View/Open - ARAN - National University of Ireland, Galway

More documents

Recommendations

Info

Introduction Metagenesis: At very high temperatures (higher than 160 ◦ C), gas evolu- tion ceases and the H:C ratio declines until only carbon is left in the form of graphite. Three types of kerogen are defined based on their source material. Type I is lacustrine algal in origin, the dominant compounds being lipids and their derivative fats, waxes and oils. The H:C ratio is ∼ 1.5 indicating a high degree of aliphacity [10]. This type shows greater tendency to produce liquid hydrocarbons. Type II kerogen is predominantly planktonic in origin and although is rich in aliphatic compounds it has a lower H:C ratio than Type I kerogen. This type of kerogen also has a greater tendency to form petroleum. Type III kerogen, or humic kerogen has a much lower H:C ratio indicating a much higher degree of aromaticity. Humic kerogen is produced from the lignin of woody plants, which grow on land. If this type of kerogen is buried as peat, it can undergo diagenesis to coal. Otherwise, it tends to generate largely gas rather than oil. Kerogens are noted by their high molecular weights and insolubility in organic solvents such as Toluene and Hexane. Because they are precursors to oil and gas, kerogen structure has long been the subject of investigation and to date realistic gen- eralisations of structure have yet to be published. Molecular weights are estimated to range from 20, 000 g/mol for Type I kerogen to 26, 000 g/mol for Type III kerogen [11]. However each kerogen is formed under unique starting conditions and a general classification of kerogens is performed by describing gross kerogen composition and relating it to hydrocarbon generation. voir: There are a number of conditions that lead to the accumulation of oil in a reser- A sedimentary rock (called the source rock) rich in kerogenic material that is buried deep enough to generate the necessary pressure and temperature. A path to allow oil and gas to move upwards. This process is called migration and is subdivided into the processes of primary and secondary migration . A porous and permeable reservoir rock to contain the oil. Primary migration is the movement of oil and gas out of the source rocks into the permeable reservoir rocks, while Secondary migration is the movement of fluids within the permeable rocks that eventually leads to segregation of the oil and gas. 4
A seal or cap-rock that prevents the oil from escaping to the surface. 1.1.2 Oil Maturity Introduction In geochemical terms, the effect of heat or thermal maturation on kerogen and its subsequent transformation to oil is most important. Maturation processes involve cracking, isomerisation and aromatisation reactions, as well as alkylation and dealky- lation of aromatic rings. These processes commence in the source rocks and continue during migration to the reservoir. Over the geological time frames (60-70 million years), maturation processes yield more thermodynamically stable small molecules as well as the transformation of saturated into aromatic hydrocarbons. The degree of maturity can be estimated by a number of methods such as the analysis of biomarker distribution and the distribution and abundance of saturated and aromatic hydrocarbons, i.e., compounds which generally constitute 95-98 % of crude oils [7, 13]. Another measure of the maturity of a crude oils is the relative density of a petroleum liquid or API gravity [14], given by the relation: API gravity = 141.5 SG − 131.5 (1.1) where SG is the specific gravity of the oil at 15.6 ◦ C or 60 ◦ F. Although mathemat- ically API gravity has no units, it is nevertheless referred to as being in ‘degrees’. The U.S. National Bureau of Standards in 1916 established the Baum scale as the standard for measuring specific gravity of liquids less dense than water. Unfor- tunately, hydrometers in the U.S. had been manufactured and distributed widely with a modulus of 141.5 instead of the Baum scale modulus of 140. The scale was so firmly established that by 1921 the remedy implemented by the American Petroleum Institute was to create the API Gravity scale recognising the scale that was actually being used [14]. Biomarkers are any organic compounds which are found in oil, bitumen, rocks and sediments that show little or no change in structure from their parent organic molecules in living organisms. These compounds are typically analyzed using gas chromatography or mass spectrometry, common examples of which are pristane, phytane, steranes and porphyrins. [12] 5
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 and 12: Abbreviations Abbrev Definition API
Page 13 and 14: Chapter 1 Introduction For many yea
Page 15: Introduction temperature increases
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
Page 63 and 64: Introduction PAH’s. It has been s
Page 65 and 66: to heavy oils (low API gravity). In
Page 67 and 68:
Introduction The balance between en
Page 69 and 70:
Introduction Figure 1.34: Fluoresce
Page 71 and 72:
Introduction used [126, 129, 132] a
Page 73 and 74:
Introduction Figure 1.36: Plot of a
Page 75 and 76:
fractional contributions over time
Page 77 and 78:
Introduction concentration and Ksv
Page 79 and 80:
Page 81 and 82:
Page 83 and 84:
1.5 Crude oil photophysics Introduc
Page 85 and 86:
Introduction stages of thermal matu
Page 87 and 88:
Introduction yellow to red fluoresc
Page 89 and 90:
1.7 Thesis goal Introduction This i
Page 91 and 92:
Materials and Methods concentration
Page 93 and 94:
Table 2.2: Fractionation Data for B
Page 95 and 96:
Materials and Methods 2.2 Frequency
Page 97 and 98:
Materials and Methods was within ±
Page 99 and 100:
Materials and Methods The dichroic
Page 101 and 102:
Figure 2.5: Transmission characteri
Page 103 and 104:
Materials and Methods Figure 2.7: S
Page 105 and 106:
Materials and Methods The variation
Page 107 and 108:
Materials and Methods Figure 2.9: L
Page 109 and 110:
Materials and Methods Figure 2.10:
Page 111 and 112:
Page 113 and 114:
Materials and Methods Comparison ca
Page 115 and 116:
Page 117 and 118:
Materials and Methods with ρ param
Page 119 and 120:
Materials and Methods 2.3 Temperatu
Page 121 and 122:
Materials and Methods IRF of the sy
Page 123 and 124:
Materials and Methods 2.4 Temperatu
Page 125 and 126:
Materials and Methods a series of w
Page 127 and 128:
Page 129 and 130:
Materials and Methods 2. Using the
Page 131 and 132:
Lifetime study on crude oils by the
Page 133 and 134:
Page 135 and 136:
Page 137 and 138:
Page 139 and 140:
Page 141 and 142:
Page 143 and 144:
Page 145 and 146:
Page 147 and 148:
Page 149 and 150:
Table 3.3: Average lifetime and sin
Page 151 and 152:
Table 3.5: Average lifetime and sin
Page 153 and 154:
Page 155 and 156:
Page 157 and 158:
Page 159 and 160:
3.5 Single Lifetime distributions L
Page 161 and 162:
Page 163 and 164:
Page 165 and 166:
Page 167 and 168:
Page 169 and 170:
Page 171 and 172:
Page 173 and 174:
Page 175 and 176:
Page 177 and 178:
Page 179 and 180:
Page 181 and 182:
Page 183 and 184:
Page 185 and 186:
Page 187 and 188:
Page 189 and 190:
Energy Transfer and Quenching proce
Page 191 and 192:
Page 193 and 194:
Page 195 and 196:
Page 197 and 198:
Page 199 and 200:
Page 201 and 202:
Page 203 and 204:
Page 205 and 206:
Page 207 and 208:
Page 209 and 210:
Page 211 and 212:
Page 213 and 214:
Influence of low temperature on flu
Page 215 and 216:
Page 217 and 218:
Page 219 and 220:
Page 221 and 222:
Page 223 and 224:
Page 225 and 226:
Page 227 and 228:
Page 229 and 230:
Page 231 and 232:
Page 233 and 234:
Page 235 and 236:
Page 237 and 238:
Page 239 and 240:
Page 241 and 242:
Page 243 and 244:
Page 245 and 246:
Page 247 and 248:
Page 249 and 250:
Page 251 and 252:
Page 253 and 254:
Conclusions and Future Work model (
Page 255 and 256:
Appendix A Reference Lifetime Stand
Page 257 and 258:
Appendix Figure A.2: FD response fo
Page 259 and 260:
A.3 SPA N-(3-sulfopropyl) acridiniu
Page 261 and 262:
A.4 Rhodamine B Appendix Rhodamine
Page 263 and 264:
A.5 Acridone Appendix The highly ph
Page 265 and 266:
Appendix Figure A.11: FD response f
Page 267 and 268:
Page 269 and 270:
Page 271 and 272:
Page 273 and 274:
Page 275 and 276:
Table B.1: Frequency Domain average
Page 277 and 278:
Appendix Table B.3: Emission λmax
Page 279 and 280:
Table B.5: Frequency Domain lifetim
Page 281 and 282:
Page 283 and 284:
Page 285 and 286:
Appendix for the determination of t
Page 287 and 288:
Appendix Figure C.3: Multifrequency
Page 289 and 290:
Appendix Figure C.5: FLIM intensity
Page 291 and 292:
Appendix Table C.1: Fluorescence li
Page 293 and 294:
Appendix D Published Work 281
Page 295 and 296:
998 J Fluoresc (2008) 18:997-1006 s
Page 297 and 298:
1000 J Fluoresc (2008) 18:997-1006
Page 299 and 300:
1002 J Fluoresc (2008) 18:997-1006
Page 301 and 302:
1004 J Fluoresc (2008) 18:997-1006
Page 303 and 304:
1006 J Fluoresc (2008) 18:997-1006
Page 305 and 306:
Bibliography [10] W. G. Dow (1977),
Page 307 and 308:
Bibliography [31] M. A. Ali and W.
Page 309 and 310:
Bibliography [53] R. D. Spencer and
Page 311 and 312:
Bibliography [75] K. Konig (2000),
Page 313 and 314:
Bibliography [93] C. Pasquini and A
Page 315 and 316:
Bibliography [113] C. Ralston, X. W
Page 317 and 318:
Bibliography [132] A. Ryder (2004),
Page 319 and 320:
Bibliography variable-angle synchro
Page 321 and 322:
Bibliography [171] R. K. McLimans (
Page 323 and 324:
Bibliography using fluorescence spe
Page 325 and 326:
Bibliography [210] H. Mishra, S. Pa
Page 327 and 328:
Bibliography [229] N. Boens, W. W.
show all

View/Open - ARAN - National University of Ireland, Galway

You also want an ePaper? Increase the reach of your titles

Delete template?

Save as template?