Sedimentary Processes Involving Aromatic Hydrocarbons
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Sedimentary organic matter contains many compounds that have no obvious biogenic precursors, so their formation and occurrence are of geochemical interest. The first part of this thesis (chapters 2-5) discusses the results obtained from studying hydrocarbon racemates. Some of the compounds identified are also suggested as intermediates in the formation of alkylnaphthalenes identified in chapters 6-7. The second part of this thesis (chapters 6-11) covers the identification of a range of alkylnaphthalenes and alkylphenanthrenes in sedimentary organic matter. Possible pathways for the formation of these hydrocarbons are outlined and their application as probes into the processes of petroleum formation are described.In chapter 2 the use of permethylated cyclodextrin capillary gas chromatography columns to separate hydrocarbon racemates are reported. Chapter 3 reports the synthesis of 1,2,2,5-tetramethyltetralin and 1,2,2,5,6-pentamethyltetralin and identifies them as racemates in crude oil. They are proposed as intermediates in the formation of sedimentary alkylnaphthalenes (identified in chapters 6 and 7).The identification of isodihydro-ar-curcumene in sedimentary organic matter is described in chapters 4 and 5. It co-occurs in crude oil with dihydro-ar-curcumene and is suggested to originate from this compound via a sedimentary rearrangement process. Chiral GC-MS techniques have been used to show the presence of both enantiomers of these compounds in crude oils. The elution order of the enantiomers has been established using reference compounds of known configuration. The effects of maturity and biodegradation on dihydro-ar-curcumene and isodihydro-ar-curcumene enantiomers is reported. Optically pure dihydro-ar-curcumene from natural products undergoes rapid racemisation in the subsurface, yielding a racemic mixture before the onset of significant oil formation. 1,2-Alkyl shifts on the aromatic ring also begin at an early stage to yield isodihydro-ar-curcumene and these processes continue with increasing maturity. Laboratory experiments using proton and clay catalysts (Lewis acid catalyst) show that the alkyl shift reaction is catalysed by both proton and Lewis acids, and racemisation is only catalysed by Lewis acids. A moderately biodegraded crude oil has been shown to be depleted in the R enantiomer of dihydro-ar-curcumene and an extensively degraded oil has dihydro-ar-curcumene depleted relative to isodihydro-ar-curcumene.The identification of a number alkylnaphthalenes and their possible origins in sedimentary organic matter is described in chapters 6 and 7. In chapter 6 a previously unreported tetramethylnaphthalene (TeMN) was identified in petroleum. This compound is structurally similar to bicyclic compounds of microbial origin and these are suggested as a likely source, via a tetralin intermediate identified in chapter 3. In chapter 7 isomeric pentamethylnaphthalenes previously unreported in sedimentary organic matter are reported. These isomeric pentamethylnaphthalenes (PMNs) were identified in a number of crude oils and sediments, ranging in age from Proterozoic to Tertiary. 1,2,3,5,6-PMN is suggested to form predominantly from the aromatisation of drimanoid precursors via 1,2,2,5,6-pentamethyltetralin identified in chapter 3. In laboratory experiments, the other pentamethylnaphthalenes were generated from 1,2,3,5,6-PMN in proportions that reflect the relative stability of the isomers. By analogy, the other PMNs in sediments are suggested to arise via acid catalysed isomerisation or transalkylation processes. A maturity parameter was developed based on laboratory experiments in conjunction with observed distributions of pentamethylnaphthalenes.The formation of alkylnaphthalenes and alkylphenanthrenes through a methylation process is discussed in chapters 8-10. Several crude oils and shales which contain anomalously high concentrations of 1,6-dimethylnaphthalene, 1,2,5-trimethylnaphthalene, 1,2,7-trimethylnaphthalene, 1,2,3,5-tetramethylnaphthalene, 1,2,3,5,6-pentamethylnaphthalene, 2-methyl-6-isopropyl-1(4-methylpentyl)naphthalene, phenanthrene, 1-methylphenanthrene, 1,7-dimethylphenanthrene and retene have been shown to contain relatively high concentrations of their corresponding methylated counterparts. In laboratory experiments carried out under mild conditions, each of the alkylnaphthalenes and alkylphenanthrenes have been shown to be methylated in specific positions when heated with a methyl donor in the presence of a clay catalyst. These observations have been interpreted as evidence for a sedimentary methylation process.The effect of biodegradation on alkylnaphthalenes and alkylphenanthrenes formed from sedimentary methylation is described in chapter 11. Land-plant-derived aromatic hydrocarbons with a range of susceptibilities to reservoir biodegradation have been identified in crude oils. These compounds are the result of reactions of natural products involving aromatisation, rearrangement and methylation in the sediments (chapters 9 and 10). They are therefore suggested as markers for land-plants in severely biodegraded oils in which most of the other biologically derived compounds cannot be recognised. The order of biodegradability of these compounds has been assessed relative to their non-methylated counterparts namely 6-isopropyl-2-methyl-1-(4-methylpentyl)naphthalene and retene. The order of degradation of the four compounds is : retene < 9-methylretene ~ 6-isopropyl-2-methyl-1-(4-methylpentyl)naphthalene > 6-isopropyl-2,4-dimethyl-1-(4-methylpentyl)naphthalene. These results have been used to assess that a crude oil is a mixture of severely biodegraded and less biodegraded crude oil.
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