are formed with a wide variety of physical and chemical properties which determine whether they are economical to extract or what extraction method to use [4]. Optimisation of pipeline conditions and the distillation process is also critical to the oil industry; both of which are dependent on the properties of the crude oil. Heavy crude oils are often diluted with low molecular weight alkanes to improve pipeline flow conditions and the determination of distillation curves (showing the relationship between crude oil boiling point and the volume fraction distilled) of the crude oil can be then be used to optimise the delivery of 1
Page 1 and 2: Time-Resolved Fluorescence Spectros
Page 3 and 4: Abstract behaviour allowing calcula
Page 5 and 6: Contents List of Publications and P
Page 7 and 8: Contents 2.3 Temperature based Life
Page 9 and 10: List of Publications and Presentati
Page 11: Abbreviations Abbrev Definition API
Page 15 and 16: Introduction temperature increases
Page 17 and 18: A seal or cap-rock that prevents th
Page 19 and 20: Introduction Figure 1.2: Crude oil
Page 21 and 22: Introduction eroatoms (O, S, N) and
Page 23 and 24: Introduction toluene, dichlorometha
Page 25 and 26: 1.2 Fluorescence Spectroscopy 1.2.1
Page 27 and 28: Introduction S1 state for a certain
Page 29 and 30: Introduction The peaks in the absor
Page 31 and 32: Introduction Figure 1.9: Jablonski
Page 33 and 34: Introduction Figure 1.10: Static qu
Page 35 and 36: Introduction the ratio of τ 0/τ i
Page 37 and 38: 1.2.5 Measuring fluorescence lifeti
Page 39 and 40: Introduction Figure 1.14: Time-reso
Page 41 and 42: Introduction The autocorrelation fu
Page 43 and 44: Introduction case, the molecules ex
Page 45 and 46: From Equation 1.26, Introduction ω
Page 47 and 48: m = 1 P 2 + Q 2 Introduction (1.36
Page 49 and 50: Introduction based average lifetime
Page 51 and 52: Introduction Figure 1.21: General p
Page 53 and 54: Introduction TAC output pulse is gi
Page 55 and 56: Introduction at each frequency acco
Page 57 and 58: Introduction diagram showing the op
Page 59 and 60: Introduction Figure 1.26: Schematic
Page 61 and 62: Introduction provides enhanced cont
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Introduction PAH’s. It has been s
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to heavy oils (low API gravity). In
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Introduction The balance between en
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Introduction Figure 1.34: Fluoresce
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Introduction used [126, 129, 132] a
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Introduction Figure 1.36: Plot of a
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fractional contributions over time
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Introduction concentration and Ksv
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1.5 Crude oil photophysics Introduc
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Introduction stages of thermal matu
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Introduction yellow to red fluoresc
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1.7 Thesis goal Introduction This i
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Materials and Methods concentration
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Table 2.2: Fractionation Data for B
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Materials and Methods 2.2 Frequency
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Materials and Methods was within ±
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Materials and Methods The dichroic
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Figure 2.5: Transmission characteri
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Materials and Methods Figure 2.7: S
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Materials and Methods The variation
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Materials and Methods Figure 2.9: L
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Materials and Methods Figure 2.10:
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Materials and Methods Comparison ca
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Materials and Methods with ρ param
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Materials and Methods 2.3 Temperatu
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Materials and Methods IRF of the sy
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Materials and Methods 2.4 Temperatu
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Materials and Methods a series of w
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Materials and Methods 2. Using the
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Lifetime study on crude oils by the
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Table 3.3: Average lifetime and sin
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Table 3.5: Average lifetime and sin
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3.5 Single Lifetime distributions L
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Energy Transfer and Quenching proce
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Influence of low temperature on flu
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Conclusions and Future Work model (
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Appendix A Reference Lifetime Stand
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Appendix Figure A.2: FD response fo
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A.3 SPA N-(3-sulfopropyl) acridiniu
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A.4 Rhodamine B Appendix Rhodamine
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A.5 Acridone Appendix The highly ph
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Appendix Figure A.11: FD response f
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Table B.1: Frequency Domain average
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Appendix Table B.3: Emission λmax
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Table B.5: Frequency Domain lifetim
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Appendix for the determination of t
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Appendix Figure C.3: Multifrequency
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Appendix Figure C.5: FLIM intensity
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Appendix Table C.1: Fluorescence li
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Appendix D Published Work 281
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998 J Fluoresc (2008) 18:997-1006 s
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1000 J Fluoresc (2008) 18:997-1006
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1002 J Fluoresc (2008) 18:997-1006
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1004 J Fluoresc (2008) 18:997-1006
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1006 J Fluoresc (2008) 18:997-1006
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Bibliography [10] W. G. Dow (1977),
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Bibliography [31] M. A. Ali and W.
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Bibliography [53] R. D. Spencer and
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Bibliography [75] K. Konig (2000),
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Bibliography [93] C. Pasquini and A
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Bibliography [113] C. Ralston, X. W
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Bibliography [132] A. Ryder (2004),
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Bibliography variable-angle synchro
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Bibliography [171] R. K. McLimans (
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Bibliography using fluorescence spe
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Bibliography [210] H. Mishra, S. Pa
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Bibliography [229] N. Boens, W. W.
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