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Contents 1.3 Spectroscopy of crude petroleum oils . . . . . . . . . . . . . . . . . . 49 1.3.1 Current spectroscopic techniques . . . . . . . . . . . . . . . . 49 1.3.2 Crude Oil Fluorescence . . . . . . . . . . . . . . . . . . . . . . 52 1.3.3 Crude Oil Dilution . . . . . . . . . . . . . . . . . . . . . . . . 56 1.3.4 Fluorescence Lifetime Analysis of crude oils . . . . . . . . . . 58 1.3.5 Fluorescence Energy Transfer and Quenching of PAH’s and crude oils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63 1.4 Temperature based Fluorometry of complex materials . . . . . . . . . 66 1.4.1 Low temperature studies on PAH’s . . . . . . . . . . . . . . . 66 1.4.2 High temperature studies . . . . . . . . . . . . . . . . . . . . . 68 1.5 Crude oil photophysics . . . . . . . . . . . . . . . . . . . . . . . . . . 71 1.6 Applications of crude oil fluorescence Hydrocarbon Fluid Inclusion Analysis . . . . . . . . . . . . . . . . . . 72 1.7 Thesis goal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77 2 Materials and Methods 78 2.1 Samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78 2.1.1 Batch 1 Oils . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78 2.1.2 Batch 2 oils . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79 2.2 Frequency Domain(FD) measurements . . . . . . . . . . . . . . . . . 83 2.2.1 FD Instrumentation . . . . . . . . . . . . . . . . . . . . . . . 83 2.2.1.1 Hardware . . . . . . . . . . . . . . . . . . . . . . . . 83 2.2.1.2 FD Electronics . . . . . . . . . . . . . . . . . . . . . 85 2.2.1.3 Excitation light source and beam shaping optics . . . 85 2.2.1.4 Detection system . . . . . . . . . . . . . . . . . . . . 86 2.2.1.5 Data Acquisition and Analysis . . . . . . . . . . . . 91 2.2.2 Reference Standards . . . . . . . . . . . . . . . . . . . . . . . 92 2.2.3 Validation of FD instrumentation . . . . . . . . . . . . . . . . 98 2.2.3.1 Resolution of a mixture of fluorophores . . . . . . . . 98 2.2.3.2 Linearity of lifetime measurements . . . . . . . . . . 101 2.2.4 Crude oil lifetime measurements . . . . . . . . . . . . . . . . . 103 2.2.4.1 Cleaning of quartz cells used for crude oil analysis . . 104 2.2.5 Estimation of the uncertainty of FD lifetimes of crude oils . . 104 v
Contents 2.3 Temperature based Lifetime Experiment - Neat Crude Oils . . . . . . 107 2.3.1 Instrumentation . . . . . . . . . . . . . . . . . . . . . . . . . . 107 2.3.2 Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108 2.4 Temperature based Lifetime Experiment - Lifetime decays of dilute crude oils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111 2.4.1 Instrumentation . . . . . . . . . . . . . . . . . . . . . . . . . . 111 2.4.2 Dilutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112 2.4.3 Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112 2.4.4 Validation Tests . . . . . . . . . . . . . . . . . . . . . . . . . . 113 2.5 Determination of lifetimes of oil within HCFI . . . . . . . . . . . . . 116 3 Lifetime study on crude oils by the FD method 118 3.1 Raw data - phase modulation plots . . . . . . . . . . . . . . . . . . . 118 3.2 Calculation of lifetimes from phase modulation data . . . . . . . . . . 125 3.3 Fitting of Phase Modulation data . . . . . . . . . . . . . . . . . . . . 135 3.4 Comparison of average lifetimes determined by FD and TD methods 142 3.5 Single Lifetime distributions . . . . . . . . . . . . . . . . . . . . . . . 147 3.6 Correlations between Photophysical parameters and Crude Oil Chem- ical Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 160 3.6.1 Correlations made with data obtained from distribution models165 3.6.2 Explanation of outliers in correlation plots . . . . . . . . . . . 168 3.7 Geological trends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170 3.8 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174 4 Energy Transfer and Quenching processes in crude petroleum oils176 4.1 Crude oil dilutions and the influence of solvent . . . . . . . . . . . . . 177 4.2 Energy Transfer and Quenching . . . . . . . . . . . . . . . . . . . . . 184 4.3 Stern-Volmer Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . 192 4.4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198 5 Influence of low temperature on fluorescence emission from crude oils 200 5.1 Effect of low temperature on the fluorescence emission of crude oils . 200 5.2 Low temperature lifetime analysis . . . . . . . . . . . . . . . . . . . . 205 vi
Page 1 and 2: Time-Resolved Fluorescence Spectros
Page 3 and 4: Abstract behaviour allowing calcula
Page 5: Contents List of Publications and P
Page 9 and 10: List of Publications and Presentati
Page 11 and 12: Abbreviations Abbrev Definition API
Page 13 and 14: Chapter 1 Introduction For many yea
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
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Introduction diagram showing the op
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Introduction Figure 1.26: Schematic
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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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