GEOCHEMICAL APPLICATIONS OF POLYCYCLIC AROMATIC HYDROCARBONS IN CRUDE OILS AND SEDIMENTS FROM PAKISTAN

Submitted By:
MUHAMMAD ASIF
05-Ph.D-Chemistry-02

DEPARTMENT OF CHEMISTRY
UNIVERSITY OF ENGINEERING AND TECHNOLOGY LAHORE – PAKISTAN

2010

GEOCHEMICAL APPLICATIONS OF POLYCYCLIC AROMATIC HYDROCARBONS IN CRUDE OILS AND SEDIMENTS FROM PAKISTAN
A Thesis Submitted To The University of Engineering & Technology Lahore In Partial fulfillment of the Requirements for the Degree of

Doctorate of Philosophy
In

Chemistry
By

MUHAMMAD ASIF
2005-Ph.D-Chemistry-02

Supervisor Prof. Dr. Fazeelat Tahira

DEPARTMENT OF CHEMISTRY
UNIVERSITY OF ENGINEERING AND TECHNOLOGY LAHORE – PAKISTAN

2010

GEOCHEMICAL APPLICATIONS OF POLYCYCLIC AROMATIC HYDROCARBONS IN CRUDE OILS AND SEDIMENTS FROM PAKISTAN
Research Thesis submitted in Partial Fulfillment of the Requirements for the Degree of

Doctor of Philosophy in Chemistry

Approved on: _______________

Signature:__________________ Prof. Dr. Fazeelat Tahira Internal Examiner

Signature:__________________ Prof. Dr. M. Akram Kashmiri External Examiner

Signature:__________________ Prof. Dr. Saeed Ahmad Chairman of the Department

Signature:___________________ Prof. Dr. Fazeelat Tahira Dean Faculty of Natural Sciences, Humanities and Islamic Studies

DEPARTMENT OF CHEMISTRY University of Engineering and Technology, Lahore-Pakistan,

Paul Greenwood Senior Research Fellow. Paul Philp Professor Petroleum and Environmental Geochemistry The University of Oklahoma School of Earth and Energy 100 East Boyd street suite 810. Professor of Organic Chemistry Dean of natural sciences. Internal Examiner Prof. Fazeelat Tahira. Board of Intermediate and Secondary Education. humanities and Islamic studies. R. Lahore. Akram Kashmiri Professor of Organic Chemistry Chairman. Dr. M. Sarkeys Energy Center Norman. Biogeochemistry The University of Western Australia 35 Stirling Highway Crawley WA 6009 Australia b) From with in the country Dr.This thesis has been evaluated by the following examiners External examiners: a) From Abroad i) Dr. OK 73019 USA ii) Dr. UET Lahore .

D. in Chemistry. _____________________ Signature .Declaration I “MUHAMMAD ASIF” declare that the Thesis entitled: “GEOCHEMICAL APPLICATIONS OF POLYCYCLIC AROMATIC HYDROCARBONS IN CRUDE OILS AND SEDIMENTS FROM PAKISTAN” is my own research work. This thesis is being submitted for partial fulfillment of the requirements for the degree of Ph. This thesis contains no material that has been accepted and published previously for the award of any degree.

Saeed Ahmad. Dean. Robert Alexander for his guidelines for understanding of kerogen chemistry of sedimentary organic matter. Dr. Department of Chemistry. Christiane Eiserbeck. Perth. University of Engineering and Technology. who’s keen interest. Dawn White. guidance and encouragement has been a source of great help throughout this research work. Zia-ulHassan and Anwar Nadeem for technical support through out my research. I would like to give respectful thanks to Prof.ACKNOWLEDGEMENTS I express my heartiest and sincere thanks to my respected and honorable Research Supervisor. Birgit Nabbefeld. Amy Bowater. I thankful to Prof. Fazeelat Tahira. source of knowledge and kind behavior towards me will be ever remembered. Muhammad Asif i . Curtin university of Technology. Her unforgettable cooperation. Arif Nazir and Imran Kaleem and many more for their friendly discussions and chat during this research thesis. Umair Akram. Christiane VVE. Hina Saleem. Dr. Sue Wang. brothers and sisters. Pierre Le Metayer. Director. Humanities and Islamic Studies. Tanya Chambers. Saleem Aboglila. Kieran Pierce. guidance. Ercin Maslen. Muhammad Irfan Jalees. Australia for providing me an opportunity to work with an excellent group. Their moral support is a great source of strength for me in every field of life. Dr. With out their prayers. Prof. Kliti Grice. Faculty of Natural Sciences. Chairman. Shahid Nadeem. Shagufta Nasir. Lahore. Dr. Special and heartiest thanks to Prof. Lahore for providing me an opportunity to complete my degree. WA-IOGC group. the present work would have been a merry dream. Ken Williford. I would like to acknowledge and thank to my friends Abdus Saleem. sacrifices and encouragements. I am happy to acknowledge the love and prayers of my parents. University of Engineering and Technology. I also thank to Geoff Chidlow. Svenja Tulipani.

high diahopane/hopane. Group C oils show higher marine OM (algal input) indicated by extended tricyclic terpanes (upto C41 or higher) and higher steranes/hopanes ratios.ABSTRACT Crude oils and sediments extracts from Kohat-Potwar Basin (Upper Indus Basin) were examined for polycyclic aromatic hydrocarbons (PAHs). Group A contains terrestrial source of OM deposited in highly oxic/fluvio-deltaic clastic depositional environment shown by high Pr/Ph. This relative abundance of heterocyclic aromatic hydrocarbons in Potwar Basin oils broadly indicate that the distribution of these compounds is controlled by depositional environment of OM where ii . The final chapter of this thesis (chapter 7) describes the formation of heterocyclic aromatic hydrocarbons and fluorenes in sedimentary organic matter through carbon catalysis reactions. Abundant biphenyls (BPs) and fluorenes (Fs) are observed in group A oils while group B oils showed higher abundance of dibenzothiophenes (DBTs) and negligible presence of dibenzofurans (DBFs) and Fs and group C oils showed equal abundance of DBTs and Fs. Diagnostic biomarker parameters along with stable bulk δ13C and δD isotope abundance reveal three groups of oils in Potwar Basin. Aliphatic biomarkers for rest of the oils indicate marine origin however two ranges of values for parameters differentiate them into two sub-groups (B and C). high diasterane/sterane. The first four chapters provide background to the research. PAHs distributions and compound specific stable hydrogen isotope compositions have been used to assess minor biodegradation in Potwar Basin oils. In chapter 6. low DBT/P ratios and higher relative abundance of C19 tricyclic and C24 tetracyclic terpanes. heterocyclic aromatic hydrocarbons. Group B oils are generated from clastic rich source rocks deposited in marine suboxic depositional environment than group C oils which are generated from source rocks deposited in marine oxic depositional environment. biomarkers and stable isotope compositions. distribution of PAHs and stable bulk carbon and hydrogen isotopes. Chapter 5 discusses the petroleum geochemistry of Potwar Basin where three groups of oils were recognized on the basis of diagnostic biomarkers. Distribution of PAHs classified Potwar Basin oils into similar three groups based on depositional environments and source OM variations.

sulfur compounds (i. Distribution of PAHs and stable hydrogen isotopic composition (δD) of nalkanes and isoprenoids has been used to assess the minor biodegradation in a suite of eight crude oils from Potwar Basin. Pakistan (group B). Pr/n-C17. Alkylnaphthalenes are more susceptible to biodegradation iii .7-dimethylphenanthrene (1. Higher abundance of aromatic biomarkers the 1.5-trimethylnaphthalene (1. The low level of biodegradation under natural reservoir conditions was established on the basis of biomarker distributions. The relative susceptibility of alkylnaphthalenes and alkylphenanthrenes at low levels of biodegradation was discussed.5-TMN). For the same oils.2. C27. C28) between the groups indicate different source origin of these compounds. The crude oils of group A and C are typically non-biodegraded mature crude oils whereas some of the oils from group B showed minor biodegradation indicated by higher Pr/n-C17. API gravity.e. Group A shows only C27 and C28 TAS while group B shows C25 to C28 TAS and absence of these compounds in group C oils revealed that the sterol precursors for these compounds are most probably different.e. The average D enrichment for n-alkanes with respect to the isoprenoids is found to be as much as 35‰ for the most biodegraded sample. δD values for the n-alkanes relative to the isoprenoids are enriched in deuterium (D). Higher abundance of C20 and C21 TAS and substantional difference in distribution of long chain TAS (C26. 1methylphenanthrene (1-MP) and 1. Variations in distribution of triaromatic steroids (TAS) in Potwar Basin oils clearly indicate source dependent of these compounds rather than thermal maturity.2. Aliphatic and aromatic hydrocarbon maturation parameters indicate higher (late oil generation) thermal maturity for all oils from the Potwar Basin. The data are consistent with the removal of D-depleted low-molecular-weight (LMW) n-alkanes (C14-C22) from the oils. The δD values of isoprenoids do not change during the minor biodegradation and are similar for all the samples. DBTs) are higher in marine source oils while oxygen compounds (DBFs) and Fs are higher in oxic/deltaic depositional environment oils.7-DMP) indicate major source of OM for group A oil is higher plant supported by abundance of conifer plants biomarker retene. Ph/n-C18 and low API gravity. Bulk stable hydrogen isotope of saturated fractions of crude oils show an enrichment in D with increase in biodegradation and show a straight relationship with biodegradation indicators i.

than alkylphenanthrenes while extent of biodegradation decreases with increase in alkyl substitution on both naphthalene and phenanthrenes. A range of biodegradation ratios (BR) are purposed from dimethylnaphthalene (DNBR), trimethylnaphthalenes (TNBR) and tetramethylnaphthalene (TeNBR) that show significant differences in values with increasing biodegradation and are suggested as good indicators for assessment of low level of biodegradation. Laboratory experiments have shown that activated carbon catalyses the reactions of biphenyls (BPs) with surface adsorbed reactants that incorporate S, O, N or methylene forming some common constituents of sedimentary organic matter namely, dibenzothiophene (DBT), dibenzofuran (DBF), carbazole (C) and fluorene (F). A relationship between the % abundance of the hetero element in kerogen and the abundance of the related heterocyclic compound in the associated soluble organic matter supports the hypothesis that these reactions occur in nature. More specific supporting evidence is reported from the good correlation observed between methyl and dimethyl isomers of the reactant BPs and the methyl and dimethyl isomers of the proposed product heterocyclics compounds i.e. DBTs, DBFs, Cs and Fs. It is suggested that these distributions reported for sediments and crude oils from the Kohat Basin are the result of a catalytic reactions of compounds with BP ring systems and surface adsorbed species of the hetero element on the surface of carbonaceous material. Similar distributions of heterocyclic aromatic hydrocarbon from Carnarvon Basin (Australia) were illustrated to show the global phenomenon of this hypothesis. Furthermore, the abundances of these compounds (DBT, DBF and BP) show similar concentration profiles throughout the Kohat Basin sediments suggesting that share a common source. These compounds also correlate well with changes in the paleoredox conditions. These data tends to point towards a common precursor perhaps lignin phenols of land plants. Coupling of phenols leads to BP, which has been demonstrated in laboratory experiments to be the source of C, DBT, DBF, and F.

iv

PUBLICATIONS AND CONFERENCE PRESENTATION

Asif, M., Grice, K., Fazeelat, T., Dawson, D., 2008. Oil-oil correlation in the Upper Indus Basin (Pakistan) based on biomarker distributions and compound-specific δ13C and δD. In: 15th Australian Organic Geochemistry Conference, 8-12th September, National Wine Centre, Adelaide, SA, Australia. Asif, M., Grice, K., Fazeelat, T., 2009. Assessment of petroleum biodegradation using stable hydrogen isotopes of individual saturated hydrocarbons and polycyclic aromatic hydrocarbon distributions in oils from the Upper Indus Basin, Pakistan. Organic Geochemistry 40, 301-311. Asif, M., Alexander, R., Fazeelat, T., Pierce, K., 2009. Geosynthesis of dibenzothiophene and alkyl dibenzothiophenes in crude oils and sediments by carbon catalysis. Organic Geochemistry 40, 895-901. Asif, M., Alexander, R., Fazeelat, T., Grice, K., 2010. Sedimentary processes for the geosynthesis of heterocyclic aromatic hydrocarbons and fluorenes by carbon reactions, Organic Geochemistry 41, 522-530. Fazeelat, T., Asif, M., Saleem, A., Nazir, A., Zulfiqar, M., Nasir, S., Nadeem, S., (2009). Geochemical investigation of crude oils from different oil fields of the Potwar Basin. Journal of Chemical Society of Pakistan 31, 863-870 Asif, M., Fazeelat, T., Grice, K., Petroleum Geochemistry of Potwar Basin, Pakistan: oiloil correlation by bulk stable isotopes and aromatic hydrocarbons distributions (In preparations for Organic Geochemistry).

v

TABLE OF CONTENTS
Chapter # ACKNOWLEDGMENTS ABSTRACT PUBLICATIONS AND CONFERENCE PRESENTATION TABLE OF CONTENTS LIST OF TABLES LIST OF FIGURES Chapter–1 INTRODUCTION 1.1 Petroleum Geochemistry 1.2 Polycyclic Aromatic Hydrocarbons (PAHs) 1.3 Hetercyclic Aromatic Hydrocarbons and Fluorenes in Crude Oils and Sediments 1.3.1 Incorporation of N, S, O Elements into Sedimentary OM 1.3.2 S Compounds from Laboratory Simulations 1.4 Carbon Catalysis 1.4.1 Kerogen 1.4.2 Coal 1.4.3 Activated Carbon 1.5 Scope and Framework of the Thesis Chapter–2 GEOLOGICAL SETTINGS AND DESCRIPTION OF SAMPLES 2.1 Geology Settings of Kohat-Potwar Geological Province 2.1.1 Depositional Settings of Kohat-Potwar Basin 2.2 Descriptions of Crude Oils and Sediments 2.2.1 Potwar Basin 2.2.2 Kohat Basin 2.2.3 Geochemical Description of Sediments Chapter–3 EXPERIMENTAL vi Description Page# i ii v vi x xi 1 1 1 8 9 11 12 12 13 13 13 16 16 18 21 21 24 25 28

3.4.1 Elemental Analysis of Sediments 3.3.3 Pentacyclic Terpanes 4.3 Isolation of Branched and Cyclic Alkanes 3.2.1.2.2 Laboratory Heating Experiments 3.1.1 Sample Preparation 3.1 n-Alkanes and Isoprenoids 4.6 Dibenzothiophene and Alkyldibenzothiophenes 4.5 Elemental Analysis-Isotope Ratio Mass Spectrometry (Bulk Isotope Analysis) Chapter–4 IDENTIFICATION OF BIOMARKERS AND AROMATIC HYDROCARBONS 4.4.3 Laboratory Experiments 3.2 Polycyclic Aromatic Hydrocarbons 4.1 Biphenyl and Alkylbiphneyls 4.1 Reference Compounds and Glass Tubes Preparation 3.3 Phenanthrene and Alkylphenanthrenes 4.2.2 Naphthalene and Alkylnaphthalenes 4.4.2 δ34S of Pyrite from Sediments 3.2 Geochemical Techniques 3.2 Tricyclic and Tetracyclic terpanes 4.4 Gas Chromatography-Isotope Ratio Mass Spectrometry 3.2.5 Diamondiod Hydrocarbons 4.2 Liquid Chromatography of Crude Oils and SOM 3.2.3 Gas Chromatography-Mass Spectrometry (GC-MS) 3.2.4 Analytical Methods and Instrumentation 3.4 Dibenzofuran and Alkyldibenzofurans 4.1 Materials and Reagents 3.3.2.2.4.1.5 Carbazole and Alkylcarbazoles 4.2.1.1.2.1 Saturated Hydrocarbons 4.4 Steranes and Diasteranes 4.4.7 Fluorene and Alkylfluorenes 28 29 29 30 31 32 32 32 34 34 35 35 36 37 39 39 39 40 41 43 44 45 46 47 48 49 50 51 52 vii .

2.2 Bulk Hydrogen Isotopic Compositions of Saturated Fractions 6.1 Alkylnaphthalenes and alkylphenanthrenes 5.2 Carbon and Hydrogen Isotopic Compositions 5.3 Polycyclic Aromatic Hydrocarbons (PAHs) 5.2.4 Affects of Biodegradation on Polycyclic Aromatic Hydrocarbons 6.2.2 Results and Discussion 5.2 Triaromatic steroids (TAS) 5.1 Heterocyclic Aromatic Hydrocarbons 5.2.1 Normal Alkanes and Isoprenoids Distribution 5.3 Compound Specific Hydrogen Isotopic compositions of nalkanes and isoprenoids 6.2.2.2.2 Results and Discussion 6.2.4.9 Compound Identification of Laboratory Experiments Chapter–5 GEOCHEMISTRY Of POTWAR BASIN CRUDE OILS Abstract 5.2.2.1 Introduction 6.2.4 Thermal Maturity of Potwar Basin Oils 5.2.6.2.5 Lithology and Depositional Environment 5.1 Assessment of Biodegradation 6.6 Source of OM 5.4.6.2.2.7 Biodegradation Conclusions Chapter–6 POLYCYCLIC AROMATIC HYDROCARBONS (PAHs) AND STABLE HYDROGEN ISOTOPE STUDY AS INDICATOR OF MINOR BIODEGRADATION Abstract 6.8 Identification of Retene 4.2.1 Introduction 5.2.5.1 Alkylnaphthalenes 53 54 55 55 56 59 59 59 63 65 70 73 74 81 83 87 91 93 93 94 95 95 100 101 106 106 viii .

3 Dimethyl homologous of heterocyclics and Fs a) DMBPs vs DMDBTs b) DMBPs vs DMCs and DMFs 7.2 Distribution of Heterocyclic Aromatic Hydrocarbon in Sediments and Crude Oils 7.1 Introduction 7.2.1 Laboratory Experiments on Active Carbon 7.6.2.2.3 Paleoredox Conditions and Heterocyclics Formation Conclusions REFERENCES APPENDIX 112 114 116 116 117 118 119 121 124 124 131 138 138 140 144 146 147 170 ix .2.4.2.1 Probable mechanism of geosynthesis reactions 7.2.2 Alkylphenanthrenes Conclusions Chapter–7 GEOSYNTHESIS OF HETEROCYCLIC AROMATIC HYDROCARBONS AND FLUORENES BY CARBON CATALYSIS Abstract 7.2.2.2.2 Results and Discussion 7.2.1.1 Parent compounds 7.2 Methylated homologous of heterocyclics and Fs 7.2.

4.1 4.1 6.2 7.3.2 6.2 5.LIST OF TABLES Table # 1.2 4.1 2.1 2. Identifications of steranes and diasteranes from Fig.14. Ring position relationships between BP and related heterocyclic compounds and Fs Concentration and Compound Ratios of Sediments and Crude Oils Page# 5 22 23 27 33 42 43 54 60 66 78 80 90 96 102 110 127 132 136 x .3 3.1 7.1 5.2 5.1 4. Concentrations of compounds and elemental kerogen composition for Kohat Basin sediments. Identification of compounds from Fig. isoprenoid ratios and bulk isotope data Thermal maturity parameters calculated from aliphatic and aromatic hydrocarbons Source OM and depositional environments parameters of Potwar Basin oils Biomarkers parameters limits for Potwar Basin oils Assessment of biodegradation results of Potwar Basin crude oils n-Alkanes.3 5. isoprenoids. 4.3 Description Aromatic hydrocarbons thermal maturity parameters Geological information of crude oils Geological settings and Rock Eval data of sediments from well Mela-1 Aliphatic biomarker maturity parameters of Mela-1 sediments Heating experiments details Identifications of pentacyclic triterpanes from Fig.2 2.3 7. 4.4.4 5. aliphatic biomarkers and diamondoids hydrocarbons ratios δD(‰)* values of n-alkanes and isoprenoids (pristane and phytane) from Potwar Basin oils Biodegradation ratios (BR) and alkylnaphthalenes ternary plot ratios. n-Alkanes.5 6.

108.6.10-trimethyltridecane (IV).6-dimethylundecane (I.2. 2. see appendix).2 40 4. Ph: phytane.6. c: 2. Generalized comparison of biodegradation sequence between aliphatic and aromatic hydrocarbons of crude oils Structurally related compounds Geological and Location map of Kohat-Potwar Basin oils (modified from [106. See section 3. C30: C30 17α(H)-hopane (Xb). Adamantane (XVIII) and methyladamantanes are shown by sum of mass chromatograms (m/z: 136+135) and diamantine (XIX) and methyldiamantanes are shown by sum of mass chromatograms (mz/: 188+ 187) from saturated fraction of representative oil sample (Adhi-5). Pakistan. Strachan et al. Peak numbers 19-41 denote carbon number of tricyclic terpane (VIII).10. d: 2. Identity of peaks refers to Table 4.LIST OF FIGURES Fig. e: 2. V). II). 2. X-XV) in Adhi-5 crude oil. C24*: C24 17.6.2 1.1 2.2 7 8 17 19 4. (a) Sum of mass chromatograms (m/z: 154+168) showing xi 41 4. and location of crude oils and sediments used in this study (Modified from Wandrey et al. Peak identity numbers refer to Table 4.10trimethyldodecane (farnesane. a: 2.6.3 for GC-MS program.4..3 Mass chromatograms (m/z: 191) showing the distribution of pentacyclic triterpanes (hopanes.14-tetramethylhexadecane (VII).6 46 .-trimethylpentadecane (nor-Pristane.4.1.4 43 4.3 2.3 for GC-MS program. Refer to section 3.4.14-tetramethylpentadecane (VI). III).21-secohopane (IX). [141].10. Pr: pristane.3 for GC-MS program Mass chromatogram (m/z: 191) illustrating tricyclic and tetracyclic terpanes in Dhurnal-1 crude oils. b: 2.4. # 1.4. Refer to section 3.5 44 4. 2004 and references therein) Total ion chromatograms (TIC) of saturated hydrocarbon fraction shows n-alkanes (n-C10 to n-C37) and isoprenoids in crude oil (Missakeswal-1).6.3 for GC-MS program. Refer to section 3. [19] and Armstroff et al.110-111]) Stratigraphy of Kohat-Potwar Basin.3 for GCMS program Mass chromatogram (m/z: 217) of Dhurnal-1 crude oil shows the profile of steranes and diasteranes.10-trimethylundecane (nor-farnesane.10.6. See section 3.1 Description Possible biological precursors and pathways for the generation of alkylnaphthalenes after Püttmann and Villar [180]. Page# 3 1.1 39 4.

NaN3. depth: 4290 m. XXVIII) and methylfluorenes in Kohat Basin sediment. tetramethylnaphthalenes are shown by sum of mass chromatograms (m/z: 170+184 respectively) in a representative oil (Adhi-5). Numbers on each peak refer to position of methyl substituent. Mass chromatograms m/z: 219 and 234 showed Retene (XXI) in aromatic fraction of Adhi-5 crude oil. Sum of mass chromatograms (m/z: 166+180) showing fluorene (F. 4710 m.14 53 54 5.11 51 4. (a) Sum of mass chromatograms (m/z: 184+198) sowing dibenzothiophene (DBT.13 4. methylnaphthalenes. Total ion chromatogram of the extract of laboratory experiment at 300 °C of reactants (biphenyl. depth. Identification is given in Table 4. diphenylmethane.8 48 4.1 62 .biphenyl (BP. numbers on each peak refer to respective methyl and dimethyl biphenyl isome 4.10 50 4. Depth: 4290 m.12 52 4. The plots (a) δ13Csats vs δ13Caros (b) δ13Caver vs δDaver to delineate xii 47 4. depth: 4690 m. methylphenanthrenes. Numbers on each peak refer to respective methyl substituent. activated carbon. dimethylnaphthalenes are shown by sum of mass chromatograms (m/z: 128+142+156 respectively) and (b) trimethylnaphthalenes.3. dimethylphenanthrenes shown by sum of mass chromatograms (m/z: 178+192+206 respectively) from aromatic fraction of Adhi5. XXIII). XXVII) and methyldibenzothiophenes and (b) mass chromatogram (m/z: 212) showing dimethyldibenzothiophenes from Kohat Basin sediment. Phenanthrene (XXIV). (a) sum of mass chromatogram (m/z: 167+181) showing carbazole (C. XXII) and methylbiphenyls and (b) mass chromatogram (m/z: 182) showing dimethylbiphenyls in aromatic fraction of a representative oil (Adhi-5). XXVI) and methylcarbazoles and (b) mass chromatogram (m/z: 195) showing dimethylcarbazoles from Kohat Basin sediment.7 (a) Naphthalene (N. Numbers on each peak refer to respective alkyl phenanthrene isomer. Numbers on each peak refer to respective methyl and dimethyl carbazole isomer. Numbers on each peak refer to methyl dibenzofuran isomer. DPM. Air) for 16 hrs. (Sum of mass chromatograms (m/z: 168+182) showing DBF (XXV) and methyldibenzofurans in Kohat Basin sediment.9 49 4. Numbers on each peak refer to respective methyl and dimethyl dibenzothiophene isomer.

Joyamir-4. c: 2. numbers on peak indicate TT. Group A. a. Distribution relationship between C20/C21 TAS and C27/C29 diasteranes from Potwar Basin oil clearly indicate three groups Representative TICs of saturated fractions from Potwar Basin oils.6.6. Distribution of triaromatic steroids in Potwar Basin crude oils a) Adhi-5. C17. 5.5 5.groupings of petroleum in the Potwar Basin.7 79 5. C25 indicate carbon number of n-alkanes. Dhurnal-1. [173-175]). b) Kal-2. C24-tetracyclic terpane and number with H indicate hopanes.4 72 5. Adhi-5.12 6. (a) Plot of Pr/n-C17 vs Ph/n-C18 and (b) API value vs.3 TICs showing distributions of aromatic hydrocarbons in representative samples from the Potwar Basin. Cross plot between C19/(C19+C23) TT and C24 TeT/(C24 TeT + C23 TT) shows difference in source material in Potwar Basin oils (c. c) Toot-12. Bar diagram shows relative percentages of DBTs. naphthalene. (a) Hopanes maturity parameters plot between C29 vs C30 of αβ/(αβ+βα) (c.10 5.10-trimethyldodecane (farnesane). Number on peaks refers to n-alkanes carbon numbers. N.f. [45] and refernces therein).6 75 77 5.10-trimethylundecane (norfarnesane). Carbon number on peak refers to corresponding TAS (XXa to XXh). []156) show different thermal maturation stages of oil generation window. group C.10. Fs in Potwar Basin oils. UCM.f. Pr. d: 2. (a) Distribution relationship between TMN ratios of Potwar Basin oils (b) higher plant aromatic biomarkers ratios 1. 24*. phytane. DBFs.9 84 5.7-DMP/X and 1MP/9-MP [5] indicated terrestrial input for group A oil. pristane and Ph. [11]) and Rc (MPI-1.-trimethylpentadecane (nor-Pristane). . e: 2.11 86 88 5.1 89 97 xiii . 2. Pr/n-C17 showing biodegradation trends in crude oils used in this study. group B. unresolved complex mixture. Mass chromatograms (m/z 191) showing distribution of tricyclic (TT) and pentacyclic terpanes (hopanes. Total ion chromatograms of saturated hydrocarbon fractions for Potwar Basin crude oils showing different degrees of biodegradation.2 5.8 82 5. H) in Potwar Basin crude oils. [152]) (b) calculated vitrinite reflectance diagram from Rcb (TNR-2.. b: 2. (a) Pr/Ph versus DBT/P plot indicates lithology and depositional environment [167] (b) C30 17α-diahopane/C30 17α-hopane vs C29 diasteranes/sterane plot shows the affects of clay and depositional environment on Potwar Basin oils (c. 64 67 5.f.6-dimethylundecane.6.6.10trimethyltridecane.

[38] for TMNr (1. trimethylnaphthalenes.3. [15]).5. 1.3. S.2 Relationship between API gravity and biodegradation parameters (BP1 and BP2.7/1.7+1.7/1.2.3 6. Each blank experiment was identical in composition.2. (a) API gravity. Numbers on each peak refer to respective alkylnaphthalene isomer and highlighted peaks show isomer components most affected by rising biodegradation Order of susceptibility of alkylnaphthalenes and alkylphenanthrenes to microbial attack in the Potwar Basin crude oils (cf. DMNs.7/1.2. MBPs. sulfur. TeMNs).3. BP.3.6.6+1. biphenyl.8 111 6. and (b) Pr/n-C17 Biodegradation susceptibility for alkylnaphthalene distributions (m/z 156+170+184.2. BP.3. TNBR and TeNBR is observed. Each blank experiment was identical in composition.1 120 7. temperature and time but without coal.2.2 122 . A combined chromatogram of MP’s and DMP’s (m/z: 192+206) shows decrease in relative intensity with in increase in biodegradations.5. temperature and time but without activated carbon. TeMNr (1. S. Plot of δD(‰) difference between LMW n-alkanes (n-C14 . δDsats vs. n-C14-n-C22.n-C22) and isoprenoids vs. Pr/n-C17 showed a good correlation. tetreamethylnaphthalenes.7+(1.4. activated carbon. A significant decrease in DNBR.5)-TeMNs and PMNr (1. TMB. Pr/n-C17 shows enrichment in deuterium of saturated fractions with increase in biodegradation. (a) n-C14 to n-C29 n-alkanes (b) significant effect of biodegradation is observed in n-alkanes.5. [203]) showing API to by controlled by biodegradation rather than any other factor such as mixing.6. Ternary plot was plotted using similar conditions for analysis and identifications as reported by van Aarssan et al.6 105 107 6.7 108 6. TICs of extracts from laboratory heating experiments at temperature 270 °C for16 hr.6)-PMNs. Polymethylnaphthalenes biodegradation ratios vs. AC.9 113 7. TMNs.5. Samples were heated at 300 °C for16 hr.7+1.4.4 100 103 6.2. dimethylnaphthalenes. methylbiphenyls. biphenyl. Numbers refer to positions of methyl substituents.2. xiv 99 6. sulfur. Total ion chromatograms (TIC) of extracts from laboratory heating experiments.5)-TMNs.6.3.3.5 6. The numbers on peaks indicate the respective alkyl substituted isomer of phenanthrene and highlighted peaks show significant depletion as move to more biodegraded sample.4-tetramethylbenzene. The δD (‰) distribution of n-alkanes from Potwar oils.

DBT. Pakistan. 1.12 141 xv . 4680 m).4 125 7. Numbers on peaks indicate dimethyl substituted isomers of BP and DBT (Table 7.7. MBPs (m/z: 168).5 126 7. TMB. DBF and F) for Kohat Basin sediments (data given in Table 7.4-tetramethylbenzene. Pakistan sediment (Depth. Relationship between compounds in SOM and the N. Representative ion chromatograms show relative distributions of MDBTs (198). MBPs. Purposed reaction pathways on activated carbon for formation of heterocyclic aromatic compounds and F from BP. 300°C and 16 hr. Upper Indus Basin. F. methylbiphenyls. activated carbon. MFs (m/z 180). b) Wanaea. Symbols relate precursor-product compounds.2). a) Mela-1.6 7. NW Australia. S: sulfur. dibenzothiophene. 123 7.1). Australia. MBPs (m/z 168). activated carbon. biphenyl.2. Distributions of MBPs and methyl homologues of DBF.7 129 130 7. DBF. AC. TICs of extract of heating experiments of BP with activated carbon using different alkyl precursor compounds. Symbols relate precursor-product compounds Relationship between MBPs and MDBTs in Kohat Basin sediments. AC.3 Mass chromatograms (m/z: 198) of the extract of heating experiments of 3-MBP with elemental S in the presence of active carbon at different temperatures. Carnarvan Basin. Relative distribution of DMBPs and DMDBTs in Kohat Basin sediments (depth. DMBPs (m/z 182). Relationship of reactant (BP)-product (DBT. BP. MDBTs (m/z 198) and DMDBTs (m/z 212). dibenzofuran. C and F in crude oils from two different basins. MDBFs (m/z 182) and MCs (m/z 181). a) Chaknaurang. MDBFs (m/z: 182). Relative distributions of methyl and dimethyl biphenyls and dibenzothiophenes in crude oils from two different basins. C. 4345 m). Pakistan. a) absolute concentration plot shows association between individual isomers of MBPs and MDBTs.1). MBPs (m/z 168). heating temperature and duration was same for all experiments i. Kohat Basin.e. Carnarvon Basin.9 135 7. Symbols relate precursor-product compounds. and O concentration of kerogen from each sample (data given in Table 7.8 133 7. fluorene. b) plot shows ratio of MBPs and MDBTs to the parent BP and DBT in sediment samples. BP.10 137 7.11 139 7. b) Barrow. carbazole.3. S. Symbols relate precursor-product compounds. MCs (m/z: 181) and MFs (m/z: 180) from the Kohat Basin. biphenyl.

14 145 xvi . DBF. 4940 m) and the Carnarvon Basin Griffin crude oil.13 Relative distribution of DMBPs (m/z: 182). BP. DMCs (m/z: 195) and DMFs (m/z: 194) in the Kohat Basin sediment (Depth. Numbers on peaks indicate dimethyl substituted isomers. Symbols show precursorproduct relationships (Table 3) δ34S(‰) of pyrite against concentrations of DBT.7. C and Pr/Ph with depth in Kohat Basin sediments Pakistan. ____ 142 7.

and their subtle structural transformation could be indicative of depositional environment.5-trimethylnaphthalene (1.2 POLYCYCLIC AROMATIC HYDROCARBONS (PAHs) Aromatic hydrocarbons are important constituents of petroleum and extracts of both recent and ancient sediments [3-7]. oxidation and reduction in sedimentary environment for millions of years [2]. where a characteristic part of the naphthenic structure has been preserved unchanged. Crude oil is a complex mixture of thousands of organic compounds.5-TMN). accumulation and alteration of crude oils and natural gas [1].2. catalytic effects of clastic minerals. formed through processes i.7tetramethylnaphthalene 9-methylphenanthrene 1 . migration.2. (9-MP). 1. thermal maturity and biodegradation. Distributions of PAHs are potentially useful in many areas of applied petroleum geochemistry. The distribution of these compounds is highly diagnostic of source organisms. A biomarker is compound in geological samples that can structurally related to the natural products of the living organism i.1 INTRODUCTION 1. higher plants. bacteria. The biological origin of a given PAHs is obvious only in favorable conditions. 1.5. animals.61. The majority of PAHs in petroleum are the products of complex chemical transformations of nephthenic and/or olefinic biological ancestors during diagenesis and catagenesis [4.2. (1.5. Abundance of certain aromatic hydrocarbons in crude oils and sediments such as 1. The relative proportions of biomarkers are routinely being used by geochemists to reconstruct ancient depositional environment and to correlate crude oils to their source rocks.6-TeMN).e.1 PETROLEUM GEOCHEMISTRY Petroleum geochemistry is the study of geochemical processes that lead to the formation. algae which are the source of OM. fungi. deposition.Chapter .9].2.e. PAHs are not synthesized in living organisms and almost absent in natural OM [8]. thermal and bacterial alteration of organic matter (OM).

1).1).aromatics [1924] (Fig. 1. coals and sediments [14-17].7-Trimethylnaphthalene is suggested to originate from compounds like β-amyrin that are constituents of angiosperms (Fig.1). 1.7-DMP) originate from diterpenoid and triterpenoid natural products [4-5] (Fig. The abundance of certain isomers of alkylphenanthrenes in geological samples indicate specific source precursors for these 2 .18-19] (Fig. Alkylnaphthalenes has been suggested to be originated from terrestrial sources [4]. The most useful application of aromatic hydrocarbons is evolution of thermal maturity of OM [10-11]. tetra. On the basis of laboratory heating experiments and examination of geological samples Bastow [30] suggested precursor-product relationship between certain isomers of tri-. affects of biodegradation of aromatic hydrocarbons has been reported in crude oils.and penta-methyl naphthalenes and reported methylation of naphthalenes and phenanthrenes is a geosynthetic process. Clay minerals act as a catalyst to enhance the alkylation and decomposition of parent aromatic hydrocarbons during sedimentary processes [31] and abundant alkylnaphthalenes has been attributed to ring isomerization and transalkylation processes [19].2. 1.dimethylphenanthrene (1. 1. Furthermore. terpenoids and alkaloids have been considered as possible pathways/precursors for the formation of mono-.9. 1.1). It is commonly observed that alkyl substituted aromatics are the major components as compared to their parent (non alkyl substituted) hydrocarbons [2529]. Specifically.and tri. Biological compounds such as cyclic sesquiterpenoids from resins of conifer plants are potential precursors of alkylnaphthalenes. diagenetic and catagentic transformations of carotenoids. Alteration of functional groups in biological structures commonly occurs through decarboxylation or dehydration and unsaturated bonds provides a starting point for cyclization and aromatization [4. The correlation of oils using aromatic hydrocarbon distributions and alteration of crude oils in reservoirs are other important application discussed [12-13]. di. Precursor compounds of PAHs The widespread occurrence of PAHs in sedimentary OM is the result of complex chemical transformation of biological precursors under sedimentary conditions. They are proposed to be the product of both the organic facies as well as the processes (diagenesis and catagenesis) through which OM passes during thermal stress [30].

1 Possible biological precursors and pathways for the generation of alkylnaphthalenes after Strachan et al. [19] and taken from Armstroff et al. 3 . 1.Fig. ([23] and references therein).

[34] refers to biphenyl carbon skeletons such as ellagic acid in natural products as possible precursors of sedimentary biphenyls.38 and references therein) shown in Table 1. Previous study by Alexander et al. Similar principal has been used to devised number of polycyclic and sulfur aromatic hydrocarbons maturity parameters [4. such as retene and pimanthrene could have formed through aromatization of tricyclic diterpenoids of plant resins [32] or by the dehydrogenation of alkylated dihydrophenanthrenes [33]. For example methylnaphthalene ratio (MNR) is thermal maturity parameter derived by dividing thermodynamically less stable isomer 1-methylnaphthalene (1-MN) (α-isomer) with thermodynamically more stable isomer 2-methylnaphthalenes (2MN) (β-isomer) [25]. Thermal maturity applications of PAHs The principal application of C10+ aromatic hydrocarbons has been as maturity indicators for crude oils and sediments extracts [10. Biphenyls have lowest relative abundance compared to other aromatic series.1.35-38].25-26.compounds. Minor amounts of these compounds and their alkyl analogues have been identified in marine sediments of Cambrian age [13]. The most common approach exploits changes in the relative abundance between isomers of aromatic hydrocarbons with increase in thermal affects. The concept is the shift of αmethyl group to β.position with increase in thermal maturity [26] whereas methyl shift resulted in a decrease in steric strain. 4 .position is thermodynamically more stable. hence β.

PMNr Methylphenanthrene index-1.3.7-TeMN/(1.3.3.5. MDR′ Definition 2-MN/1-MN (2.5DMN 2.7-TMN + 1.6. MP: methylphenanthrene.5-TMN) (1.7-TMN/(1.7-TeMN + 1. PMN: pentamethylnaphthalene.5.3. MPI1 Methylphenanthrene ratio.3.3.7-TMN + 2.6-PMN) 1.5-TMN) 1.5-TMN + 1. 5 .2. MDBT: methyldibenzothiophene. TNR-1 Trimethylnaphthalene ratio-2.7-PMN + 1.2.3. DNR-1 Trimethylnaphthalene ratio-1. MNR Dimethylnaphthalene ratio-1. TeMN: tetramethylnaphthalene.6.3. DMN: dimethylnaphthalene.6-TMN) 1.1 Aromatic hydrocarbons thermal maturity parameters Name and abbreviation Methylnaphthalene ratio. TMNr Tetramethylnaphthalene ratio.6.3.2.6-TMN/(1. TNR-2 Trimethylnaphthalene ratio-1.3.4.6. MDR Methyldibenzothiophene ratio.6-DMN + 2.6-TMN + 1. TMN: trimethylnaphthalenes.4.2.6-TeMN + 1.5 × (2-MP + 3-MP)/(P + 1MP + 9-MP) 2-MP/1-MP 4-MDBT/1-MDBT 4-MDBT/(4+1)-MDBT Reference [26] [26] [10] [11] [38] [38] [39] [25] [26] [11] [40] MN: methylnaphthalene.3.2.2.7-PMN/(1.6-TMN)/ (1.4. TeMNr Petnamethylnaphthalene ratio.5TeMN) 1.4.6-TMN + 1. MPR Methyldibenzothiophene ratio.Table 1.3.5-DMN)/1.

[43] on Chinese biodegraded oils has reported higher susceptibility of trimethylnaphthalenes over dimethylnaphthalenes and methylphenanthrenes over phenanthrene [43]. 6 .g. Biodegradation of alkylphenanthrenes indicates that depletion of methylphenanthrenes starts after complete removal of n-alkanes while dimethylphenanthrenes show resistant to biodegradation till steranes are altered [15.41.43]. In reservoir biodegradation of PAHs starts with smaller rings e.44].41-43]. A comparison biodegradation sequences between aliphatic and aromatic compound classes is shown in Fig.2. However study by Huang et al. Biodegradation susceptibility order of saturated and aromatic hydrocarbons shows that alkylbenzenes alter along with n-alkanes but persist till the depletion of isoprenoids [45]. benzenes are depleted first followed by naphthalenes and then phenanthrenes [15.Biodegradation of PAHs The effects of biodegradation on PAHs have been reported in different studies [15.41. Demethylation of alkylnaphthalenes and alkylphenanthrenes was purposed as biodegradation process as reason for this reverse susceptibility orders of depletion [43]. Alkylated PAHs show a range of susceptibility difference but generally methyl substituted isomers are degraded in preference to dimethyl and trimethyl isomers of benzene. naphthalene and phenanthrene [15. Minor alteration of methyl and dimethylnaphthalenes are observed during depletion of nalkanes however trimethylnaphthalenes show depletion along with isoprenoids while tetramethylnaphthalenes are resistant to biodegradation till the substantional removal of steranes [15]. 1.43-44].

[49]. Arrows indicate extent of depletion of compound class where first altered (dashed lines).48]. For more detail see Peters and Moldowan. significant depletion (solid grey line) and completely removed (black arrow). 7 . [46] indicates change in oil quality with extends of biodegradation.Wenger et al. 1. [47].2 Generalized comparison of biodegradation sequence between aliphatic and aromatic hydrocarbons of crude oils [45-46]. Fisher et al. H: heavy. Wenger et al..and trimethylbiphenyls L 1 M 2 H 3 4 5 6 Severe 7 8 9 10 Fig. L: light. Triolio et al. [15. M: moderate. [46] Biomarker Biodegradation scale 0 n-alkanes Alkylcyclohexanes isoprenoids C14-C16 bicyclic terpanes Hopanes (25-norhopane present) steranes Hopanes diasteranes C26-C29 aromatic steriods Porphyrins Methyl.and dimethylnaphthalenes Trimethylnaphthalenes Methylphenanthrenes Tetramethylnaphthalenes Dimethylphenanthrenes Methylbiphenyls Ehtylphenanthrenes Ethyl.

dibenzofurans (DBFs). It is noteworthy that biphenyl shows a structural associations with these heterocylics compounds (Fig.50-51]. N) within the benzene structures. Here it may be supposed that these heterocyclics compounds may have same origin and/or source precursors in sedimentary organic matter. It is interesting to see that all these compounds show similar structural features except heteroatoms (Fig. O.3 Structurally related compounds 8 . The heteroatomic aromatic hydrocarbons i. carbazoles (Cs). Some of them only contain benzene structures like naphthalene and phenanthrenes while some have heteroatoms (S. 1.e.11-12. heterocyclics such as dibenzothiophenes (DBTs).3).3 HETEROCYCLICS AROMATIC HYDROCARBONS AND FLUORENES IN CRUDE OILS AND SEDIMENTS PAHs in petroleum are abundant with various structural features. 1. Knowledge of specific source precursors and reaction pathways for the formation of these compounds in crude oils and sediments has not been reported.1. and fluorenes (Fs) are important constituents of sedimentary OM [6. The origin of these compounds in sedimentary OM is under debate for last three decades.3). Biphneyl S O Dibenzothiophene Dibenzofurane N H Carbazole Fluorene Fig. 1.

DBTs) are higher in marine water depositional environments while oxygen heterocyclics (i. Although contrasting results have been reported concluded from Canadian oils that carbazoles concentration are not affected by variation in thermal maturity and depositional environments [56]. The abundance of heterocyclics aromatic hydrocarbons and fluorenes in crude oils and sediments has been shown a relationship with sedimentary depositional environments.e DBFs and Fs) are higher in freshwater depositional environments [12-13]. coals and crude oils [4.The sulfur heterocyclics aromatic hydrocarbons (dibenzothiophene and alkyl dibenzothiophenes. The N containing biomacromolecules e.e. The oxygen heterocyclic aromatic hydrocarbon.1 Incorporation of N. So the incorporation of hetero-elements in to sedimentary OM is important and brief description about the topic is given below. DBFs and related compounds are present in significant abundance in terrestrial OM [6] and have also been suggested as oxidative degradation products of coals [54]. For example sulfur heterocyclics (i. It is commonly observed that the generation of heterocyclics in sedimentary environments is controlled by oxic/anoxic depositional conditions. O Elements into Sedimentary OM The incorporation of heteroatoms into the sedimentary OM takes place during the early diagenesis [2]. Moreover.3. benzocarbazoles are reported as good migration indicators in petroleum reservoirs [57]. DBTs) have been used to determine the thermal maturity of sediments.58] where it is indicated that the distribution of these compounds depends on the depositional environments of source OM while alkylfluorenes are not yet reported in any from of sedimentary OM so for. A limited geochemical significance of F are only reported for oil correlation studies along with DBT and DBF distributions [12. These finding could be used to build an idea that the formation of heterocyclics aromatic hydrocarbons may depend on the abundance of heteroatomic species in sedimentary OM. S.7. Pyrrolic nitrogen (N) compounds have shown dependence on organic facies and thermal maturity of OM [5051].52-53].37. Moreover. amino acids interact 9 . 1. thermal maturity and lithology of source rocks are shown to control the distribution of dibenzofuran and alkyldibenzofurans [55].g.

The occurrence of thiophenes in the S-rich kerogen pyrolysates does not necessarily reflect a ubiquitous contribution of thiophenic moieties to kerogen structure. However the structure of N containing molecules varies with increase in thermal maturity of kerogen and coal [60-61]. The former process results in the formation of cyclic alkyl sulfides (like thiolanes. at least partly. heating (poly)sulfide-linked macromolecules results in the rapid formation of thiophenic compounds [70-72]. [66] while Intermolecular sulfurization leads to the formation of (poly) sulfide linkages between alkyl chains [67-68]. N content of OM do not change substantially up to the formation of petroleum and natural gas [59]. The abundance of N incorporation depends on the biological source of OM i.and intermolecular reactions [65].and incorporate into OM at early diagenesis. terrestrial plants contribute less N than phytoplanktons. The sulfate reducing bacteria produces S which is the source of S at the water/sediment interface and results its incorporation at early stage of diagenesis through abiotic reactions [63-64]. A minor contribution of NH4+ ion in kerogen is always observed which decreases with increase in thermal maturity. However. 10 . Brassell et al. Immature coals and kerogen show the presence of N in the form of amide/amine groups [61] whereas pyrrole and pyridine N structures are observed during the formation of petroleum [62]. such aromatic sulfur compounds may originate. The mechanism of S incorporation into the OM depends on the nature of sulfurized functional groups and can be incorporated via intra. Depositional settings of OM also affect the relative preservation of N for example clay rich contents interacted with biological OM and incorporate more N [59]. In fact.e. Sulfur (S) is the most abundant hetero-element in all types of sedimentary OM found both in soluble and insoluble OM. These findings reflect the importance of incorporated S in kerogen for the formation of sulfur compounds. Secondary thermal reactions of (poly)sulfide-bound linear carbon skeletons were observed upon kerogen pyrolysis [73]. this could be due to the interaction of pyridine and OH groups in the kerogen [60].g. thianes and thiophenes. e. from secondary transformation of (poly)sulfide-containing moieties [69]. At the end of diagenesis.

These findings show that there are such examples where heteroatoms species chemically react with sedimentary molecules with and with out catalyst.During early diagenesis. A brief introduction for carbon catalysis and 11 .2 Sulfur (S) Compounds from Laboratory Simulations Examples of laboratory experiments of heteroatom species other than S with hydrocarbons are scarce however there are many examples of laboratory chemical reactions between S species and different biological compounds are reported. A new approach is established where activated carbon has been successfully used as catalyst to evidenced different sedimentary reactions [81].77]. [74] studied the kerogen pyrolysates from Kashpir oil shale (Russia) high abundance of oxygen functional groups (C=O) on different carbons of alkyl chains was observed. alkylated aromatic hydrocarbons. S reactions with unsaturated isoprenoids followed by cyclization and aromatization were reported for the formation of benzothiophenes [65. oxidation is the partial degradation of immature OM and increase in oxygen/carbon (O/C) ratio in the kerogen. The temperature (450-630 °C) involved in these reactions is considerably higher than sedimentary temperatures.3. amino acids and humic acids has been used in these simulation experiments [75-76]. oxidation of OM is the major cause of decrease in TOC and enrichment of residual OM in oxygen. However in contrast to S incorporation. O incorporation may occur at any stage of kerogen evolution [59]. Riboulleau et al. Common sedimentary hydrocarbon precursors such as terpenes. the formation of dialkylated dibenzothiophenes was reported and related to sulphurized triterpeniods source precursors [78]. Insertion of S in aromatic hydrocarbons at mild temperatures has been reported using elemental S/pyrite with and without additives as catalyst [80]. Furthermore. This study was related to obtaining information about the early stage of the coalification processes when elemental S is present. steroids. Direct insertion of a heterosulfur bridge into biaryls and angulary condensed arenes has been reported using hydrogen sulfide and a heterogeneous catalysis [79]. 1. Thus. These results showed the O insertion at C=C in the kerogen after diagenetic isomerization and random migrations.

[90] was balanced in all aspects of functional group analysis of the whole kerogen and heteroatoms (N.34 while start of catagenesis introduced aromatic moieties which further increased the aromatic clusters at 12 . Behar and Vandernbroucke [91] reported a detailed structure evolution with change in diagenesis and catagenesis of the kerogen type II. This comparison provides an overview that the structure and nature of surface adsorbed species in different forms of carbonaceous material is broadly same. First. N and S atoms. Following section describe a structure comparison of different form of carbonaceous material i. Kerogen structure purposed by Siskin et al. O) distribution. Carbon catalyst concept extends to study the formation of different sedimentary hydrocarbons where it is supposed that carbonaceous material (kerogen and coal) provide a catalyst support. Evidence that the solid–state carbonaceous material promotes chemical reactions in sediments has been suggested from data obtained from hydrogen exchange reactions between hydrocarbons [81. S. coal and activated carbon.4 CARBON CATALYSIS Activated carbons have long been used as a catalysts and catalyst support [82-84].structure comparison between different form of sedimentary OM (kerogen and coal) with activated carbon is given in following section. Second. Chemical structure of kerogen at the beginning of diagenesis showed higher aliphatic structures with higher hydrogen/carbon (H/C) ratio 1. 1. it has been shown that carbon surface adsorbed species reacted with provided compounds to produce structurally related compounds.4.e. methoxyl groups.85]. 1. Later substantional work has been performed on kerogens structure particularly on Green Rive Shale [87-89]. alkoxy and S bridges which attached the aromatic nuclei with hydroxyl. In these studies. kerogen.1 Kerogen Forsman [86] recognized two types of kerogen on the basis of functional groups and degradative studies. coaly kerogen which contains macromolecules consisting of condensed aromatic rings interconnected by ether. non-coaly type kerogen showed nearly open chain structure with cycloparaffine or aromatic rings attached through O.

2 Coal Significant work has been done on the coal structure models (for review see. HCN and reported the formation of nitrogen species such as amide. and coals. Although the elemental compositions (C. In the case of activated carbons. carbon blacks. as move from peat to bituminous to anthracite indicated different coalification stages. the aromatic moieties of coal structure increases. H) changed in same pattern as was reported in case of kerogen but oxygen is exclusive part of bituminous coals [95]. H2S [103] and SO2 [104]. they are generally formed by heating the carbon in the presence of elementary sulfur [101] or sulfurous gases such as CS2 [102]. activated carbons.4. pyrroles and pyridines [100]. The carbon-sulfur surface compounds have been reported on a wide variety of charcoals. carboxylic. phenolic.3 Activated Carbon Activated carbons structure has been proposed similar to the structure of coal [96] and successful conversion of coal to active carbon has been reported by different studies [97-98]. carboxyl. [92]) and mostly focused on the quantitative distribution of functional groups and carbon-carbon bond types.73). ether and quinone. Different oxygen containing functional groups were reported such as.5 SCOPE AND FRAMEWORK OF THE THESIS Previous studies have described oil correlations from Pakistani crude oils and sediments from Upper Indus (Kohat-Potwar) Basin however these studies have focused on basic geochemical analysis such as total organic carbon (TOC) and Rock Eval 13 . 1.4. imide. van Krevelen. These kerogen structures contain different macromolecular composition depend on rank/stage of diagenesis and catagenesis. lactam.the end of catagenesis (H/C ratio 0. Boehm [99] studied the structure of active carbon and devised acidic and basic surfaces groups. N adsorption on active carbon has been devised by treatment with different nitrogen substances such as NH3. 1. lactoles. 1. The coal structure showed similar type of saturated and aromatic macromolecules as that of the kerogen [94]. Coal structure at different coalification ranks has been assumed to differ only in functional groups content and bond types [93]. Generally. carbonyl.

Second.e. first. it is shown that activated carbon plays a key role in the geosynthesis of heterocyclics aromatic hydrocarbons in subsurface environments. In chapter 6 affects of minor biodegradation on alkylnaphthalenes and alkylphenanthrenes. The study gave an insight to petroleum geochemistry of the area which is first ever of its kind. source of OM. Moreover. In chapter 7. Very little information is available on biomarkers and virtually no information is available on aromatic hydrocarbons present in Pakistani crude oils and sediments so for. In chapter 5 saturated and aromatic hydrocarbon parameters used to establish oil-oil correlation study in a suite of 18 crude oils.analysis. depositional settings and lithology of OM and affects of biodegradation on hydrocarbons. stable hydrogen isotopic composition of n-alkanes and pristane and phytane were reported. The main objectives of any organic geochemical study are to establish i. geosynthesis of heterocyclic aromatic hydrocarbons and fluorenes by carbon catalysis laboratory simulation experiments. Pakistan. Australian crude oils. This thesis broadly contained three objectives. It shows that susceptibility to biodegradation of alkylnaphthalenes and alkylphenanthrenes varies with the extent of biodegradation. carbon catalysis geosynthesis is supported by adding distribution of heterocyclics and fluorenes from Carnarvon Basin. assessment of minor biodegradation using PAHs distributions and stable hydrogen isotopes compositions of nalkanes and isoprenoids from selective Potwar Basin crude oils and third. Bulk stable carbon and hydrogen isotopic compositions of saturated and aromatic hydrocarbon fraction were used to delineate the oil groupings of Potwar Basin. classification of Potwar Basin oils using aliphatic and PAHs distributions along with stable carbon and hydrogen isotope compositions of saturated and aromatic fractions. Distribution of heterocyclics and fluorenes is determined in sediments and crude oils from Kohat Basin. Compound specific isotope analysis of n-alkanes and isoprenoids revealed that microbes preferentially consumed isotopically lighter n-alkanes and residual compounds become enriched in D of n-alkanes while isoprenoids D values are not affected at minor biodegradation. Different heteroatomic species show adsorption on carbon surface at moderate heating 14 . thermal maturity.

These heteroatom adsorbed species reacted with biphenyl and methylbiphenyls to produce heterocyclics aromatic hydrocarbons i. Natural sedimentary OM has been shown a structure association between biphenyls and these heterocyclics aromatic hydrocarbons. The evidences of various carbon surface species are reported to devise the reaction intermediate and pathways for geosynthesis of these compounds. dibenzothiophene (DBT). Australia. dibenzofuran (DBF). ____ 15 . Pakistan and Carnarvon Basin.e. Abundance of these compounds are used to show the product precursor relationship between biphenyls and these compounds in sediments and crude oils from Kohat Basin.temperatures. carbazole (C) and fluorene (F) and their methyl homologous.

1 GEOLOGY OF KOHAT-POTWAR GEOLOGICAL PROVINCE The Kohat-Potwar Basin also called Upper Indus Basin is situated in northern Pakistan and located between lat. 32° and 34° N and. The basin infilled started with thick InfraCambrian evaporate deposits overlain by relatively thin Cambrian to Eocene age platform deposits followed by thick Miocene-Pliocene molasses deposits. The detailed petroleum geology of the area has been described by different authors [106-108]. The Infra-Cambrian salt provided an easy detachment of Eocene-to-Cambrian (E-C) sequence as a result of intense tectonic activity during Himalayan Orogeny during Pliocene to middle Pleistocene time. 16 .2 GEOLOGICAL SETTINGS AND DESCRIPTION OF SAMPLES 2. the East and West of river represent the Potwar and Kohat Basins respectively (Fig. The geological division between Kohat and Potwar is done naturally by river Indus. The Kohat-Potwar Basin is a portion of Indian plate deformed by Indian and Eurasian plate collision and overthrust of Himalayas on the north and northeast [105]. The eastern Potwar contains carbonate reservoir rock of Cambrian to Tertiary ages. The geological structure of the Potwar Basin is one of the most complex structures of the world which is the result of the Tertiary Himalayan collision between Eurasian and Indian plates [105]. 70° and 74° E (Fig. 2.1).2). on the South by Surghar and Salt Ranges and on the East by Jehlum fault.1).Chapter . long. The E-C layer varies from a few meters to 400 m in the eastern Potwar [109]. The crude oils discovered from this area showed a range of reservoir formations (section 2. 2. This thinner E-C sequence in eastern Potwar affected by compressional forces has generated large number of fold and faults. on the West by Kurram fault. This intense tectonic activity has affected Eastern Potwar the most compared to Western Potwar. It is an onshore basin bounded on the North by Parachinar-Muree fault.

Fig. 17 .108.2.110-111]).1 Geological and Location map of Kohat-Potwar Basin oils (modified from [106.

This whole sequence is marine in origin and terminated by a major unconformity [106]. 2. Eocene through Pliocene are involved in a complex fold and thrust belt in which Eocene salt occupies the cores of many of the anticlines. siltstone. 18 . shale and dolomite represented by Kussak. Permian Nilawahan Group (Fig. 2. Mesozoic to late Permian and Eocene to Oligocene. massive sandstone and marine shales of Lower Cambrian Jhelum Group. This emergence was higher in south and east of the Basin evidenced by less deposition in cretaceous sections [112]. Three major unconformities in the area are Ordovician to Carboniferous. the geological information of Kohat Basin is scarce but unconformities and sharp variation in deposition made this area is very unpredictable (see [112]). Some fluvial sandstone with occasional shale and coal seams were deposited within the marine sequence of Warcha and Sardhai Formations [106]. 2.2). Kohat Basin showed absence and/or very thin deposition in Cretaceous times due to erosion and emergence out of the area from sea. Sedimentation in the Kohat-Potwar area began in the Precambrian and lasted until the Pleistocene. Jutana. Upper Eocene is more deformed than Lower Eocene where this area deformation resulted in duplex structures in Kohat formation of Eocene [112].The Kohat Basin is tectonically complex area of northern Pakistan and is a tilted plateau where moderate-steeper dips and asymmetrical structures resulted in a large number of thrusts/normal faults [112].2.1. The basin infilled started with thick infra-Cambrian evaporates with carbonates and oil-impregnated shales represented by Salt Range Formation which is overlain metamorphic rocks reported as the oldest sedimentary rocks in the Kohat-Potwar Basin [106]. Khewra Formation are deposited. Cambrian rocks comprised sandstone. marl and fossiliferous limestone overlie the Cambrian rocks after an unconformity. The lower Permian Tobra and Dandot Formations are comprised of glacial tillits and coarse-grained sandstones with shales. Although. and Baghanwala Formations (Fig.2) consists of sandstone. clay.1 Depositional Settings of the Kohat-Potwar Basin Depositional record of the Kohat-Potwar geological province is given in Fig 2. The salt lies unconfirmably on the Precambrian basement above the Salt Range.

Crude oil Sediment P2.3 for the identity of crude oils (P1-P22) and sediments (S1-S14) respectively. P11-P16 S1-S3 S4 -S7 S8-S9 S10 S11 P17-P18. Pakistan and location of crude oils and sediments used in this study (Modified from [108] and references therein).2 Stratigraphy of Kohat-Potwar Basin. P19 P22 P20 S12-S13 S14 P8-P9 P3-P5 P1. Refer to Tables 2.1 and 2. 2. 19 . P6-P10 Fig.

The Sembar and Goru Formations from Cretaceous strata are present in Kohat Basin while are not deposited in the Potwar Basin (Fig. the Indian plate entered into warmer latitudes.2) are composed of shallow marine foraminiferal limestone and grey fossiliferous shale [106].2). dolomite. Tredian Formations contains limestone.The Permian rocks are generally preserved in the Potwar Basin but this section is missing in the Kohat Basin [113] (Fig. The Cretaceous sequence mainly contained shale and sandstone of Chichali and Lumshiwal Formations with marl and limestone in some of the areas (Fig. The Jurassic Shinawri Formation consists of marine shales. 2. 2. 2. swamp.2). mud flat and delta front [107]. In early Paleocene. beginning with sedimentation of Hangu sandstone is coastal setting with greater marine influence followed by Lockhart limestone depositions in shallow water environments and that of Patala Formation in shallow marine to deltaic environment [107]. The Lumshiwal Formation composed of siltstone and shelly limestone represent marine environment [107]. Eocene Nammal and Panoba Formations show transitional contact with Patala Formation which is deposited in shallow marine to lagoonal shales with 20 . The shale layers of Chichali Formation indicate reducing environments for sedimentation.to fine-grained sandstone and shale. The depositional environment of Datta Formation is versatile and represents nearshore. During early Cretaceous times. Paleocene-Eocene depositions represented by Makarwal Group (Fig.2). 2. The Shinawari overlaying Samana Suk Formation contained thick carbonates. bay. coarse. The Jurassic and Triassic times of deposition are absent or very thin in Kohat and Potwar Basin. The Musa Khel Group from Triassic strata represented by Mianwali. with occasional sandstones and thin bedded limestones and contains frequent fluctuations of the shelf and terrigenous material which is decreased at the top. The origin of Triassic sediments is mainly shallow marine while freshwater sandstone was also reported in Tredian Formation [106]. marine shale and limestones were deposited over regional erosional surface on the Sulaiman group. Upper Jurassic is represented by the interbedded shales and thick limestone as much as 1400 m of middle and upper Jurassic Sulaiman limestone group (Fig. 2.2). This erosional surface is present at the top of the Samana Suk Formation and is overlain by sandstone and shales of lower Cretaceous Chichali Formation.

2. Tables 2. The sediments mainly consist of well cuttings obtained from Oil and Gas Development Corporation Limited. The collision of Indian and Eurasian plates made regional uplift and transport direction of south to north sediments on the Indian plate was reversed. A carbonate platform was buildup as a result of large volumes of sediments shed by Eurasian plate from Eocene through Miocene [108].2 show geological and geochemical informations.1) have been found in the small area of the Potwar Basin and causes of the vast diversity in physical characteristics of crude oils are unknown so for. 2. The overlaying Chorgali and Sakaser Formations consist of marine carbonates and shale facies in the Potwar Basin area while evaporite facies consist of anhydrite. 18 Crude oils of different API gravity from very light to heavy (16-48°) and reservoired in various geological formations were selected from the basin (Table 2.1 and 2. These crude oils from Carnarvon Basin have been reported previously and indicate typical non-biodegraded mature hydrocarbon profile [114]. Australian crude oils obtained from Carnarvon Basin were also studied in order to compare the distribution of aromatic hydrocarbons with Pakistani oils and sediments (Table 2. Since then Potwar is the main source of hydrocarbons and about 25 wells of crude oils and condensates are explored in the Potwar Basin [115].2 DESCRIPTION OF CRUDE OILS AND SEDIMENTS A total of 23 crude oils and 14 sediments were analyzed. Petroleum reservoirs containing significant amount of hydrocarbons in range of medium to high density oils (Table 2. Kohat Formation comprised of shales with carbonate of the Oligocene Kirthar Formation.1). 2. Pakistan (OGDCL).limestone. Following sections describe geological information of crude oils and sediments from Pakistan. gypsum with minor oil shales in the Kohat Basin. Oligocene was deposited only in Kohat Basin and small area of northern Potwar while missing in most of the Potwar Basin. The Upper Eocene.1 Potwar Basin Potwar Basin is one of the oldest area explored for petroleum in the world while first commercial oil discovery was made in 1914 which was the first of South Asian sub-Continent [106].1). 21 .

1 Geological information of crude oils No Name Samples Depth (m) 2680 2187 2063 3645 2773 2694 3063 3318 2687 2179 2103 3612 4096 4174 4485 4450 4750 4990 4960 Age Cambrian Eocene Cambrian Cambrian Cambrian Cambrian Cambrian Cambrian Cambrian Cambrian Eocene Eocene Eocene Eocene Eocene Eocene Jurrasic Jurrasic Jurassic Triassic Jurassic Reservoir Formation Khewra Chorgali Jutana Jutana Jutana Khewra Khewra Khewra/Tobra Khewra/Tobra Khewra Chorgali Chorgali/Sakaser Chorgali/Sakaser Chorgali/Sakaser Chorgali/Sakaser Chorgali/Sakaser Datta Datta Datta Kingriali Datta API Gravity (degree) 48.9 - Potwar Basin P1 Adhi-5 P2 Missakeswal-1 P3 Missakeswal-3 P4 Rajian-1 P5 Rajian-3A P6 Kal-1 P7 Kal-2 P8 Fimkassar-1 P9 Fimkassar-4 P10 Chaknaurang-1A P11 Minwal-1 P12 Joyamir-4 P13 Turkwal-1 P14 Pindori-4 P15 Dhurnal-1 P16 Dhurnal-6 P17 Toot-10A P18 Toot-12 Kohat Basin P19 P20 P21 P22 P23 Chanda-1 Chanda -2 Mela-1 Wanaea Griffin Carnarvon Basin.4 33.0 36. OGDCL.2 32.4 34.1 41.0 18. Pakistan PPL.2 22.2 37. 8 23.4 16.6 24.9 38.0 37. Islamabad.7 26. Islamabad 22 .0 22.5 37. Australia Note: Oil samples were collected from follwing oil companies of Pakistan.5 38.1 33.Table 2. Pakistan OXY. Pakistan POL.0 16.

8 0. clayston Cretaceous Lumshiwal Cretaceous Chichali Jurassic Jurassic Jurassic Shinawri Shinawri Datta S14 4940-42 Claystone a : OGDCL. Pakistan 23 . S10 4710-12 siltstone S11 4741-42 Shale S12 4834-50 Shale S13 4860-62 Shale.49 3.29 2.90 0. Paleocene Shale Paleocene Paleocene Paleocene Paleocene Paleocene Paleocene 4410-40 Limestone 4510-12 Limestone 4534-60 Limestone 4650-52 Sandstone 4680-82 Sandstone 4690-92 Shale.7 1.3 1.78 3.19 2.4 2.00 7.4 0.71 0.01 2. siltstone Shale.3 0.35 0.4 3.24 2.33 295 347 182 55.0 4.Table 2.2 No S1 S2 S3 S4 S5 S6 S7 S8 S9 Geological settings and Rock Eval data of sediments from well Mela-1a Age Paleocene Paleocene TOC Geological S1 average Formation (mg/g) (%) Patala 1.61 S2 (mg/g) Depth range Lithology (m) 4290-95 Marl 4310-15 Marl 4345-70 HI (mg/g) Tmax (°C) 3.4 1.5 241 71 257 250 82 55 427 431 431 442 433 431 - Limestone.75 Patala Patala Lockhart Lockhart Lockhart Lockhart Hangu Hangu 0.01 0.0 0.78 0.1 1. Islamabad.38 2.6 3.8 0.78 4.4 0.77 1.45 1.75 5.

2. siltstone. Kal-2. the most active area for exploration in Upper Indus Basin is Kohat Basin. [112]). In early nineties a number of wells were abandoned (e. Kal-1. Kahi-1 and Sumari-1. for details see Paracha. The sandstones of Datta formation produced Chanda-1 and Mela-1 are mainly continental in origin. Few studies using geochemical properties from cuttings. Tolanj-1.2. Khewra Formation have reservoir potential.g. Chorgali and Sakaser Formation consist of medium-bedded limestones and fine crystalline dolomites. Rajian3A and Missakeswal-3 oil fields. The Jurassic Datta Formation has produced oils from Toot-10A and Toot-12 fields. Tobra Formation composed of glacial tillites. Dhurnal-6. 2.The locations of crude oils are shown in Fig. joyamir-4. Shallow marine carbonate strata of the Eocene Chorgali and Sakaser Formations form an important hydrocarbon producing horizon in the northern Potwar Basin.2. Minwal-1 and Missakeswal-1 are producing from Chorgali and Sakersar Formations. Turkwal-1. The source origin of these crude oils is not fully correlated with any specific source rock of the area. Khewra Formation has produced Adhi-5. discoveries of oil and gas (Chanda. outcrops and core samples from different geological formations were undertaken and correlated partially with Potwar crude oils [116-117]. Chaknaurang-1A. Both Formations are oil and gas producing reservoirs. The details of crude oils used from the Kohat Basin are shown in Table 2. While Kingriali formation is predominantly composed of dolomites with minor limestone. Makori and Manzalai) have increased the interest of exploration geoscientist in the area. It consists of thick carbonates overlain by evaporates. The oldest producing reservoir in the Potwar Basin is Precambrian Salt Range Formation. But later on. The Permian. Fimkassar-1 and Fimkassar-4 oils used in this study. Mela. and shales. 2. and Fimkassar oil field is produced Khewra/Tobra Formation. Marine shales and massive sandstones of lower Cambrian. Dhurnal-1. The crude oils 24 .1 and marked on stratigraphic chart in Fig. Pindori-1. The overlying Jutana Formation primarily consists of sandy carbonates and nearshore sandstones has reservoired Rajian-1.2 Kohat Basin Currently. 2. with fine to coarse grained and very high porosity characteristics.

3 Geochemical Description of Sediments Fourteen sediments cuttings were selected from the Mela-1 well of the Kohat Basin. S1 & S2 show very good potential in terms of generated hydrocarbons and poor for residual hydrocarbons. HI 241 mg/g TOC indicates both oil and gas prone OM (Type-II/III kerogen). 2. Tmax.show a similar range of API gravities (Table 2. 2. Anonymous reports showed recent discoveries of oils and gas condensate in Hangu formation in the area (news).1%). 25 .2. 2. 427-431 °C reveals that sediments are at the onset of hydrocarbon generation. HI 257 mg/g TOC indicates OM derived from type II and type-III kerogen.78 and 5. Hangu Formation sample (6490-92 m) shows organic rich sediments (TOC: 2. Patala Formation contains total organic carbon (TOC) in fair range (0. Lumshiwal Formation also contains good amount of TOC.3 %).2) and the source rock origin of Kohat Basin oils and gas is not yet reported. The location of well is marked in Fig.1 and samples locations marked on the stratigraphic section in Fig. most likely both liquid and gaseous hydrocarbons as supported by hydrogen index (HI) in the range of 182 to 347 mg/g TOC and suggest both type II and type III as main components of OM. Chichali Formation data is not available while Rock Eval data of single sample of Shinawari Formation shows very good TOC with fair genetic and residual potential but low values of HI (82 mg/g TOC) are consistent with type III/IV kerogen.2. Lockhart Formation sediments contain poor to fair amount of TOC. S1 and S2 show fair and good potential in terms of generated and residual hydrocarbons. Datta Formation shows poor TOC and low values for both S1 and S2 also indicate very lean potential for hydrocarbons which is further supported by low HI (55 mg/g TOC) and indicate type III kerogen. The geological information along with Rock-Eval data is shown in Table 2. the genetic potential of the Formation is poor except one sample (4510-12 m) where S1 shows good genetic potential. S1 and S2 values (7.7-1.2.78 mg/g TOC) suggest very good potential in terms of both generated and residual hydrocarbons.

61 and 0.42-0.67) are a consistent with marginal range of maturity.Thermal maturity of sediments Tmax data for most of the sediments was not available therefore aliphatic biomarkers parameters were used to assess thermal maturity of sediments from the Kohat Basin.52-0. The thermal maturity parameters from steranes and hopanes (Table 2.3) indicate contrasting results where hopanes show immature thermal maturity while steranes show marginal to mature thermal maturity of Kohat Basin sediments. Table 2. sterane maturity parameters show variation in thermal maturity where C29 20S/(20S+20R) ratios (0. The C32 22S/(22S+22R) hopane ratio (0. Lumshiwal.3.3) and C29 ββ/(αα+ββ) ratios (0. The sterane thermal maturity parameters C29 ββ/(αα+ββ) and C29 20S/(20S+20R) ratios in the range of 0.50.42-53) indicate immature to onset oil generation thermal maturity.50-52) indicate mature range while C29 ββ/(αα+ββ) ratio (0.41-0.51-59) indicate marginal range of thermal maturity of these sediments. Chichali and Shinawri Formations sediments revealed immature thermal maturity while C29 20S/(20S+20R) ratio (0.48 respectively indicate a immature nature of OM for Patala Formation sediments.58) of Hangu.44) show immature range of thermal maturity for all sediments except single sample (4834-50 m) which indicates marginal thermal maturity. The parameters were calculated from branched/cyclic fractions of sediments extracts and reported in Table 2. The C32 22S/(22S+22R) ratios (0.58 to 0.43 to 0.42-0. 26 . The Ts/(Ts+Tm) ratios (0. In case of Lockhart Formation sediments.

55 0. C29-Ster.49 0.56 0.61 0.59 0.61 0.49 0.67 0.3 Aliphatic biomarker maturity parameters of Mela-1 well sediments No S1 S2 S3 S4 S5 S6 S7 S8 S9 S10 S11 S12 S13 S14 Sample depth (m) 4290-95 4310-15 4345-70 4410-40 4510-12 4534-60 4650-52 4680-82 4690-92 4710-12 4741-42 4834-50 4860-62 4940-42 S/S+R C32-Hop.43 0.46 0. 0.Table 2.59 0.44 0.43 0.43 0.52 0.44 0.41 0.50 0.42 0.42 0.43 0.44 0.52 0.58 0.43 0.48 0.50 0.42 0.58 0.42 0.49 0.42 0.42 0.49 0.42 0.58 0.56 0.62 0.44 ββ/ββ+αα.53 0.52 0.51 0.44 0.43 0.52 0.52 0. 0.54 0.45 27 .55 0.55 0.60 0.43 Ts/ (Ts+Tm) 0.61 0.52 0.45 S/S+R C29-Ster 0.50 0.

Merck) for column chromatography was activated at 160 °C for at least 24 hrs and pre-rinsed with solvent (n-pentane or n-hexane) prior to use. The GC-MS analysis and stable carbon and hydrogen analysis was performed in geochemistry and isotope labs in Australia. 3. Silica gel Silica gel 60 (0. cyclohexane. methanol. sodium bicarbonate (AR grade. 28 . Drying and neutralizing agents Anhydrous magnesium suphate (AR grade. chemsupply) was dissolved in milli-Q water until saturated solution obtained. However. Molecular sieves Molecular sieves Type 5A (Merck) were activated at 240 °C for at least 24 hrs prior to every use. UET.200 mm. the work was repeated in order to keep consistencies in the data. For use as a neutralizing agent.063-0.Chapter . Unilab) was pre-rinsed with solvent before use as a drying agent. The purity of these solvent were checked by evaporating 10 mL of each solvent to 500 µL followed by analysis of the residue by gas chromatograph-mass spectrometer. n-hexane.3 EXPERIMENTAL The experimental work excluding GC-MS analysis and stable carbon and hydrogen isotope analysis reported in this thesis was performed at chemistry department. USA) were used without further purifications. dicholoromethane (Mallinkckrocdt.1 Solvents MATERIALS AND REAGENTS n-Pentane. Lahore.

1. covered by cotton wool and extracted using mixture of dichloromethane and methanol (9:1. 200 mL).2. thimble. and then sequential rinsing with milli-Q water till neutral pH. Fresh solvent mixture was introduced as required. respectively. cotton wool.18. The solvent was removed by a rotary evaporator to obtain SOM.1 GEOCHEMICAL TECHNIQUES Sample Preparation Sediments The samples (well cuttings) were washed with water and air dried prior to grinding. Hydrochloric acid (specific gravity. The extraction was allowed to proceed for at least 72 hrs for each sample or until the solvent became colorless. activated copper turnings and anti-bumping granules were extracted with mixture of solvents (9:1 v/v dichloromethane : methanol) for at least overnight. Merck) was used for activation of copper turnings. Hydrofluoric acid and hydrochloric acid Hydrofluoric acid (50 % w/v. methanol (5 mL). The samples were ground to particle size of about 150 µm or less using a ringmill (Rocklabs). Prior to each run the apparatus. The grounded sediment was weighed into a thimble. Merck) was used for digestion of molecular sieves. DBH chemicals) were activated by rinsing with 3M HCl (5 mL). 3.Copper (precipitated) Precipitated copper powder and/or turnings (5 g. dichloromethane (5 mL) and n-hexane (5 mL).2 3. Extraction of soluble organic matter (SOM) from sediments The extraction of SOM was performed in a Soxhlet apparatus. 29 .

the aromatic fraction with a mixture of n-hexane : dichloromethane (35 mL. The SOM adsorbed silica or crude oil was introduced on the top of the packed column. Each fraction was recovered by removal of solvent on a sand bath by maintaining temperature up to maximum 60 °C.3. 30 . The SOM solution was carefully adsorbed on activated silica. The dried silica adsorbed SOM was fractionated using column chromatography. the aromatics with a mixture of n-pentane and dichloromethane (2 mL.5 gm) was taken in clean vial (10 mL). Activated silica gel (10 g) was packed as slurry in nhexane.) with cotton wool at bottom was washed with dichloromethane prior to use.d. adsorbed on activated silica) and crude oil (50 mg) were separated by large open column chromatography with following details: A glass column (40 × 0. 7:3. respectively) and aromatic/polar (fraction-3) with dichloromethane and polar fraction with methanol (35 mL). and polar fraction with a mixture of dichloromethane and methanol (2 mL.d. The dichloromethane was evaporated by heating vial on sand bath at 50 °C. The aliphatic hydrocarbons (saturates) were eluted with n-pentane (2 mL).5 × 0. The aliphatic hydrocarbons (saturates) fraction was eluted with n-hexane (35 mL).2 Liquid Chromatography of Crude Oils and SOM Preparation of SOM sample The soluble organic matter (up to 70 mg) was dissolved in minimum amount of dichloromethane. Small scale column chromatography In a typical small scale separation. 1:1).5 cm i. 7:3. respectively).2. The activated silica (up to 1. the SOM adsorbed silica gel sample (maximum up to 20 mg SOM)) or crude oil (10 mg) was applied on the top of the column (5. pasture pipette) of activated silica gel (pre-rinsed with n-pentane).9 cm i. Large scale column chromatography Soluble organic matter (up to 70 mg.

The excess HF was neutralized by adding saturated solution of sodium bicarbonate while stirring.2. Hydrofluoric acid (50 %. The removal of excess cyclohexane under a slow stream of nitrogen yielded branched and cyclic fraction.5 i. n-Pentane (2-3 mL) was added to cover the sieves along with 1 mL of milli-Q water. The resulting mixture was filtered through a small column of silica (5.3.) and rinsed thoroughly with cyclohexane. Quantification of aromatic hydrocarbons Deutrated phenanthrene (d10) was used as internal standard for quantification of aromatic hydrocarbons.3 Isolation of Branched and Cyclic Alkanes A saturated fraction obtained by liquid chromatography separation was used to isolate branched and cyclic alkanes from straight chain alkanes. 3 × 1 mL). 31 . The internal standard was prepared by dissolving 4 mg of deutrated phenanthrene in 100 mL of isooctane solution. Excess pentane was removed carefully using sand bath (60 °C). The aqueous mixture was further extracted with pentane (approx. The cyclohexane containing branched/cyclic alkanes was collected in preweighed vial. The autosampler vial was capped and placed into pre-heated aluminum block (85 °C) for at least 8 hrs. Recovery of straight chain alkanes from molecular sieves The molecular sieve containing n-alkanes were air dried and transferred to a 20 mL Teflon tube. The saturated fraction (up to 15 mg) in cyclohexane (1-2 mL) was added in to a 2 mL autosampler vial quarter filled (2 g) with activated 5A molecular sieves.5 × 0.d. 20-30 drops) was added drop wise while stirring until the sieve had dissolved (45-50 minutes). The n-alkanes from sieves were dissolved in n-pentane and separated by passing through a small column of anhydrous magnesium sulfate. The mixture was homogenized by stirring magnetically while placing on an ice bath. so each microliter (µL) of solution contained 40 ng of deutrated phenanthrene.

Glass tubes (15cm × 0. 32 . secondary amine (diisopropyl amine).d) were soaked in hydrochloric acid (1M) for at least 12 hours. 5% solution in toluene) for more than 24 hours. NaN3 (Sigma-Aldrich). acetonitrile (Sigma-Aldrich). 3-MBP (TCI chemicals). NH3 gas (unknown).7-DMF (Chron AS.1 and 10 mg activated carbon (or coal) were flushed with N2. Asia Pacific Suppliers).1 LABORATORY EXPERIMENTS Reference Compounds and Glass Tubes Preparation Reference compounds were purchased from commercial suppliers: biphenyl (Acros Organics). After washing tubes subsequently with methanol and acetone were ready for heating experiments.2 Laboratory Heating Experiments In a typical experiment 1 mg of the biphenyl or 3-methylbiphenyl reactant with 1 mg of heteroatomic and methylene (alkyl) species compound mentioned in Table 3. 1-methylfluorne (1-MF).3. The reaction products were extracted with dicholormethan and chromatographed by passing the extract through a small-scale silica column.3cm i. 9-MF.3. Fluorene. 1. The glass tubes were then deactivated by keeping them in dichlorodimethylsilane solution (Alltech. 4MF. Active carbon was conditioned at 340 °C (minimum 2 hrs) before use. After that one end of tube was sealed on oxygen-methane flame. 3. It was sieved to pass 90 mesh. tetramethylbenzene (TMB) (SigmaAldrich) and activated carbon (Technical Grade. Heating time was 15-16 hrs for all experiments. Blank experiments without carbon (or coal) were carried out in parallel. The coal used in heating experiments was from Collie in Western Australia [118] from the Hebe seam. Norway). Asia Pacific Suppliers) were used in laboratory simulation experiments. nonyl amine. The reaction products were analyzed using gas chromatography-mass spectrometry (GCMS).3 3. elemental sulfur (Technical Grade.3. and sealed under vacuum before heating in a thermostat at selected temperatures between 200 °C and 300 °C.

a (°C) 300 300 300 300 300 300 270 300 300 Tetramethylbenzene Active carbon (TMB) 3-methylbiphneyl 3-methylbiphneyl 3-methylbiphneyl 3-methylbiphneyl 3-methylbiphneyl a Air (Source of O) Elemental S Elemental S Elemental S Elemental S Active carbon Active carbon Active carbon Active carbon Active carbon 300 300 250 225 200 : heating time was 15-16 hrs for all experiments Note: Blank experiments were performed with out active carbon/coal 33 .1 Heating experiments details Reactant Precursor compound Biphenyl Biphenyl Biphenyl Biphenyl Biphenyl Biphenyl Biphenyl Biphenyl Biphenyl Species compound Elemental Sulfur Elemental Sulfur Acetonitrile NH3 gas Nonyl amine NaN3 NaN3 Air (source of O) Active carbon /coal Active carbon Coal Active carbon Active carbon Active carbon Active carbon Coal Active carbon Temp.Table 3.

Samples were weighed into tin capsules and dropped into a combustion tube at 1000 °C through which a constant stream of helium was maintained. sulfur and other interferences. The resulting combustion gases are passed over catalysts to ensure complete oxidation and absorption of halogens. The system response was calibrated to known calibration standards. Just prior to sample introduction the helium stream was dosed with a precise volume of pure oxygen. Just prior to sample introduction the helium stream was dosed with a precise volume of pure oxygen.4 3. The system response was calibrated to known calibration standards. Excess oxygen was removed as the 34 .1 ANALYTICAL METHODS AND INSTRUMENTATION Elemental Analysis of Sediments Analysis was performed on Carlo Erba NA1500 elemental analyzer. Any oxides of nitrogen were reduced to nitrogen. The resulting combustion gases were passed over catalysts to ensure complete oxidation.3.4. For sulfur analyses samples were precisely weighed into tin capsules and dropped into a combustion tube (at 1000 °C) through which a constant stream of helium was maintained. The sample was instantaneously burned followed by intense oxidation of the tin capsule at 1800 °C (flash combustion). The resulting pyrolysed gases were passed over catalysed carbon to ensure complete conversion of oxygen in the sample to carbon monoxide. carbon dioxide (C) and water vapour (H) and quantitatively measured by a thermal conductivity detector (TCD). The sample was instantaneously burned followed by intense oxidation of the tin capsule at 1800 °C (flash combustion). Excess oxygen was removed as the gases were swept through a reduction tube containing copper at 650 °C. The gas stream was then dried by means of a water scrubber. For oxygen analyses samples were precisely weighed into silver capsules and dropped at preset times into a combustion tube (at 1050 °C) through which a constant stream of helium was maintained. The gases were separated on a chromatographic column into nitrogen (N). The carbon monoxide was separated from other pyrolysis gases on a chromatographic column and quantitatively measured by a thermal conductivity detector (TCD).

25 µm 5% phenyl 95% methyl polysiloxane stationary phase (DB-5 MS. The GC oven was programmed from 40 °C to 310 °C at 3 °C/min with initial and final hold times of 1 and 30 minutes. [121].4. Data was acquired in full scan 35 . Finally the sulfur dioxide was separated from other interfering gases on a chromatographic column and quantitatively measured by a thermal conductivity detector (TCD). [120] and Grice et al.3 Gas Chromatography-Mass Spectrometry (GC-MS) Full scan mode for compound identification GC-MS analysis was performed using a Hewlett-Packard (HP) 5973 Mass Selective Detector (MSD) interfaced to a HP 6890 gas chromatograph (GC). The MS source and quadrupole temperatures were at 230 °C and 106 °C. Helium maintained at a constant flow rate of 1.1 mL/min was used as carrier gas. The system response was calibrated to known calibration standards. The injector was operated at 280 in pulsed splitless mode. J & W scientific) was used for the analysis. Details of this method are outlined in Jørgensen et al.4. 3. A 60 m × 0. respectively.gases are swept through a reduction tube containing copper at 650 °C. respectively. The transfer line between the GC and the MSD was held at 310 °C. 34 S/32S ratios were measured by means of combustion isotope-ratio mass spectrometry (C-irmMS) using a Thermo Finnigan Delta+ coupled to an elemental analyzer (Eurovectro) via a split interface (Thermo Finnigan Conflo III). 1µL of the saturated or aromatic fractions (1 mg/mL in n-hexane) was introduced into the split/splitless injector using the HP 6890 auto-sampler. 3.2 δ34S of Pyrite from Sediments The total reduced sulfur from the sediment was obtained by a distillation method described by Fossing and Jorgsensen [119]. Measured isotope ratios were calibrated with in-house and international reference materials and are reported in the δ-notation relative to the V-CDT (Vienna Canon Diablo Troilite) standard.25 mm ID capillary column coated with a 0.

to increase the resolution between individual isomers of alkylnaphthalenes was obtained by running GCMS in SIM mode using WAX column (0. IsoScience Australia Pvt.25 mm × 0. 3.4 Gas Chromatography-Isotope Ratio Mass Spectrometry Gas chromatography-isotope ratio mass spectrometry (GC-irMS) was performed using micromass IsoPrime mass spectrometer interfaced to an agilent technologies 6890N Gas Chromatograph for compound specific stable hydrogen isotopic compositions (δD). with a scan rate of ~3 scans/sec.u. Full scan mode for heating experiment extracts GC-MS analyses were performed using an Agilent Technologies 6890 gas chromatograph coupled to an Agilent Technologies 5973 mass spectrometer with similar condition as above for heating experiments (section 3. δD values were calculated by integration of the m/z 2 and 3 ion currents of the H2 peaks produced by pyrolysis of the GC separated hydrocarbons using chromium powder (350-400 µm. Selected ion monitoring (SIM) mode Aliphatic and aromatic hydrocarbons were analyzed by GC-MS in selected ion monitoring mode for better resolutions of compound classes.3. H3+ ions are produced in the mass spectrometer ion source as a result of H2+ ion and H2 36 . In these analyses GC-MS conditions were kept same as described in full scan mode except MSD was operated in SIM mode.mode from 50 to 550 amu. The MS mass range was 10-500 a.60 m × 0. During the analysis of a mixture of organic reference compounds (hexadecane and docosane). An interfering species.2) extracts except following difference. J & W scientific). GC was operated with column of same dimensions used for GC-MS analysis above for δD. The GC oven was programmed from 40 °C for 1 minute then at 5 °C/min to 310 °C for 10 minutes. the GC oven was programmed from 50 °C to 310 °C at 3° C/min with initial and final hold times of 1 and 10 minutes respectively. DB-WAXETR. Ltd. Similarly.4.) at 1050 °C. with the MS ionization energy 70 eV and the electron multiplier voltage 1800 V.m.25 µm.

After removing of oxides of nitrogen. passed through an oxidation catalyst (chromium oxide). BOC Gases Australia Ltd. δD values are reported relative to that of H2 reference gas pulses produced by allowing hydrogen (UHP. contributions from H3+ produced in the ion source are corrected by performing m/z 3 measurements at two different pressures of the H2 reference gas to determine the H3+ factor.5 Elemental Analysis-Isotope Ratio Mass Spectrometry (Bulk Isotope Analysis) Bulk isotope analyses were performed on a micromass IsoPrime isotope ratio mass spectrometer interfaced to a EuroVector EuroEA3000 elemental analyzer. The amount of H3+ formed depends on the partial pressure of hydrogen. The oxidation products then passed through a reduction reactor at 650 °C containing copper granules. where the tin promoted flash combustion. An electrostatic sector is used to separate HD+ from the leading edge of the large signal produced at m/z 4 by the constant flow of helium (carrier gas) into the mass spectrometer. where any oxides of nitrogen (NO. and the species interferes isobarically at m/z 3. For bulk δ13C analysis.05-0. The tin capsule containing sample was dropped into a combustion reactor at 1025 °C with help of autosampler.4. N2O and N2O2) are reduced to N2 and SO2 were separated on a 3 m chromatographic column (PoropakQ) at ambient temperature. The sample and capsule melted in an atmosphere temporarily enriched with oxygen. the sample was accurately weighed (0.15 mg) into a small tin capsule which was then folded and compressed carefully to remove any tracers of atmospheric gases. Thus. oxidation products are then passed through a thermal conductivity detector (TCD) followed by the irMs. The D/H content of the H2 reference gas was monitored daily via analysis of mixture of reference compounds (see above).) of a known D/H values into the mass spectrometer. Isotopic 37 . in a constant flow of helium. The combustion products. Average values of at least two analysis and standard deviations are reported. Isotopic compositions are given in the delta notation relative to Vienna Standard Mean Ocean Water (VSMOW). An internal standard (Squalane) with a predetermined δD value of -167‰ was used to monitor accuracy and precision of δD measurements. 3.molecule collisions [122].

the sample was accurately weighed (0. The pyrolysis products were separated on a 1 m 5A molecular sieve packed chromatographic column held in an oven at 80 °C (isothermal).05-0.compositions are given in the delta notation relative to Vienna Peedee belemnite (VPDB). The sample was pyrolyzed to form H2 and CO. For bulk δD analysis. along with N2 if applicable.15 mg) into a small silver capsule which was then folded and dropped into a pyrolysis reactor containing glassy carbon chips held at 1260 °C. δD values were calculated and reported similar to as above for compound specific isotope analysis (CSIA). then into the irMS. ____ 38 . before passing through a TCD.

4.10-trimethylundecane (nor-farnesane. 39 .6dimethylundecane (I.10. III). d c a b e Ph.3 for GC-MS program. 123-125 and references therein]. V). 2. II).10.4 IDENTIFICATION OF SATURATED AND AROMATIC HYDROCARBONS 4.6.1 n-Alkanes and Isoprenoids n-C 17 Pr. c: 2.-trimethylpentadecane (nor-Pristane. Ph: phytane.1 Total ion chromatograms (TIC) of saturated hydrocarbon fraction shows n-alkanes (n-C10 to n-C37) and isoprenoids in crude oil (Missakeswal-1).10-trimethyldodecane (farnesane.Chapter . d: 2.14-tetramethylhexadecane (VII).6.1.6. Refer to section 3. e: 2. b: 2.4.6. a: 2. mass spectra and comparison with literature data [45. see appendix).1 SATURATED HYDROCARBONS Saturated hydrocarbons were identified using relative retention times.14tetramethylpentadecane (VI). n-C 25 n-C 10 20 40 60 80 100 120 Relative retention time (min) Fig.6.10.6. 2.10-trimethyltridecane (IV). 4. Pr: pristane.

4.4. C30: C30 17α(H)-hopane (Xb).1. C24*: C24 17. Peak numbers 19-41 denote carbon number of tricyclic terpane (VIII).4. IX).2 Tricyclic and Tetracyclic Terpanes C30 23 20 21 19 25 22 26 28 29 30 31 33 34 35 36 24 m/z :191 24* 38 39 40 41 60 70 80 Relative retention time (min) 90 100 Fig.2 Mass chromatogram (m/z: 191) illustrating tricyclic and tetracyclic terpanes in Dhurnal-1 crude oils.21-secohopane (TeT: tetracyclic terpane. Refer to section 3.3 for GC-MS program. 40 .

4. X-XV) in Adhi-5 crude oil.4. Refer to section 3.1.3 Mass chromatograms (m/z: 191) showing the distribution of pentacyclic triterpanes (hopanes.1.4.3 for GC-MS program. 41 . Identity of peaks refers to Table 4.3 Pentacyclic Triterpanes 30 m/z : 191 29 31 29Ts Ts Tm 30D 30M 29M S R S R 32 33 S R 34 S R S 35 R 86 92 98 Relative retention time (min) 104 Fig.

Peak# Ts Tm 29 29Ts 30D 29M 30 30M 31S 31R 32S 32R 33S 33R 34S 34R 35S 35R Identification 18α(H)-22.C31.29.C32.21α(H)-Hopane. XIa 17α(H).C31.C35. C27. Xg 22R 17α(H).C32.C34. Xb 17β(H).3. Xe 22R 17α(H).C33.C33. Xf 22S 17α(H).30-trisnorhopane.C34. XII 17α(H).21β(H)-trishomohopane. Xc 22R 17α(H).Table 4. 4.21β(H)-Hopane. C29 (moretane). Xd 22S 17α(H). C29 Xa 18α(H)-30-norneohopane. XV 17α(H)-diahopane.21β(H)-homohopane. Xf 22R 17α(H). C30 (moretane).21α(H)-30-norhopane.21β(H)-tetrakishomohopane. Xd 22R 17α(H).30-trisnorneohopane. XIb 22S 17α(H). C27.1 Identifications of pentacyclic triterpanes from Fig. XIII 17α(H)-22.21β(H)-pentakishomohopane. C30.21β(H)-bishomohopane.21β(H)-trishomohopane.21β(H)-homohopane.29.C35.21β(H)-30-norhopane.21β(H)-tetrakishomohopane. Xe 22S 17α(H).C30.21β(H)-bishomohopane.18β(H)-pentakishomohopane.C29Ts. Xc 22S 17α(H). Xg 42 . XIV 17β(H).

C27.4. (24 (S+R)). C28.4. C28. XVIc 20R 24-ethyl-5α. XVIIa 20S 24-methyl-13β. XVIe 20R 24-methyl-5α. C29. XVIIa 20R 13β.14β.2 Identifications of steranes and diasteranes from Fig.4. 4.17α-diacholestane. C28.4 Mass chromatogram (m/z: 217) of Dhurnal-1 crude oil shows the profile of steranes and diasteranes.17α-Cholestane. (24 (S+R)).14α.4 Steranes and Diasteranes 6 15 m/z:217 16 1 5 2 3 4 7 8 9 10 13 11 12 14 17 80 84 88 Relative retention time (min) Fig. C29. C29. XVIb 20R 24-methyl-5α.17β-cholestane. XVIe 20S 24-methyl-5α. Table 4.17β-cholestane.17α-diacholestane.17α-diacholestane. C27. XVIIc 20S 24-methyl-5α. See section 3. C29.17α-diacholestane.17β-cholestane. C27.14β. XVIIb 20S 5α.17β-cholestane.14α.17β-cholestane.1. 4.17α-cholestane. XVId 20R 5α. C28. C29.17α-cholestane. C28.17α-cholestane.17α-cholestane. XVIa 20S 24-ethyl-13β.14β. C28. C27.14β. 14α.14α.14α.17β-cholestane. Peak identity numbers refer to Table 4. C29. XVIf 20R 24-ethyl-5α. C27.14β. XVIa 20R 24-ethyl-13β. XVId 20S 5α.17α-diacholestane.3 for GC-MS program. XVIc 43 . Peak # 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 Identification 20S 13β.17α-diacholestane. XVIIb 20R 24-methyl-13β. XVIf 20S 24-ethyl-5α.17α-cholestane. C27.14β.2. XVIb 20S 24-ethyl-5α 14α. XVIIc + 20R 5α.

4. 4. See section 3.5 Diamondiod Hydrocarbons m/z: 136+135 1-methyladamantane 2-methyladamantane adamantane 21 23 25 diamantane 4-methyldiamantane m/z: 188+187 1-methyldiamantane 3-methyldiamantane 40 42 44 Relative retention time (min) Fig.4.1.5 Adamantane (XVIII) and methyladamantanes chromatograms (m/z: 136+135) and are shown by sum of mass diamantine (XIX) and methyldiamantanes are shown by sum of mass chromatograms (mz/: 188+ 187) from saturated fraction of representative oil sample (Adhi-5).3 for GC-MS program. 44 .

126-133]. 1-MF.7-dimethylfluorene (1.49.30.e.2 POLYCYCLIC AROMATIC HYDROCARBONS Aromatic hydrocarbons were identified using relative retention times.4. mass spectra and comparison with the literature data [6. 45 . Methylfluorenes are not reported in sedimentary OM as per my knowledge and they were identified using relative retention times and comparison with mass spectra of available internal standards i. 4-MF and 1. 9-methylfluorene (9-MF).7-DMF).

numbers on each peak refer to respective methyl and dimethyl biphenyl isomer. XXII) and methylbiphenyls and (b) mass chromatogram (m/z: 182) showing dimethylbiphenyls in aromatic fraction of a representative oil (Adhi-5).6' 40 3.3' 2. diphenylmethane.5 2.4' 2.5 3. 4.4' 3.2' 2.1 Biphenyl and Alkylbiphenyls (a) BP 3 m/z: 154+168 4 2 39 40 41 DPM 42 43 44 45 (b) m/z: 182 3.2. DPM. 46 .6 (a) Sum of mass chromatograms (m/z: 154+168) showing biphenyl (BP.4 4.4+2.4.3 2-E 42 44 46 48 Relative retention time (min) Fig.4' 3-E 2.3' 2.

XXIII). 4.7 1.6 43 45 47 49 51 1.6+ 1.2.5 1. 47 .2.6.3+1.4.2 Naphthalene and Alkylnaphthalenes (a) 2 1 N 2.5 1.5 1.6 1.7 2.3.7 1.3.2.7 53 Relative retention time (min) Fig.3.5.7 1.3 1.2.2.6 2.7 2.6. dimethylnaphthalenes are shown by sum of mass chromatograms (m/z: 128+142+156 respectively) and (b) trimethylnaphthalenes.2.7 1.2.5 1.3.7+ 1.4.5.6.7 1. Numbers on each peak refer to position of methyl substituent.7 30 32 34 36 38 40 42 (b) 1.6 1.2.2.3.4.6.7 1. methylnaphthalenes.2 m/z: 128+142+156 1.6+ 1.3.4+2.4 1.3.3.7 1.2.6 m/z: 170+184 1.6.3 1.7 (a) Naphthalene (N.4.3.6+ 1.3.4.5.6 1. tetramethylnaphthalenes are shown by sum of mass chromatograms (m/z: 170+184 respectively) in a representative oil (Adhi-5).2.2.2.2.7 1.

8 1. 48 .8 Phenanthrene (XXIV).6 1. 4.5+ 2.10 9.3 Phenanthrene and Alkylphenanthrenes P 9 2 3 1 m/z:178+192+206 1.6 3.2 3-E 55 57 59 61 63 65 Relative retention time (min) Fig.10+3. dimethylphenanthrenes shown by sum of mass chromatograms (m/z: 178+192+206 respectively) from aromatic fraction of Adhi-5. methylphenanthrenes.3 1.5+2.9+4.2+1-E+3.4.2.9+ 2.7 1.3+3.10 2.7 2.6 2.9+ 1. Numbers on each peak refer to respective alkyl phenanthrene isomer.9+4.

9 Sum of mass chromatograms (m/z: 168+182) showing DBF (XXV) and methyldibenzofurans in Kohat Basin sediment. 49 . 4. depth: 4290 m.4.2.4 Dibenzofuran and Alkyldibenzofurans m/z: 168+182 DBF 4 3+2 1 45 46 47 48 49 50 Relative retention time (min) 51 Fig. Numbers on each peak refer to methyl dibenzofuran isomer.

10 (a) sum of mass chromatogram (m/z: 167+181) showing carbazole (C.6 1. depth: 4690 m. XXVI) and methylcarbazoles and (b) mass chromatogram (m/z: 195) showing dimethylcarbazoles from Kohat Basin sediment.2 1.4.8 1.3 2.5 Carbazole and Alkylcarbazoles (a) 1 m/z :167+181 C 2 3 4 56 57 58 59 60 (b) m/z:195 1.6 2.4+4-E 60 61 62 63 64 Relative retention time (min) Fig.5+3-E 2.2.7 1.5 1. Numbers on each peak refer to respective methyl and dimethyl carbazole isomer. 50 . 4.4 2.7+1.

8 2. depth. Numbers on each peak refer to respective methyl and dimethyl dibenzothiophene isomer.6+1.3 1.6 1.4 1. 51 .7 3.6 3.2+1. 4. XXVII) and methyldibenzothiophenes and (b) mass chromatogram (m/z: 212) showing dimethyldibenzothiophenes from Kohat Basin sediment.9 59 60 61 62 63 64 Relative retention time (min) Fig.6 4-E 2. 4710 m.4+1.4 3.6 Dibenzothiophene and Alkyldibenzothiophenes (a) 4 DBT m/z: 184+198 3+2 1 53 54 55 56 57 58 (b) m/z: 212 4.2.4.11 (a) Sum of mass chromatograms (m/z: 184+198) sowing dibenzothiophene (DBT.

XXVIII) and methylfluorenes in Kohat Basin sediment.4.2.12 Sum of mass chromatograms (m/z: 166+180) showing fluorene (F.7 Fluorene and Alkylfluorenes m/z: 166+180 F 1 2 3 9 4 47 48 49 50 51 52 53 Relative retention time (min) Fig. Depth: 4290 m. Numbers on each peak refer to respective methyl substituent. 4. 52 .

4. m/z: 219 Retene m/z: 234 68 69 70 71 Relative retention time (min) Fig.2.8 Identification of Retene Identification of Retene was confirmed by monitoring ions 219 and 234 to avoid any interference from tetrmethylphenanthrenes (m/z: 234).4.13 Mass chromatograms m/z: 219 and 234 showed Retene (XXI) in aromatic fraction of Adhi-5 crude oil. 53 .

51 1539.25 mm × 0.14.2 Kovat and Lee 308. Identification is given in Table 4.9 Compound Identification of Laboratory Heating Experiments 1 4 3 2 28 30 32 34 36 Relative retention time (min) 38 5 Fig.59 1384 - 259.25 µm) 50 °C (3 min) 3 °C /min 280 °C (20 min) ≠: DB-5 (30.5 1598 309.) 40 °C (1min) @ 5 °C/min.2 MS 257. NaN3.22 1851 *:Column and temperature program: DB-5MS (60 m × 0.14 Total ion chromatogram of the extract of laboratory experiment at 300 °C of reactants (biphenyl.79 1605.D. 4.3.9 Kovat 259.96 1529. [132]# Kovat Rostad and Pereira. m × 0.2.3 identification compounds from Fig. 310 °C (10min) MS: Mass spectra #: HP-5 (30.25 µm) 50 °C (4 min) 6 °C /min 300 °C (20 min) ____ 54 .25 mm × 0. Compound name Retention Indices * Lee Kovat Zenkevich et al. Table 4.8 MS 269.4..3 MS 1379 1506 - 236. activated carbon. Air) for 16 hrs.64 1394.75 1526 271. m × 0.25 µm I.25 mm × 0. [126]≠ Lee Kovat Peak# Identification 1 2 3 4 5 Biphenyl orthoHydroxybiphenyl Dibenzofuran orthoAminobiphenyl Carbazole 235.55 1866. 4.

Chapter . depositional environments. Pakistan was carried out using carbon and hydrogen bulk isotope abundance and distribution of saturated and aromatic hydrocarbons. high diasterane/sterane. GC-MS analysis and bulk stable isotopic compositions of saturated and aromatic fractions reveal that at least three different groups of crude oils are present in the Potwar Basin. tricyclics /hopanes. low DBT/P ratios and higher relative abundance of C19 tricyclic and C24 tetracyclic terpanes. Abundant biphenyls (BPs) and fluorenes (Fs) are observed in group A oils while group B oils 55 . C23-tricyclic/C30 hopane. Aliphatic biomarkers were used as supporting tool to deduce the geochemical characteristics such as thermal maturity. high diahopane/hopane. Group A contains terrestrial source of OM deposited in highly oxic/fluviodeltaic clastic depositional environment shown by high Pr/Ph.5 GEOCHEMISTRY OF POTWAR BASIN CRUDE OILS ABSTRACT Geochemical classification of eighteen crude oils from the Potwar Basin (Upper Indus). C24-tetracyclic/C30 hopane. Group C oils show higher marine OM (algal input) indicated by extended tricyclic terpanes (upto C41 or higher) and higher steranes/hopanes ratios. source OM and extent of biodegradation. PAHs distributions in regard to these geochemical characteristics were reported and comprehensive oil correlation of the Potwar Basin was established. Aliphatic biomarkers for rest of the oils indicate marine origin however two ranges of values for parameters such as steranes/hopanes. Group B oils are generated from clastic rich source rocks deposited in marine suboxic depositional environment than group C oils which are generated from source rocks deposited in marine oxic depositional environment. diasteranes/steranes. C31/C30 hopane ratios differentiate them into two groups (B and C). Distribution of PAHs classified Potwar Basin oils into similar three groups based on depositional environments and source OM variations.

C27. Variations in distribution of triaromatic steroids (TAS) in Potwar Basin oils clearly indicate source dependent of these compounds rather than thermal maturity. Higher abundance of C20 and C21 TAS and substantional difference in distribution of long chain TAS (C26.e. Higher abundance of aromatic biomarkers (1-MP) the and 1. physicochemical and biological processes during generation as well as accumulation in reservoirs. and bear a close spatial relationship [134]. 5. Group A shows only C27 and C28 TAS while group B shows C25 to C28 TAS and absence of these compounds in group C oils revealed that the sterol precursors for these compounds are most probably different. Biomarker analysis of selected sediments and crude oils has been performed and source to oil correlation has been 56 .2. Aliphatic and aromatic hydrocarbon maturation parameters indicate higher (late oil generation) thermal maturity for all oils from the Potwar Basin. heavy oils are genetically related to light oils.showed higher abundance of dibenzothiophenes (DBTs) and negligible presence of dibenzofurans (DBFs) and Fs and group C oils showed equal abundance of DBTs and Fs. C28) between the groups indicate different source origin of these compounds. DBTs) are higher in marine source oils while oxygen compounds (DBFs) and Fs are higher in oxic/deltaic depositional environment oils.7trimethylnaphthalene (1. The crude oils of group A and C are typically non-biodegraded mature crude oils whereas some of the oils from group B showed minor biodegradation indicated by higher Pr/nC17. This relative abundance of heterocyclic aromatic hydrocarbons in Potwar Basin oils broadly indicate that the distribution of these compounds is controlled by depositional environment of OM where sulfur compounds (i. The properties and composition of these petroleum systems are controlled by complex geological.2. 1-methylphenanthrene dimethylphenanthrene (1. Ph/n-C18 and low API gravity.51.1 INTRODUCTION The Potwar Basin has shown a number of small and medium size oil and gas discoveries and still active for further explorations.5-TMN).7-DMP) indicate major source of OM for group A oil is higher plant supported by abundance of conifer plants biomarker retene. Both heavy and light oils have been discovered in the basin.

however their ubiquitous occurrence in sedimentary OM suggests that the compounds are the product of sedimentary reactions [4]. The principal behind is that the methyl group shifts from α..position with increase in thermal maturity [26]. 136-139].38. organic geochemical data particularly PAHs and isotopic compositions from potential source rocks in the Potwar Basin have never been reported. many of the above factors are often interrelated and have been considered collectively for correlation studies [135]. The potential application of aromatic hydrocarbons has been recognized as thermal maturity indicator of source rocks and crude oils [25-26.reported in a study [116]. Thermal maturity parameters derived by comparing concentrations of thermodynamically least stable isomers (α) to the thermodynamically most stable isomers (β). In alkylphenanthrenes. depositional environment and thermal maturity indicators of source rocks and petroleum [5-6. [5] suggested aromatic biomarker.11.e. shale) (iv) relative thermal maturity of potential source rocks and v) extent of biodegradation of petroleum hydrocarbons. retene (XXI) as indicator of terrestrial OM and related it to araucariaceae family of conifers and later on source of retene was specified to the conifer resin [135].marine. nor has detailed an oil-oil correlation ever been undertaken up to my knowledge. Prokaryotes and Archeae) ii) paleoenvironmental depositional conditions . hypersaline or fluviodeltaic iii) lithology of potential petroleum source rocks (carbonate vs. Biomarkers (on structural grounds) in bituminous OM can provide valuable information on: i) the source of their natural product precursors (i.25. However rock-eval pyrolysis of some Precambrian source rocks has reported and partially correlated with Potwar Basin crude oils [117]. However. The variation in biomarkers abundances has been used successfully for oil correlation studies between source rocks and/or other oils [e. The alkylnaphthalenes maturity parameters have been described by van Aarssen et al.140-141]. The application of biomarkers and stable isotope analysis has been recognized as powerful tool in exploration petroleum geochemistry. Alexander et al. [38]. However.38].g. The distribution and relative abundance of these compounds have been used as source. lacustrine. methylphenanthrenes ratio (MPR) are derived 57 . Aromatic structures are almost absent in biological OM.to β. Eukaryotes.10-11.

Among aromatic sulfur hydrocarbons. The calculated vitrinite reflectance (Rc) from MPI-1 differentiates crude oils thermal maturity into immature (0. The bulk isotope compositions of saturated and aromatic fractions from crude oils has been applied to represent the source OM input in hundred of oils in the world [142-144] while compound specific isotope analysis is used as a powerful tool in the oil correlation studies [145-146]. lithology and extent of biodegradation of hydrocarbons. depositional paleoenvironmental information.70). Bulk isotope analysis represents the measurement of stable isotopes of total carbon and hydrogen in the samples which indicate the average values of all complex compounds. methyldibenzothiophene ratio (MDR. Methylphenanthrene index 1(MPI1) is the most significant molecular maturity parameter from aromatic hydrocarbons which is successfully calibrated with mean vitrinite reflectance (Rm) for source rocks and crude oils [4].52 to 1. moreover MDR showed variation relevant to the expulsion stage of aromatic sulfur hydrocarbons from type II/III kerogens [40]. In this chapter organic geochemical parameters based on PAHs and stable carbon and hydrogen isotopes of saturated and aromatic fractions supporting with aliphatic biomarkers have been used to investigate the source OM of the Potwar Basin crude oils.95).32% [11].by dividing α-isomer (1-MP) to the β-isomer (2-MP). mature (0. 4-/1-MDBT) are sensitive to maturity changes which shows good correlation with vitrinite reflectance in range of 0. Results were successfully applied to delineate the oils groupings of the Potwar Basin. However MDR showed different thermal maturity trends in early maturation stages [11]. Variations in stable isotopic compositions or “isotope fractionation” occur in nature due to different physical and chemical processes. A selection of saturated and aromatic biomarker parameters has been determined for oils and source-rocks to establish thermal maturity of OM. saturated fraction or aromatic fraction of crude oils and sediment extracts are being under use for bulk isotope determinations. The entire sample such as whole oil. Stable isotopes of carbon and hydrogen are the most useful tracers in crude oils and sediments because they are the most abundant elements in any shape of sedimentary OM. 58 .85) and postmature (0.

therefore bulk δ13C of saturated and aromatic fractions of 59 .4-0.2 Carbon and Hydrogen Isotopic Compositions The isotopic composition of crude oil is mainly dependent on the δ13C and δD value of the kerogen which in turn. n-Alkanes from n-C10 to n-C37 are present in Adhi-5 with no odd or even preference of n-alkanes as measured by CPI and OEP (Table 5.1. The P15-P18 oils contained full suit of n-alkanes. a group of oils (P2-P14. CPI and OEP of some samples are <1 suggesting even preference for C22-C30 n-alkanes. Biodegradation and thermal maturity have little effect on the stable carbon isotopic composition of the whole oil [149].9 and 0. Group A comprising a single oil Adhi-5. consists of P15-P18 oils. Ratios of isoprenoids to n-alkanes are very low (0. Their isoprenoids to nalkanes ratios are higher. probably because of evaporative loss during sample processing. generated from highly oxic depositional conditions. 4.1).1).5. Table 5.2 for Pr/n-C17 and Ph/n-C18 respectively) but Pr/Ph ratio is highest (3. 5.147-148].7 respectively.6-0.1. Pr/Ph ratio 1-2 and less abundance of low molecular weight n-alkanes. The Group B samples show low maturity likely to be affected by biodegradation.e. depends on the biological OM and the depositional environment [143. shows characteristics of narrow range medium gravity (API: 34-38°). This data in combination with API gravity (Table 2. non-biodegraded light oil (API: 48°). The source rocks generating Group B oils appear to have deposited under sub-oxic depositional conditions. Low molecular weight hydrocarbons (<n-C10) were not observed.2. chapter 2) broadly classify the samples into three groups.4 and 0.2. mature. Compared to Adhi-5. The total ion chromatogram (TIC) of the saturated fraction of a representative oil sample is shown in Fig.2 5. Table 5.1) display different characteristics i.2). Since isotopic compositions of oils change with type of OM.1 (Chapter 4). of typically mature. low values of Pr/n-C17 and Ph/n-C18 (0. non-biodegraded petroleum. Group C.1 RESULTS AND DISCUSSION Normal Alkanes and Isoprenoids Distribution The crude oils analyzed in this study are listed in Table 5. Group B (P2-P14) of medium to heavy (API: 16-41°) oils.

5 -22.4 1.3 1.0 1.0 1.3 1.2‰.0 0.8 -23.0 1.4 1.0 0.0 1.2 1.8 0.3 -23.0 1.5 0.3 1.5 δDsats (‰) -117 -155 -132 -149 -126 -132 -136 -130 -145 -145 -148 -129 δDaros (‰) -111 -130 -125 -135 -132 -141 -136 -134 -129 -139 -139 -122 - δ13Caver (‰) -25.9 0.7 δDaver(‰) -114 -142 -128 -142 -129 -137 -136 -132 -137 -142 -144 -126 - Group A B B B B B B B B B B B B B C C C C Adhi-5 Missakeswal-1 Missakeswal-3 Rajian-1 Rajian-3A Kal-1 Kal-2 Fimkassar-1 Fimkassar-4 Chaknaurang-1A Minwal-1 Joyamir-4 Turkwal-1 Pindori-4 Dhurnal-1 Dhurnal-6 Toot-10A P18 Toot-12 1.0 1.0 -21.8 0.4 -21.8 -21. isoprenoid ratios and bulk isotope data Oil and well Pr/Ph 3.2 1.6 -21.0 -20.9 1.8 0.0 OEP 1.9 0.7 0.0 1.9 0.5 0.3 1.0 0.5 1. OEP: (C21 + 6×C23 + C25)/(4×C22 + 4×C24) δ13C (‰) with respect to VPDB reported with in standard deviation of 0.3 1. δD (‰) with respect of VSMOW with in standard deviation of 3.0 1.0 1.1 -21.8 0.0 1.0 1.9 1.6 0.0 1.7 -22.1 -21.0 1.0 1.9 -21.4 CPI: 2(C23 + C25 + C27 + C29)/[(C22 + 2(C24 + C26 + C28) + C30].0 0.1 -22.8 0.3 1.6 0.6 -23.2 0.0 1.1 δ13Caros (‰) -24.9 0.6 Pr/nC17 0.6 Ph/nC18 0.9 1.0 -25.1 -25.2 -21.0 -22.6 -23.9 -22.5 -22.1 0.8 0.5 -23.9 1.0 1.5 -20.1 -21.3 1.0 1.1 -21.0 δ13Csats (‰) -26.4 -23.4 1.4 1.6 1.8 -23.9 0. -: not determined δ13Caver: (δ13Csats+ δ13Caros)/2 δDaver: (δDsats +δDaros)/2 60 .0 -22.5 1.7 0.0 1.2 1.0 -22.9 0.0 1.8 1.4 1.5 2.0 1.7 -21.9 0.0 1.0 1.0 -22.0 1.1 -21.0 1.2 -22.1 0.2 1.4 CPI 1.Table 5.0 0.0 -26.1 No P1 P2 P3 P4 P5 P6 P7 P8 P9 P10 P11 P12 P13 P14 P15 P16 P17 n-Alkanes.9 1.9 -21.0 1.9 0.9 0.3 -22.4 -23.3 1.2 1.1 -22.7 0.9 0.1 -26.

1a. group B). The crude oils P2-P14 showed higher values of δ13C (isotopically heaviest) and cluster together on right hand side of the plot (Fig. Adhi-5 was isotopically lightest (more negative) in δ13C of both saturated and aromatic fractions. The isotopic composition of crude oils with in each group is most probably controlled by both source and depositional settings as indicated by n-alkanes and isoprenoid distributions and saturated and aromatic hydrocarbons distributions (following sections). 5. 61 .1b). More negative (isotopically lighter) δ13C values (-25 to -26.1a. The difference in stable carbon and hydrogen isotopic compositions of saturated and aromatic fractions is consistent with source variations. Table 5. 5. P1). 5. 5.1‰) are observed from the Dhurnal and Toot well samples (Fig. The difference observed between δ13C of the saturated hydrocarbon fractions between the groups indicates the difference in source organisms.1a.1. Table 5. Table 5.1a.1).1 were examined for bulk stable carbon and hydrogen isotopic compositions. P15-P18). It was designated as group A (Fig. group C.1) and same results were achieved (Fig.oils are useful along with biomarker parameters in distinguishing crude oils from different source and depositional settings [143-148]. The crude oils were separated into similar three groups hence provided an additional evidence for the existence of at least three groups of petroleum in the Potwar Basin. 5. Among the sample suite of oils analysed.1a.1). Crude oils listed in Table 5. Group B oils showed enrichment in δ13Csats having values up to 3-4‰ compared to group C (Fig. Another plot represents the difference between δ13C and δD average values of both saturated and aromatic fractions of crude oils (Table 5. 5. Cross plots δ13C of saturated and aromatic fractions were used to clearly delineate different groups of petroleum in the Potwar Basin (Fig.

-20.1 The plots (a) δ13Csats vs δ13Caros (b) δ13Caver vs δDaver to delineate groupings of petroleum in the Potwar Basin.0 -23.0 -23.0 -26. 5.0 -23.0 (a) B -21.0 δ CSats (‰) -100 (b) -110 A δDaver (‰) -120 C -130 B -140 -150 -26.0 -21.0 -24.0 δ13Caver (‰) Fig.0 -25.0 -27.0 C δ13CAros (‰) -22.0 -22.0 -24.0 -25.0 A -25. 62 .0 13 -24.0 -22.

5.2. and BPs in representative chromatogram of group C oil differentiates this group from other groups. Representative TICs of aromatic fractions from each group of the Potwar oils are shown in Fig. 5.3 Polycyclic Aromatic Hydrocarbons (PAHs) Distributions of PAHs were evaluated from GC-MS analysis of aromatic fractions.2). lithology and depositional environment in combination with commonly used aliphatic biomarkers.2b). Fs. Similarly naphthalenes and phenanthrenes are the predominant aromatic components in group B representative chromatogram (Fig. DBTs.5. 5. Group A chromatogram shows higher abundance of diaromatic than triaromatic hydrocarbons where BPs are the most abundant compounds from the all diaromatic hydrocarbons. However variations in relative distribution of aromatic hydrocarbons indicate a difference in source and depositional environment of OM.2c). 5.2a). Following sections explained the distribution of each class of above described aromatic compounds in Potwar Basin oils and they were used for evaluation of thermal maturity and source of OM. 5. Distribution of PAHs indicate that at least three types of crude oils are present in Potwar Basin.2.2c) and low abundance of TAS. Significant abundance of BPs and Fs from naphthalenes and phenanthrenes separated group A oil from other groups of oils (Fig. 63 .2b and 5. However significant presence of triaromatic steroids (TAS) and DBTs differentiates group B from group A and C where later groups showed less or absence of TAS and comparatively low abundance of DBTs (Figs. The PAHs profiles of oils generally show variations in relative abundance between different classes of aromatic hydrocarbons where diaromatic (two rings) and triaromatic (three rings) are the predominant components in each representative oil chromatogram (Fig. naphthalenes and phenanthrenes are present in higher abundance in group C oil however naphthalenes showed a double order of the abundance than phenanthrenes (Fig. Generally aromatic hydrocarbons are not diagnostic compounds for the evaluation of source OM characteristics of mature crude oils and sediments. 5. Again. Similarly Fs are comparatively abundant than phenanthrenes in the triaromatic hydrocarbons of the same oil.

naphthalene. methylfluorenes. phenanthrene. methyldibenzothiophenes. MF. TMN. DMN. MN. methylnaphthalenes. TeMN. DMBP. MDBT. dimethylnaphthalenes. methylbiphenyl. dimethylphenanthrenes. methylphenanthrenes. DMF.MBP DMN Group-A a) Adhi-5 DMBP TMN MN BP MF P TeMN DMF N TMN MP DMP Group-B b) Kal-2 TMP DMP DMN MDBT MP TeMN P TAS DMDBT Relative intensity MN DMN MN TMN Group-C c) Toot-12 MP DMP TMP TeMN P N 30 40 50 60 70 80 90 100 Relative retention times (min) Fig. trimethylnaphthalenes. dimethyldibenzothiophenes. TMP trimethylphenanthrenes. BP. triaromatic steroids 64 . P. MBP. dimethylfluorenes. DMP. N. DMDBT. tetramethylnaphthalenes. 5. TAS. biphenyl. dimethylbiphenyl.2 TICs showing distributions of aromatic hydrocarbons in representative samples from the Potwar Basin. MP.

21β(H)hopane to 17β(H). which are known to have effects on these ratios [153154].62 [150]. During maturation the ratio 22S/(22S + 22R) shows distinct change from 0 to 0.67 to 0.70.5.0 (Table 5.2 was obtained from GC-MS analysis of branched/cyclic and aromatic hydrocarbon fractions.53).31 to 0. however narrow range of this ratio is observed within individual groups. The observed values for the parameter are in the range of 0. which equilibrate at somewhat higher thermal maturities [45. Pindori-4 (P14. which are the factors known to have a control on this ratio [155].73 which is different from other oils of group B.151].21α(H)-hopanes [αβ/(αβ+βα)] for C29. The proportion of 22S relative to (22S + 22R) for C32 homohopanes (Xd) is a maturity parameter for immature to early oil window.73. The data listed in Table 5.31 to 0. The slight difference in αβ/(αβ+βα) ratios with in the Potwar Basin shows the affects of source and depositional environment variations on these values. The plot of hopane maturity parameter between C29.57 and 0. 65 . The Ts/(Ts+Tm) ratios show a wide range from 0. For example.57 and 0.9) which are typical of oils generated from mature source rocks [152]. most of the oil samples fall within an equilibrium and higher range of thermal maturity except Adhi-5 which show low thermal maturity. These ratios reach equilibrium in the early oil window so have limited application for studying the relative maturities of crude oils and condensates.45 while group C shows exceeding values of 0.2. Group A representing a single oil Adhi-5 shows intermediate value (0. mostly > 0. group B shows Ts/(Ts+Tm) ratio in the range of 0.4 Thermal Maturity of Potwar Basin Oils A combination of saturated and aromatic hydrocarbons parameters were used to determine the thermal maturity of the Potwar Basin oils. The other hopane based maturity parameter is the ratio of 17α(H).2). Table 5.64 suggesting high maturity for all the oils samples analysed in this study from the Potwar Basin (Table 5.2) shows maximum value of 0. 5. The hopane based parameters were calculated from peak areas of 191 Dalton mass chromatograms.3a [152].6 whereas equilibrium lies between 0.and C30.2. For C32 homologue 22S/(22S+22R) ratio varies between 0.αβ/(αβ+βα) is shown in Fig.81 to 1. Three different ranges of Ts/(Ts+Tm) indicates that this ratio is controlled by the source organic facies and depositional environment.and C30.compounds.

61 MDI 0.96 1.7 7.52 0.Table 5.63 0.92 (S/S+R) C32Hop 0.29 1.7 4.37 0.85 0. MDI: methyl diamantane index (4MD/1-MD + 3-MD + 4-MD).92 0.1 7.47 0.64 0.12 1.59 0.64 0.29 1. [25]. Rc: calculated vitrinite reflectance (0.00 1. MDR′: 4-MDBT/(4-MDBT + 1-MDBT).21α(H) + 14β(H).21α(H)-30-norhopane).23 TNR2 0.57 0. MDR: 4-MDBT/1-MDBT.86 0.29.6.92 1.07 0. C30-Hop 0.9 5.03 0.50 0.1 8.02 0.45 0.83 0.04 1.30-trisnorneohopane + 17α(H)-22.36 0.01 0.5 4.73 0.40 0.2 6.62 0.93 0.7 6. Rcs: 0.8 4.95 0.63 0.63 0.93 0.15 1.64 0.97 1.31 2.6 7.98 1.6 7.97 1.91 0.04 1.+ 1.11 0.88 0.31 0.05 Rcs (%) 0.65 0. [10].21β(H)-30-norhopane + 17β(H).81 0.07 1.85 0.04 0.45 0.57 0.94 0.4).43 0.85 0.61 1.92 0.39 1.38 0.29. MPI-1: methylphenanthrenes index {1.00 0.61 0.7-DMN/1.2 Thermal maturity parameters calculated from aliphatic and aromatic hydrocarbons Ts/ (Ts+Tm) 0. DNR-1: dimethylnaphthalene ratio 1 (2.59 0.2 7.85 1.53 0.5 6.90 0.89 Ts/(Ts + Tm): 18α(H)-22.23 1.85 0.93 0.59 0.85 0.44 0.91 0.61 0. [156].21β(H)] 20R-ethylcholestane.21β(H)-hopane/(17α(H).60 0.5 6. Rcb: 0.87 0.94 1.4 8. [26].6.92 0.6.08 1.48 0.94 0.62 (S/S+R) C29-ster 0.59 0. (ββ/αα+ββ) C29-Ster: 14β(H).96 2.64 0.16 1. [4].2 8.8 7.82 0.59 0.47 0.61 0.4 8.62 0.13 No P1 P2 P3 P4 P5 P6 P7 P8 P9 P10 P11 P12 P13 P14 P15 P16 P17 P18 Oil and Well Adhi-5 Missakeswal1 Missakeswal3 Rajian-1 Rajian-3A Kal-1 Kal-2 Fimkassar-1 Fimkassar-4 Chaknaurang1A Minwal-1 Joyamir-4 Turkwal-1 Pindori-4 Dhurnal-1 Dhurnal-6 Toot-10A Toot-12 MAI 0.5 MDR′ 0.04 1.+ 1.5-TMN).61 0.94 Rcb (%) 1.12 1.61 1. 17α(H)-bishomohopane.86 0.91 0.40+0.6-TMN).87 0.26 1.53 0.50 MDR 6.46 0.84 0.5 10.81 0.87 0.92 0.85 0.64 1.83 1.89 0. αβ/(αβ + βα).47 0.93 0. C30 hop: 17α(H).07 1.88 0.53 0.63 0.05 1.5-DMN).43 1.47 0.87 0.07 1.62 0.91 0.98 1.00 0.99 0.53 0. C32 hop: 22S/(22S+22R).30-trisnorneohopane/(18α(H)-22. [162].8 5.3.59 0.96 1.00 1.4.96 0.41 0.59 0.6 × MPI-1 + 0.09 Rc (%) 0.90 0.90 0.6 5.4 5.3.00 0.48 0.35 0.80 0.94 0.94 0.21β(H)-30norhopane/(17α(H).00 1.50 1.44 1.99 1.92 1.08 1.70 0.18 1.82 0. TNR-2: trimethylnaphthalene ratio 2 (2.92 0.+ 2.3.98 1.25 1.+ 1.63 0.64 0.38 0.85 1.45 0.00 1.40 0.94 0.51.88 0. TNR-1: trimethylnaphthalene ratio 1 (2.02 1.3.8 7.7 6.96 MPI1 0.073×MDR + 0.8 8. -: not determined 66 .62 0. [11].64 0.45 0.00 1.38 1.63 0.4 8.46 0.41 0.90 0.45 0.58 0.97 1.21β(H)-hopane + 17β(H).95 0.60 0.6-TMN/1.36 1.61 (ββ/ αα+ββ) C29Ster 0.70 αβ /(αβ+βα). C29-Hop 0.39 1.61 0.35 1.60 0.4 6.45 0.5 × [3-MP + 2-MP]/[P + 1-MP + 9-MP]}.01 0.21α(H)-ethylcholestane.14 1.91 0.6 11. [40].89 0.03 1.94 0.62 0.61 0.93 0.98 1.48 0.7-TMN)/1.89 0.00 0.75 1.56 0.63 0.11 1.88 0.24 1.4.18 0.02 0.66 0.3.50 0.08 1.94 1.02 1.3.5 5.00 0.29.9 6.30-trisnorhopane).13 1.36 0. S/(S+R) C29 ster: 20S/(20S+20R) 14α(H).86 0.+ 1.47 0.66 0.85 0.61 0.47 DNR1 6.91 0.67 0.90 0.6×(TNR-2). S/(S+R).16 1.04 1.43 0.7 9.89 0.6.90 αβ /(αβ+βα).0 8.03 0.95 1.5 TNR1 1.62 0. [162].44 0.63 0.5.00 1.87 0. [11].21β(H)/[14α(H).10 1.45 0.62 0.93 0. C29 hop: 17α(H).14 1.95 0. MAI: methyl adamantane index (1-MA/1-MA + 2-MA).17 1.01 0.90 1.65 0.08 0.2 11.14 1.92 0.41 0.3 5.21α(H)hopane).45 0. αβ/(αβ + βα).

90 Early oil generation 0.95 αβ/(αβ+βα).7 Early 0. C30-Hop Equilibrium 0.00 αβ/(αβ+βα).1 1.0 Rc (%) 0. [11]) and Rc (MPI-1.1.f. 5. [152]) (b) calculated vitrinite reflectance diagram from Rcb (TNR-2.00 (a) 0.95 1.6 0.80 0.80 0.1 Late 1.9 Peak 0.6 0.0 1.9 1.85 0.75 0. C29-Hop 1.3 (a) Hopanes maturity parameters plot between C29 vs C30 of αβ/(αβ+βα) (c.8 0. 67 .7 0.85 0.2 R cb (% ) Fig. [156]) show different thermal maturation stages of oil generation window.8 0.2 (b) 1.75 0.90 0.

66 respectively. [162] suggested methyl adamantane index (MAI) and methyl diamantane index (MDI) as maturity indicators for crude oils and condensates from Chinese basins. could be responsible for lower values. therefore not very effective for mature oils and condensates [161]. Chen et al.1 and Ro > 1. [162] for Chinese crude oils and condensates show that MAI > 0.53) values clearly indicate the same range of thermal maturities for these crude oils. Despite the fact that 20S/(20S+20R) ratio is a useful maturity parameter. The calibration of MAI and MDI with vitrinite reflectance (Ro) reported by Chen et al.52 to 0. The MAI (0. respectively from saturated fractions and are listed in Table 5.3.The sterane based maturity parameters. respectively.55 and 0. S/(S + R) parameters reach effective end-points or equilibrium before the main part of oil window. However in this study it is suggested that the highest values of 20S/(20S+20R) and ββ/(αα+ββ) to reach equilibrium for the Potwar basin oils is 0.41 to 0.71 respectively [150].5 and MDI > 0. 68 . In this scenario parameters based on diamondoid and aromatic hydrocarbons are more effective for better evaluation of thermal maturity of mature oils and condensates. where equilibrium for carbonate source oils is reached at comparatively lower values [159] and more migrated oils show higher values of this ratio [160].2.59-0. factors other than thermal maturities which are likely to affect this ratio are reversal of this ratio within high maturity interval [157-158].65) and MDI (0.4 is equivalent to Ro > 1.2) whereas the equilibrium for these parameters occurs between 0. sterane and hopane isomerization i. Few limitations have been put forward to thermal maturity parameters described above.59 to 0.48 and 0. Moreover. The MAI and MDI values were calculated using m/z 136. lie with in a close range of 0.e.66 respectively (Table 5. 187. 20S/(20S+20R) ethylcholestane and ββ/(αα+ββ) ethylcholestane.48 and 0. The thermal maturity of Potwar Basin oils is based on equivalent vitrinite reflectance shows the post oil generation window. The observed values are lower than equilibrium values supporting a similar moderate maturity of analysed samples [150].46-0. 137 and m/z 188.67 to 0. ββ/(αα+ββ) ratio is also influenced by source rock mineral matrix and migration. for example.

2) for all samples indicate maturity of source rocks generating these oils reached to postmature level [10].2 that show >1 (mostly >1. Table 5. trimethylnaphthalene ratio 2 (TNR-2. see Table 5.163].95.2). The MPI-1 and Rc is in the range of 0.3b) were drawn from calculated vitrinite reflectance values i.2 for definition) has been calibrated with sterane isomerization ratio (20S/20R) where sterane isomerization ratio of oils reached to equilibrium value when TNR-1 ratio became >1 [10]. TNR-1 values for Potwar Basin oils are shown in Table 5.2. Table 5. Dimethylnaphthalene ratio (DNR-1. Trimethylnaphthalene ratio 1 (TNR-1.2) showed mature status of thermal maturity while all other values (>0. TNR-1 shows a wide range of values from 1. see Table 5.15 respectively show higher maturity of source rocks generating these oils. These differences in TNR-1 ratios are most 69 .31 for Potwar Basin oils although most of the oils lie between 1 and 2 but high values for some of the group B oils are observed (TNR-1 > 2.04 to 2.75 to 1.2.9-1.85 to 1.2 for definition) is another useful aromatic hydrocarbon thermal maturity parameter which was calibrated with mean vitrinite reflectance (Ro) and show good agreement with increase in thermal maturity. mostly ~7-8) clearly revealed that thermal maturity of the Potwar Basin oils is reached late oil generation window. Table 5. The TNR-2 value (0.e.9) indicate postmature level of thermal maturity for Potwar Basin oils [4].0.2 for definition) is another useful aromatic hydrocarbon maturity parameter for samples having mean vitrinite reflectance (Ro) equal or higher than 1% where it shows linear increase in value from 2 to 12 with increase in thermal maturity [4. Few anomalies are observed in alkylnaphthalenes maturity parameters. The MPI-1 and calculated vitrinite reflectance (Rc) values of the samples are listed in Table 5. Rcb (TNR-2) vs Rc (MPI-1) clearly indicate thermal maturity of Potwar Basin oils reached to late oil generation window. The DNR-1 > 5.2) from TNR-2 indicate thermal maturity of the oil samples from the Potwar Basin reached to late oil generation window [11].2. For example.26 and 0. Table 5.The commonly used thermal maturity parameter from aromatic hydrocarbons is methylphenanthrene index 1 (MPI-1) and appears to be as useful as vitrinite reflectance for maturity assessment [4. Similarly.2) and calculated vitrinite reflectance Rcb values (>0. The Rc for Adhi-5 (0.5 (Table 5.25]. A cross plot (Fig.85. 5. see Table 5.

164].40. A wide rang of values are observed for DMR (4.165]. Pristane (VI) to phytane (VII) (Pr/Ph) ratio is a commonly used for depositional environment.e. MDR was calibrated with vitrinite reflectance and reported as Rcs [165]. methyldibenzothiophene ratio (MDR) derived based on similar chemical phenomenon as for MPI-1 i. 45].1 were examined for lithology and depositional environment using aliphatic and aromatic hydrocarbon parameters. The values for MDR′ given in Table 5. [166] pointed out its limitation for coal samples where it does not show linear relationship between 0. 5.81-0. < 1 indicate anoxic/hypersaline or carbonate environment while Pr/Ph ratios 1 to 3 have been associated with marine oxic/dysoxic conditions [1.e. The 70 . Radke and Willsch [40] introduced a revised form of MDR as MDR′ where it was calculated by traditional biomarker maturity parameters way i. Commonly used parameter.83-1.4-11.6) and Rcs (0.2.2 indicate narrow range of values (0. DMR has shown to be affected by variation in expulsion stages of 1-MDBT and 4-MDBT isomers from kerogen [40] and Dzou et al.92) and results revealed higher thermal maturity for Potwar Basin oils [40].0% vitrinite reflectance.53. 4MDBT/(4-MDBT + 1-MDBT). DMR and calculated vitrinite reflectance (Rcs) from Potwar Basin crude oils are shown in Table 5. Moreover. Pr/Ph ratios > 3. a methyl shift from thermally less stable isomer (1-MDBT) to thermally more stable isomer (4-MDBT) with increase in thermal maturity [11].37.2.probably due to the effects of biodegradation on aromatic fractions in group B oils (Chapter 6). Affects of biodegradation on alkylnaphthalenes have been shown to affect different isomers and thus different susceptibilities towards biodegradation [17] and thermal maturity parameters are adversely changed using certain isomers in thermal maturity ratio calculations [38. A number of studies have used alkyldibenzothiophenes as maturity parameters [11.0 have been described for terrestrial input deposited under oxic conditions and low Pr/Ph ratios i.5 to 1.36) indicate peak to late oil generation window thermal maturity of these oils.e.5 Lithology and Depositional Environment The crude oils listed in Table 5.

DBT/P were measured from GC-MS analysis of the aromatic fraction using m/z 184 and 178 for DBT and P respectively. Low diasterane/sterane ratios in petroleum indicate anoxic clay-poor source rocks that are characteristics of carbonates while higher diasterane/sterane ratios refer to oxic clastic source rocks indicative of marine and deltaic environments [45]. sulfur poor lithology/depositional environment and caution was referred to use this Hughes diagram [7]. [167] has been used to infer lithology-depositional environment of the OM and results are shown in Fig. the regular steranes change to rearranged steranes by clay mediated rearrangement reactions in source rocks [169] and diasterane/sterane ratios have been widely used for evaluation of source rock lithology of OM [45].2) indicating highly oxic fluvio-deltaic depositional environment of OM. where oxic/clay rich depositional conditions rearrange hopanes to diahopanes [45].0 to 2. a study on crude oils from NW Germany showed contrast results where marine sulfur rich samples indicate lacustrine. Cross plot of DBT/P vs Pr/Ph suggested by Hughes et al. The largest set of oils from the Potwar Basin (Group B and C) are shown to have originated from marine-lacustrine shale source rocks and Pr/Ph ratio in the range 1. where sulfur reacts with iron species in the clay minerals and in turn produces less DBT.ratio of dibenzothiophene (XXVII) to phenanthrene (XXIV) (DBT/P) is an indicator of source rock lithology. Similarly.1). whereas incorporation of sulfur into OM produces higher DBT while DBT/P ratio <1 indicates a shale type lithology. However. XIV) has been suggested to be a rearranged product of regular hopanes [168] by clay-mediated acidic catalysis and it mostly occurs in marine clastic oxic-suboxic depositional environments. The C30 17α-diahopane/ C30 17αhopane ratio is shown to be high in clastic source rocks and oxic depositional environment. While group A oil (Adhi-5) shows a higher Pr/Ph ratio (3.4a. while Pr/Ph ratios were determined from TIC of saturated fractions. The DBT/P ratio >1 indicates a carbonates type facies.0 support a marine oxic/dysoxic depositional environment (Table 5. 5. C30 17α-diahopane (C30*. 71 .

6 0.C30 Pindori Fig.0 0.4 (a) Pr/Ph versus DBT/P plot indicates lithology and depositional environment [167] (b) C30 17α-diahopane/C30 17α-hopane vs C29 diasteranes/sterane plot shows the affects of clay and depositional environment on Potwar Basin oils (c.8 1.6 0.0 4.4 C 0.0 2.0 1. 1995 (a) 1 2 3 Group B & C 4 Group A 0 0.0 29 (b) A Diasterane/steranes.5.0 Pr/Ph 3. C 0.f. 72 .0 Diahopane/hopane. [45] and refernces therein).4 1A 3 1B DBT/P 2 1A: marine Carbonate 1B: marine carbonate and marl 2: Lacustrine hypersaline 3: marine shale and lacustrine 4:fluvio-deltaic shale Hughes et al.8 B 0.2 0.2 0.4 0.0 0.0 1.

5. 5.4b) which indicate a clay rich oxic depositional environment as indicated by Hughes diagram (Fig. 5.4b). The oil from group A (Adhi-5) shows higher values of diahopane/hopane and diasteranes/sterane ratio (0.2. dibenzofurans (DBFs) and Fs has been related to the source rock lithology and depositional environment 73 . Although both groups located near to each other in the diagram but showed two different places in diagram indicate slight variation in lithology and depositional environment of OM between these groups (Fig.A plot between C30 17α-diahopane/C30 17α-hopane vs C29 diasteranes/sterane ratios is shown in Fig.4b).23) indicating an oxic environment of deposition. The Adhi-5 was probably generated from oxic/clay rich source rocks and is consistent with the C30 17α-diahopane/C29 18α-30-norneohopane (C29Ts. The reason for this anomaly could be related to any factor such as source organic facies. while group C show higher diahopane/hopane ratios indicating that the group C oils were generated from comparatively more oxic deposited source rocks [45].38 and 0. 5. Groups B and C were similar in Hughes diagram (Fig. however both groups (B and C) showed consistent for depositional environment is marine.170] and references therein). XV) ratio. amount of clay contents and total organic carbon that has been suggested to be affecting diahopane/hopane and/or diasteranes/sterane ratios ([45.1 Heterocyclic aromatic hydrocarbons Distribution of heterocyclic aromatic hydrocarbons such as DBTs. respectively) separating this oil from all the other oils (Fig. 5. 5. An anomaly (high value) is observed in the C30 17α-diahopane/C30 17α-hopane vs C29 diasteranes/sterane diagram for the Pindori-4 crude oil (Fig.4a). This variation revealed that group B shows relatively higher diasteranes/sterane ratios compared to the group C indicating that the group B oils are generated from comparatively more clastic rocks.4b and samples from the Potwar Basin fall into three groups. 5.5.4a) are separated into two different groups.97. The C30 17α-diahopane/C29Ts ratio has been suggested as a good indicator of oxic/suboxic depositional settings of OM [45] and this ratio for group A oil is significantly high (2.

Specifically. These results reveal that group B oils showed a strong influence of marine suboxic deposition of OM [12] where sulfur heterocyclic aromatic hydrocarbons (DBTs) are present in abundance.2.3. Distribution of tricyclic terpanes (TT) and hopanes is shown in m/z 191 mass chromatograms (Fig. Groups A show abundance of Fs than DBTs while DBFs are also present in considerable abundance. 5.5). 5. These results most probably indicate indigenous variation in depositional environment.171-172]. three mixed concentration profiles of Fs and DBTs distribution has been reported from marine source rocks and crude oils for oil-source rock correlation study [13]. Whereas abundance of DBTs was related to marine source rocks while abundant Fs and DBFs were referred to freshwater source rocks [12]. Relative distribution of DBTs. DBFs and Fs in Potwar Basin oils (Fig. alkylphenanthrenes and triaromatic steroids are reported as aromatic biomarkers from Potwar Basin oils.of OM [12-13. Similarly. Group C crude oils showed mixed distribution of Fs and DBTs where Dhurnal oils (P15 and P16) showed comparable equal abundance of Fs and DBTs while Toot oils (P17 and P18) indicate higher Fs than DBTs. alkylnaphthalenes.6 Source of OM Source OM of Potwar Basin oils were initially assessed using distribution of aliphatic biomarkers and subsequently PAHs distributions are used to classify the source origin of the petroleums. A bar diagram was constructed that indicate relative percentages of DBTs. While group A show oxic depositional environment of OM indicated by abundant Fs consistent with previous reported results [12-13]. Group A oil shows significantly 74 . The parameters for the assessment of source OM from tricyclic and pentacyclic terpanes and steranes are listed in Table 5.6) of the representative samples from all delineated groups of Potwar Basin. Group B oils show higher abundance of DBTs while DBFs and Fs are present in almost negligible concentrations while group C oils show almost equal abundance of Fs and DBTs except last two oils (P17-P18). DBFs and Fs were calculated from sum of the peak areas of parent compounds (non-alkylated) and methyl substituted isomers. 5.

5 Bar diagram shows relative percentages of DBTs. Fs in Potwar Basin oils. 75 .P18 P17 P16 P15 P14 P13 P12 Fs P11 Oils P10 P9 P8 P7 P6 P5 P4 P3 P2 Group A Group B Group C DBFs DBTs P1 0 20 40 60 80 100 Relative percentage Fig. 5. DBFs.

Table 5.3 and 5. higher total sterane/hopane ratio >0. However difference in positions of group B and C in the diagram (Fig.7) revealed slight variation in source OM for these oils.4) for group C oils reflects greater eukaryotic input (higher algal input). Group A oil (Adhi-5) located in the top right corner of the plot indicating source OM is terrestrial origin. This is the important feature of group C oils to differentiate from other groups of oils. 5. and C24 TeT/C30 17α(H)hopane ratios (Table 5. Moreover. A comprehensive Table 5. The triterpane distribution of group B oil is typical mature marine crude oil (Fig. 5.3) indicated typically marine OM for group B and C oils [45] however two different ranges of these ratios indicate difference in source input in Potwar Basin oils (Table 5.173]. 76 . It could be conclude that at least three groups of petroleum have been produced from different source rocks within the Potwar Basin.6 (~1. both compounds are indicator of terrestrial source OM [45.6b) and the major compounds in the chromatograms are 30 and 29 17α(H)-hopanes. TT and hopane parameters such as C23 TT/C30 17α(H)-hopane. 5. Total TT/hopanes ratio for group C oils is significantly high compared to the rest of the oils indicate a difference in source OM for this group (Tables 5. The higher abundance of TT in Potwar Basin oils is probably associated with algal source of OM.4).7 clearly differentiates three groups of petroleum on the bases of difference in source OM [174175]. The representative mass chromatogram m/z 191 for group C oil shows significantly higher abundance of extended TT upto C41 and possibly higher (Fig. 5. Similarly.6c) whereas C23 TT is the most abundant compound while hopanes show significantly lower abundance.4 is constructed to show different ranges of aliphatic and aromatic biomarkers ratios of source and depositional environment interpretations for Potwar Basin oils. The correlation diagram C19/(C19+C23) TT vs C24 TeT/(C24 TeT + C23 TT) shown in Fig.7). Group B and C located in lower left corner of the diagram indicate marine source OM (Fig.0 for most of the oils.4). IX).low concentration of tricyclic terpane except for C19-TT and C24-tetracyclic terpane (TeT. Hopanes are in higher relative abundance compared to TT and this feature differentiates group B oils from other two groups. 5.

5. numbers on peak indicate TT. 24*. H) in Potwar Basin crude oils. C24-tetracyclic terpane and number with H indicate hopanes.6 Mass chromatograms (m/z 191) showing distribution of tricyclic (TT) and pentacyclic terpanes (hopanes. 77 .a) Group-A Adhi-5 19 24* 30H 29H b) Group-B Chanknaurang-1A Tm 24* 23 21 19 20 Ts 31H S 32H R S 29Ts R 33H 34H S R S R c) Group-C Dhurnal-1 35H S R Relative intensity 23 20 21 19 25 28 29 30 31 32 33 34 24 24* 35 36 38 39 40 41 61 71 81 91 Relative retention time (min) 101 Fig.

74 1.11 0.33 2.44 0.74 0.58 C19/ (C19+C23) TT: C19-tricyclic terpane/(C19-tericyclic terpane + C23 tricyclic terpane).33 0.40 0.79 0.49 0.48 0.49 0.00 1. C30*/C29 Ts: 30.28 0.76 1.66 1.34 0.45 0.77 0.97 0.37 0.03 1.42 0.52 0.18 1.10-DMP). αβ-diahopane/ C30 αβ.28 1.58 1.79 0. C20/C21 triaromatic steroids.55 0.7-DMP/X.85 0.39 0.52 1.78 0. TMN: trimethylnaphthalene 78 .04 2.34 0.27 0.23 0.7DMP/X 0.47 2.83 0.58 0.75 0.51 0.52 0.24 0.30 0.65 0.49 1.38 0.53 2.19 0.93 1.55 0.27 C20/C21 TAS 1.72 0.30 0.61 0.25 0.56 0. 1.46 1. Ster/hop: total steranes/total hopanes.44 0.39 0.hopane.32 0.10 + 3.27 1.hopane.79 0.45 0.63 0.55 0.75 0.75 1.53 0.22 0.04 2.57 1.68 0.15 C27/C29.50 2.20 1.57 1.76 0.90 0.54 0.70 1.38 0.49 0.50 C24TeT/C30 hopane 0.69 0.77 0.51 0.43 0.25 1.20 0.54 1.63 0.57 0.76 0.49 0.3 Source OM and depositional environments parameters of Potwar Basin oils C19/ (C19+C23) TT 0.58 0.07 0.58 0.18 0.84 0.23 1.46 2.34 0.87 0.45 0.15 0.54 0.86 0.+ 2.44 0.45 1.38 0.23 0.55 0.33 0.40 0. 1.45 0.20 0.23 0.35 0.43 0.75 0.06 0.28 2.37 0.75 0.35 1.34 0.42 0.28 0.26 0.75 0.74 0.26 0.32 C24TeT/ (C24TeT +C23TT) 0.46 0.20 0.40 0.77 1.34 0.47 1.41 0.52 1. C27/C29 dia.30 0.47 0. αβ-diahopane/18α(H)-30-norneohopane.25 0.60 0.78 0. dia 0.93 2.74 0.9.22 0.84 0.40 C29/C30 αβ hop 0. 1-MP/9-MP: 1-methylphenanthrene/9methylphenanthrene.33 0.68 0. βα-cholestane/βα-ethylcholestane.Table 5.79 1.52 0.71 0.40 1.19 2.25 0.38 0.75 0.26 0.84 2.46 1.77 1.38 0.2.86 0.23 0.64 0.32 0.28 1.2.03 1.70 0.77 0.76 0.28 0.44 2.24 1. C24TeT/ (C24TeT+C23TT): C24-tetracyclic terpane/(C24-tetracyclic terpane + C23 tricyclic terpane).99 2.60 0.59 0.16 0.22 0.61 0.51 0.26 0. C20/C21 TAS.69 0. total TT/Hop: total tricyclics/hopanes.29 0.29 0.24 0.+ 3. C31 (R+S)/C30 hop: C31 αβ-homohopane (22S+22R)/C30 αβ.24 0.45 0.44 1.46 0.39 0. R+S.35 0.75 0.93 0.51 0.22 0.31 1.36 0.32 0.36 1.04 1MP/9MP 0.7-dimethylphenanthrene/(1.6/1.43 0.3.74 0.64 1.23 1.26 0.88 0. C30*/C30 αβhopane: 30.68 1.17 0.27 0.27 0.54 1.24 1.57 C30*/C30 αβ hop 0.35 1.40 0.15 No P1 P2 P3 P4 P5 P6 P7 P8 P9 P10 P11 P12 P13 P14 P15 P16 P17 P18 oil and well Adhi-5 Missakeswal1 Missakeswal3 Rajian-1 Rajian-3A Kal-1 Kal-2 Fimkassar-1 Fimkassar-4 Chaknaurang1A Minwal-1 Joyamir-4 Turkwal-1 Pindori-4 Dhurnal-1 Dhurnal-6 Toot-10A Toot-12 Ster/hop 0.28 0.16 125/127TMN 3.36 1.15 0.23 Dia/Ster C29 0.07 0.55 1.19 0.4TMN 2.72 0.24 0.28 0.36 0.38 1.44 C23 TT/C30 Hopane 0.55 1.33 0.19 1.27 Total TT/Hop 0.31 0.57 0.97 0.49 0.83 0.33 1.50 1. C23 TT/C30-hopane: C23 tricyclic terpane/C30-αβ hopane C24 TeT: C24 tetracyclic terpane/C30-αβ hopane.81 0.28 0.25 0.76 0.72 0.65 0.49 0.77 0.38 0.27 0.15 0.27 0.87 0.40 0.37 2.82 0.84 1. Dia/ster C29: βα/(αα+ββ) ethylcholestane.96 1.83 1.44 0.07 1.61 0.

0. 173-175].3 0.8 A 0.4 0.5 0.7 0.3 0. 79 .2 0.7 Cross plot between C19/(C19+C23) TT and C24 TeT/(C24 TeT + C23 TT) shows difference in source material in Potwar Basin oils [c.0 Fig.2 0. 5.f.6 C19/(C19+C23) TT 0.6 C24 TeT/(C 24 TeT + C 23 TT) Terrestrial 0.8 0.9 1.7 B 0.5 0.4 C 0.

45 <0.5-0.65-1.4 >0.3-0.177] [45. 175] [173-175] [45] [45] [45.8 <0.6 (~1.2 and 5. C higher marine input 0.7-DMP/X ~0.4 Biomarkers parameters limits for Potwar Basin oils Group A Group B Group C ~0.6 1.0 <0.5 >0.αβ hopane Steranes/hopanes βα/(ββ+αα) C27 βα/(ββ+αα) C29 Total diasteranes/steranes Retene Present 1.46 >0.3 GP A and Gp B showed greater clay affects 0.3 ~1.176] [45.0 >1.32] [5] Parameters* C19/(C19+C23) TT C24TeT/ (C24TeT+C23TT) C23 TT/C30 hopane C24-TeT/C30 hopane Total TT/Hopanes C31(R+S)/C30.45 Gp B generated from more clastic than Gp C >0.5 Gp C shows algal source OM >0. 178] [45.Table 5.3 Gp A terrestrial.3 Gp: Group 0.2 ~0.5 Gp B showed more reducing depositional settings than Gp C <0. >0.5 Gp B and C marine OM input 0.9 ~0.0) Higher marine (algal) input in Gp C >0.0-2.3-0.3 ~0.8 <0.32 GP A indicate terrestrial input 80 .5 (~1.1 <0.53 *: definition in Tables 5.23-0.4 Gp B shows higher clastic/mineral affects Absent Absent Gp A terrestrial <0.5 <0.28 > 0.3 ~0.4 <0.0 Interpretation References [45.5 Gp A terrestrial 0. 179] [45. 155] [45] [5.0) Gp B and C marine.

182]. [181] related a range of alkylphenanthrenes with marine and terrestrial source OM along with affect of thermal maturation. In Potwar Basin oils.5-TMN relative to 1.2.7-TMN in group A oils indicate different source precursor for these naphthalene isomers than those of angiosperms which is further supported by the absence of oleanane (a angiosperm biomarker) and its related products in saturated fractions (Fig.6-TMN.2.7-TMN. 1.180].2.6). abundance of 1.2.2.7-TeMN and 1.2. 1.4-TMN ratios differentiate Potwar Basin oils into three groups. Similarly abietane and pimarane type biological precursors from diterpenoids are more likely the source of alkylphenanthrenes [32].6-TeMN [180]. Budzinski et al.7-TMN vs 1. Aromatic seco-hopanes are also reported as source for 1.2.5-TMN and 1. there is no noticeable abundance of any certain isomer of alkylnaphthalenes were observed.5. 5.5-/1.2.5-TMN and 1.5-TeMN are supposed to be generated from microbial origin [183] while 1. 81 . The 1.6-TeMN (see XXIII for naphthalene numbering system) in sediments and crude oils are suggested to be originate from angiosperms [19.5.6-/1. Distribution of certain isomers of alkylnaphthalenes and alkylphenanthrenes were determined to evaluate the contribution of specific class of biological precursors to the source OM of Potwar Basin oils.2.5-TMN in boghead coals is drimanes by reporting similar δ13C values for both compounds.5.2.3.2.2. 1.7-TMN and 1.5-TMN [141].2. Fig. β-Amyrine from higher plants angiosperm has been showed a source precursor for alkylnaphthalenes [19.2.2.2.4TMN in marine sediments suggested as biomarker for tocopherole [66a].6.3.1 Alkylnaphthalenes and alkylphenanthrenes Abundance of certain methyl substituted isomers of naphthalene (XXIII) and phenanthrene (XXIV) has been reported as aromatic biomarkers derived from specific class of natural products [5.5. 5. In alkylnaphthalenes.2. [184] suggested that the origin of 1.8a shows a cross plot between 1.2.19.5-TMN has been exclusively suggested as angiosperm markers [19] however non-angiosperm natural products are also related to the source of 1. Grice et al. The abundance of 1.180].2. However different alkylnaphthalenes ratios were calculated and reported in Table 5.2.

3 0. 5.5 3.2.7-TMN 2.5 3.7 0.5 0.0 2. 82 .3 0.0 1.2.2.6-/1.5 1.4 C B 0.0 0.5 0.7-DMP/X and 1-MP/9-MP [5] indicated terrestrial input for group A oil.5 1.2.5 1.0 1.8 0.5 2.0 0.5 1.4 0.6 (b) A 0.4-TMN 2.0 3.0 0.0 (a) A B C 0.5-/1.6 1-MP/9-MP 0.8 (a) Distribution relationship between TMN ratios of Potwar Basin oils (b) higher plant aromatic biomarkers ratios 1.4.7-DMP/X 0.2 0.9 Fig.0 1.

8b).. XXa to XXc) and long chain (C25 to C28. 2.12.19].2.7-DMP/X ratio (X is 1. 3. Fig. [11]) is successfully used for correlation study of crude oils having different source OM from various ages [5].5-TMN in group A oil is also most likely the drimanes which are significantly abundant components in branch/cyclic fraction of group A oil (result not showed). Moreover the significant abundance of conifer resin aromatic biomarker retene (XXI.2. 1.185]. Short (C19 to C22.7-DMP clearly indicate terrestrial source precursor for these compounds in group A oil. 1. Chapter 4) is observed in group A oil indicate that major contribution of source OM for this oil is higher plant resins. 3.3-.9 shows representative ion chromatograms (m/z: 231) from each group of Potwar Basin oils.9. 9-MP is related to the marine character of OM while 1-MP related to the terrestrial origin [181] and 1-MP/9-MP ratio was calculated from Potwar Basin oils reported in Table 5. 4. Group B and C oils show similar place in the diagram that show similar origin of alkylphenanthrenes however different position in the diagram indicate some difference in OM input. While 83 . Generally.Source of 1. The abundance of 1-MP and 1. short chain C20 and C21 compounds are present in higher abundance than long chain compounds.7-DMP has been suggested a biomarker from pimarane type diterpenoids abundant in ambers and resins [32. 5. XXe to XXh) TAS with different distributions are observed within the groups.3.7-DMP/X ratios (Fig. 5. Group B and C oils locate near to each other in the TMN ratios diagram indicate similar type of source for TMNs however both groups cluster at different places in the diagram indicate some difference in the source input [4.6.10-DMP isomers coeluted peak Radke et al. A plot between 1-MP/9-MP vs 1.8b) separated Potwar Basin oils in three groups where group A oil shows a separate place in the top right corner of the diagram (Fig.10. 5.2 Triaromatic steroids (TAS) The distribution of TAS was monitored by ion 231 from aromatic fractions and Fig. In alkylphenanthrenes. 5.

R C27.Triaromatic steroids m/z: 231 (a) Group A C20 C21 C27.R C27.S C25.S C28.S C28.S C25.R+C27. Carbon number on peak refers to corresponding TAS (XXa to XXh).R C20 R C22 S (b) Group-B Relative intensity C21 C26.R C28.9 Distribution of triaromatic steroids in Potwar Basin crude oils a) Adhi-5. 5.R c) Group-C 72 76 80 84 88 92 Relative retention time (min) Fig. c) Toot-12.S C19 C26. b) Kal2.S C28. 84 .

9c). TAS from C26 to C28 compounds have been supposed to be originated from demethylation and aromatization of monoaroamtic steriods from corresponding C27 to C29 compounds [47. Significantly higher abundance of C20 and C21 compounds and comparatively negligible concentrations of C19 and C22 compounds in oils indicate a different source precursor for these compounds. But the presence and absence of certain carbon number triaromatic steroids indicate different source precursor for these compounds. Where group A shows only C27 and C28 compounds while group B shows C25 to C28 compounds (Fig. C28 are not fully observed in all samples of Potwar Basin oils. Generally. C27.e. Because full range of regular and rearranged steranes (C27. C28) has been shown effective correlation parameters and indicate similar associations with biological precursors (terrestrial. In long chain TAS. marine and lacustrine input) as referred by regular steranes and monoaromatic steroids [45. however short chain compounds (C20 and C21) are present all samples.9). The absence (or below detection limit) of long chain TAS in group C oil representative chromatogram clearly differentiate this group from other two groups (Fig. 5. A correlation diagram (Fig. C25 to C28 compounds in group B and totally absent in group C oils clearly revealed that TAS from Potwar Basin are source dependent. While short chain compounds has been apparently generated from homolytic scission of long chain triaromatic steroids with increase in thermal maturity [187-188]. TAS (C26.189-190]. C26. C27. 5. 5. Monoaromatic and TAS are very effective thermal maturity parameters for late oil generation window although it has been reported that these parameters are potentially source dependent [45]. C29) are significantly abundant in Potwar Basin oils that has been suggested as source for aromatic steroids [45].10) between C20/C21 triaromatic steroids and C27/C28 diasteranes differentiate Potwar Basin oils into three groups revealed that variation in relative abundance of aromatic steroids is controlled by source input. the presence of only two compounds (C27 and C28) in group A. 85 . C28. Long chain TAS i.distribution of long chain TAS clearly differentiates Potwar Basin oils into three groups.186].

0 2.2 0.0 C20/C21 TAS 1.10 Distribution relationship between C20/C21 TAS and C27/C29 diasteranes from Potwar Basin oil clearly indicate three groups 86 . 5.0 0.2 C27/C29 diasteranes 1.4 1.5 2.1.6 0.4 0.5 1.0 0.8 0.0 0.5 B C A Fig.

While TIC of saturated hydrocarbon fraction from representative group B oil shows substantional UCM and lack of n-alkanes indicating that these oils have been biodegraded and the remaining fraction has become enriched in high molecular weight unresolved components. 5. The Potwar Basin crude oils show a wide range of API gravities (16-48°. Isoprenoids show resistance to biodegradation compared to the n-alkanes because n-alkanes are removed earlier than isoprenoids by bacteria during biodegradation. The results shows that extent of biodegradation for some of the crude oils in this study reaching up to level 3 on the biodegradation scale [46]. Light to very heavy oils from Potwar Basin are present that indicate the alteration of hydrocarbons composition in reservoirs. The plot of Pr/n-C17 vs.5.5.2. 87 . water washing and phase separation [14.5). these latter ratios increase with rising biodegradation.45-46]. 5. It is observed that some of the oils from group B are affected by minor biodegradation while group A and C are non-biodegraded (Table 5. Table 5. 5. The extent of biodegradation on each crude oil of Potwar Basin is represented with level of biodegradation in Table 5. Low API gravity (16-26. The API gravity is a bulk property that directly relates to gross compositions of crude oils.12b) indicative of the oils affected by biodegradation. Hence isoprenoid/n-alkane ratios from saturated fractions increases with increase in biodegradation [191] and Pr/n-C17 and Ph/nC18 ratios greater than 1 typically show the affects of biodegradation on crude oils. 5.12a) shows a trend consistent with biodegradation.12a) shows Pr/n-C17 ratio > 1 indicates the affects of biodegradation on these oils.12b) shows inverse relationship.11. a high Pr/n-C17 and low API gravity (Fig.6°) for some of the oils particularly from eastern Potwar is consistent with biodegradation. Ph/n-C18 (Fig.7 Biodegradation The presence of heavy oils in reservoirs is mostly related by secondary processes such as biodegradation. 5. A number of commonly used parameters have been used to assess the extent/level of biodegradation in Potwar Basin oils. The chromatograms from group A and C show full suite of n-alkanes and isoprenoids with no unresolved complex mixture (UCM) that indicates no signs of biodegradation. The tope right corner of the diagram (Fig.1). Representative total ion chromatograms (TICs) of the saturated hydrocarbons fractions from each group of oils are shown in Fig. A plot of API gravity vs Pr/n-C17 (Fig.

group C. Adhi-5.11 Representative TICs of saturated fractions from Potwar Basin oils. Dhurnal-1. Joyamir-4. Number on peaks refers to n-alkanes carbon numbers. 5. 88 . Group A.C17 C25 Group-A C10 C35 Group-B Relative intensity UCM Group-C 20 40 60 80 100 120 Relative retention time (min) Fig. group B.

6 Fig.2 0.2 1.4 0.5.6 0.8 1.6 0.0 (a) Biodegradation Ph/n -C18 0. 89 .0 1.2 1.8 Pr/n -C17 1 1.1.0 0.4 1.2 0. Pr/n-C17 showing biodegradation trends in crude oils used in this study.2 1.4 0.6 0.2 0.12 (a) Plot of Pr/n-C17 vs Ph/n-C18 and (b) API value vs.8 0.6 Pr/n -C17 60 50 40 API gravity 30 20 10 0 0 (b) Biodegradation 0.0 0.4 1.4 0.

Table 5.5 Assessment of biodegradation results of Potwar Basin crude oils Group# A B B B B B B B B B B B B B C C C C Bio/non-biodegraded Non-biodegraded Non-biodegraded Non-biodegraded Biodegraded Biodegraded Biodegraded Biodegraded Biodegraded Biodegraded Biodegraded Biodegraded Biodegraded Biodegraded Non-biodegraded Non-biodegraded Non-biodegraded Non-biodegraded Non-biodegraded Biodegradation Level* 0 0 0 2 2 3 2 1 1 3 3 3 1 0 0 0 0 0 No Oil and well P1 P2 P3 P4 P5 P6 P7 P8 P9 P10 P11 P12 P13 P14 P15 P16 P17 P18 Adhi-5 Missakeswal-1 Missakeswal-3 Rajian-1 Rajian-3A Kal-1 Kal-2 Fimkassar-1 Fimkassar-4 Chaknaurang-1A Minwal-1 Joyamir-4 Turkwal-1 Pindori-4 Dhurnal-1 Dhurnal-6 Toot-10A Toot-12 *Wenger et al. [46] 90 ..

aromatic and heterocyclic aromatic hydrocarbons separated these oils into 2 sub-groups (B and C). • Rest of oils from Potwar Basin analysed in this study are marine in origin however δ13C and δD stable isotopes and biomarker parameters including TT. Abundant BPs along with MFs is also important feature of this group separate it from other groups. Group B oils showed heaviest δ13C of both saturated and aromatic fractions. in order to evaluate source OM.5-TMN.e. TeT. 1.CONCLUSIONS The hydrocarbon compositions of 18 crude oils from the Potwar Basin were examined using biomarkers. Group A oil showed more negative (isotopically lighter) in δ13C of both saturated and aromatic fractions from all other oils clearly differentiates. hopanes. B and C) with following key geochemical differences. Some of the group B crude oils are showed depletion in low molecular weight hydrocarbons particularly n-alkanes. maturity. aromatic and heterocyclic aromatic hydrocarbons distribution and stable isotopic compositions of saturated and aromatic fractions. 1-MP. TT are less abundance than hopanes. 2. These geochemical characteristics differentiate Potwar Basin oils into three groups (A. by minor biodegradation (upto level 2-3) while OM is generated from marine clastic rocks deposited in marine suboxic/dysoxic depositional environments.2. lithology and depositional environment and level of biodegradation. The saturate hydrocarbons profile showed typical non biodegraded crude oil. Abundance of C19 TT and C24 TeT along with higher abundance of diagnostic aromatic biomarkers i. DBTs aromatic hydrocarbons are abundant components in group B along with significant presence of short and long chain TAS distinguished this group from others.7-DMP and retene revealed terrestrial source OM for group A oil. 91 . • Group A oil showed higher Pr/Ph with low DBT/P reveals fluvio-deltaic source rocks deposited in highly oxic depositional environments.

92 . Group C oils showed light δ13C of saturated fractions than group B oils however δ13C of aromatic fractions of group B and C are not very different.• Group C represented typically non-biodegraded matured marine crude oils deposited in marine oxic environments which are generated from source OM enriched in algal source input indicated by higher extended TT. Significant presence of short chain TAS and totally absent of long chain TAS are important feature of this group oils. TT are more abundant than hopanes.

The relative susceptibility of alkylnaphthalenes and alkylphenanthrenes at low levels of biodegradation was discussed. The low level of biodegradation under natural reservoir conditions was established on the basis of biomarker distributions.6 POLYCYCLIC AROMATIC HYDROCARBONS (PAHs) AND STABLE HYDROGEN ISOTOPE STUDY AS INDICATOR OF MINOR BIODEGRADATION ABSTRACT Distribution of PAHs and stable hydrogen isotopic composition (δD) of nalkanes and isoprenoids has been used to assess the minor biodegradation in a suite of crude oils from Potwar Basin.Chapter . Pakistan. The δD values of isoprenoids do not change during the minor biodegradation and are similar for all the samples. The data are consistent with the removal of D-depleted low-molecular-weight (LMW) n-alkanes (C14-C22) from the oils. API gravity. The average D enrichment for n-alkanes with respect to the isoprenoids is found to be as much as 35‰ for the most biodegraded sample. Bulk stable hydrogen isotope of saturated fractions of crude oils show an enrichment in D with increase in biodegradation and show a straight relationship with biodegradation indicators i. The biomarker study revealed that crude oils share a similar source and thermal maturity. trimethylnaphthalene and tetramethylnaphthalene biodegradation ratios were purposed that showed significant differences with increasing biodegradation and are suggested as good indicators for assessment of low level of biodegradation. 93 . δD values for the n-alkanes relative to the isoprenoids are enriched in deuterium (D). For the same oils. Pr/n-C17.e. The dimethylnaphthalene.

6.6. Table 5. The effects of biodegradation on PAHs in reservoirs have been reported in several studies [15.149. so the . In general.41]. a suite of eight crude oils from Potwar Basin (group B. whereas the HMW n-alkanes show little isotopic change [193].6-TeMN) in sediments and thermally immature oils is generally related to source(s) [38.2. Susceptibility of PAHs to biodegradation is dependent on the number of aromatic rings and alkyl substituents on the rings.156] and multiple accumulation histories of oils in reservoirs [38]. Generally. a D enrichment in the n-alkanes of up to ca. The application of compound specific isotope analysis (CSIA) has become a powerful tool for assessment of source. [149] reported a significant isotopic fractionation in moderately biodegraded oils.6-DMN. the susceptibility to biodegradation decreases with an increase in the number of aromatic rings and in the number of alkyl substituents on the aromatic moieties [41. carbon) results in a larger fractionation.129].2. residue becomes enriched in 13C and D [202]. For alkylnaphthalenes and alkylphenanthrenes the thermodynamically more stable isomers are generally more susceptible to biodegradation [15.g. In this study.2. biodegradation leads to compounds by removing isotopically lighter 12 13 C enrichment in the residual C compounds from crude oils [44. Sun et al.41.44]. 1.38.48. nC15 to n-C18) can lead to 25‰ enrichment in D.10.2. Microbes preferentially utilize the lighter isotopes i.198- 201].181].e. 1. 35‰ being observed. section 5. The higher relative abundance of certain PAHs isomers (e.17.7-TMN and 1.g.5.5) was analyzed for compound specific stable hydrogen isotopes of 94 12 C and H. In vitro biodegradation studies of crude oils have demonstrated that fractionation of the LMW n-alkanes (i.193-197]. the sterically-hindered isomers with alkylation in the 4 position are less susceptible than other isomers [49].192].e.1 INTRODUCTION Polycyclic aromatic hydrocarbons (PAHs) from sedimentary OM have been widely used to assess thermal maturity [4.44. thermal maturity and biodegradation [17. Alkylbenzenes are the first aromatic compounds to be removed from oil during in-reservoir biodegradation [43. For the alkylbiphenyls. 1. The greater mass difference between hydrogen and deuterium compared with other stable isotopes (e.5-TMN.

7). In the Joyamir-4 oil (Fig. API gravity) and it has been observed that a range of non-biodegraded to minor biodegraded crude oils are present in Potwar Basin (Chapter 5. These finding show that crude oils from this set of oils show a range from non-biodegraded to minor biodegradation up to level 2 to 3 [46]. For the Missakeswal-1 oil. Section 5. API gravity with in this set of eight 95 .1). group B). 6. the n-alkanes are significantly lower in abundance and there is a lack of the lower MW isoprenoids. Ph/n-C18. A suite of eight crude oils show similar source OM and thermal maturity were selected for detail assessment and affects of biodegradation on hydrocarbons (Table 6. the saturated hydrocarbons (Fig. The affects of biodegradation on δD values of n-alkanes and isoprenoids (Pr. 6. during minor biodegradation. The notion behind the approach is that.saturated hydrocarbons and PAHs distributions.2 RESULTS AND DISCUSSION Bulk and compound specific hydrogen isotope analysis and distribution of PAHs have been used to evaluate their applications for assessment of minor biodegradation in Potwar Basin crude oils.1 Assessment of Biodegradation Evaluation of the extent of biodegradation was reported using different biodegradation indicators (Pr/n-C17. 6.1). A sample suit composing non-biodegraded to minor biodegraded crude oils has been used (Table 6.1c) there is a significant increase in the relative abundance of the UCM.2. 6. Ph) and susceptibility to biodegradation of PAHs is investigated.1a) show a typical non-biodegraded profile. Similarly. Biodegradation susceptibilities order for individual isomers of alkylnaphthalenes and alkylphenanthrenes is suggested from non-biodegraded to minor biodegraded crude oils from Potwar Basin.2. 6. The sequential affects of biodegradation on saturated fractions from these selected crude oils is shown by TIC of saturated hydrocarbons fractions in Fig 6.1. microbes consume isotopically lighter compounds and the remaining compound classes become enriched in isotopically heavy compounds. having a full suite of n-alkanes. The crude oils believed to share a similar source and thermal maturity (Chapter 5.1b) shows a lack of the lower MW n-alkanes. while the Rajian-3A oil (Fig.

C18 from m/z 57[203] BP2: 17α 21β(H) hopane/(Pr+Ph).9 MDIA/ DIA 2.4 2.2 5.crude oils show a subtle change from very light oil (Pindori-4.0 1.5 2.3 1.0 Pr/ Ph/ n-C17 n-C18 0.4 5.3 0. Peak areas of 1-MA + 2MA from m/z 135 and adamantane from m/z 136 [204.203. Peak area of hopane from m/z 191 and pristane.205]. isoprenoids.3 6.7 18.5 0.2 1. XVIII).9 4.9 0.8 0.1 Pr/Ph 1.4 Pr / Ph: Pristane / Phytane BP1: (Pr+Ph)/(n-C17+n-C18).124] 96 .65 0.06 0.84 0.11 0.6 2.5 2.6 22. Table 6.0 1.99 1.06 MA/ A 5.1c) indicates the possibility of mixing of heavy biodegraded oils with non-biodegraded oils in the reservoirs [124.9 0.4 16 16.07 1.0 BP1 0. A significant presence of n-alkanes in saturated fractions along with substantional UCM in very heavy oil (Fig.5 1.3 1.09 0.3 1.0 5.7 0. API gravity: 16.8 1.0 1.2 1.124] MDIA/DIA : ratio of methyldiamantanes (1-MD + 3-MD + 4-MD)/Diamantane (DIA. Peak areas of 1-MD + 3-MD + 4-MD from m/z 187 and adamantane from m/z 188 [204.2 26.9 1.15 0.3 2.3 1.3 5.04 0. API gravity: 41°) to very heavy oil (Joyamir-4.11 1. XIX).93 0.2 4.3 1. 6. Peak areas of pristane and phytane from m/z 183 and n-C17 and n.6 2. phytane from m/z 183 [203] MA/A : ratio of methyladamantanes (1-MA +2-MA)/adamantane (A.15 BP2 0.18 0. aliphatic biomarkers and diamondoids hydrocarbons ratios Oil# Name P14 P2 P13 P7 P5 P10 P11 P12 Pindori-4 Missakeswal-1 Turkwal-1 Kal-2 Rajian-3A Chaknaurang-1A Minwal-1 Joyamir-4 API Gravity 41 36.1°).10 1.01 0.4 2.1 n-Alkanes.2 1.5 1.1 1.

10trimethyltridecane. UCM. 6.Missakeswal-1 API: 36.6.C17 (a) P2. Pr. 97 Increase in biodegradation .10-trimethyldodecane (farnesane).1 UCM Relative Retention Time Fig.10-trimethylundecane (nor-farnesane).6. C11 to C36 indicate carbon number of n-alkanes.6.2 C25 Pr d c b a e Ph C11 C36 (b) P5-Rajian-3A API: 22.-trimethylpentadecane (nor-Pristane).7 Relative intensity (c) P12-Joyamir-4 API: 16. a: 2. e: 2.10.1 Total ion chromatograms of saturated hydrocarbon fractions for Potwar Basin crude oils showing different degrees of biodegradation.6. b: 2. phytane. d: 2. unresolved complex mixture.6-dimethylundecane. pristane and Ph. c: 2.

3) and so appear not to be mixtures.83. In the case of the Potwar Basin oils herein. and showed some correlation with biodegradation and with viscosity. Interestingly the Potwar Basin oils show a similar range of thermal maturity (Chapter 5. Components such as the 25-norhopanes are associated with oils that have undergone significant biodegradation [205-206]. Section 5. other hydrocarbon classes were examined to assess the level of mixing of the samples (e.g. The available biomarker distributions in the samples do not provide any firm evidence for in-reservoir mixing. 98 . Koopmans et al. None of the oils from the Potwar Basin was found to contain these components. The diamondoid ratios for the Potwar oils are similar (Table 6.21β(H) hopane/(Pr + Ph). 6.207]).1c) might suggest petroleum being comprised mixture of non-biodegraded oil with a severely biodegraded oil. [124]). Further work for the determination of possible biodegradation mixing is carrying on. The mixing of non-biodegraded with heavily biodegraded oils has shown variations in the ratio of methyl adamantanes/adamantanes (MA/A) and methyl diamantanes/diamantanes (MDIA/DIA. [124. but the possibility of in-reservoir mixing cannot be conclusively excluded since many petroleum reservoirs appear to contain mixtures.203. The mixing of a severely biodegraded crude oil with a fresh oil charge has also been shown to affect various thermal maturity parameters [203. Fig.2.1. [203] proposed a mixing model for biodegraded petroleum. 6. respectively.21β(H) hopane/(Pr + Ph) values for the Potwar Basin oils are shown in Table 6. based on (Pr + Ph)/(n-C17+n-C18) and 17α.1). again indicating little or no mixing.207] and results in significant changes in δ13C and δD [208]. the presence of both UCM and n-alkanes (Fig. These ratios have been plotted against API values and show a very good correlation (R2 0.2) indicating that the oils do not appear to mixtures.In reservoir mixing The relative abundance of the UCM in saturated hydrocarbon fractions rises when the LMW components are removed [46].95 and 0. The API gravity of 16° (Joyamir-4) in the most biodegraded oil point to the possibility of inreservoir petroleum mixing. These parameters are strongly affected when oils consist of mixtures with different levels of biodegradation. The (Pr + Ph)/(n-C17 + n-C18) and 17α. Diamondoids are one of the most resistant hydrocarbons to biodegradation [124]. Other than des-methylhopanes.

15 0. 21β (H) hopane/(Pr+Ph) 0.83 0.20 Fig.0 1.2 Relationship between API gravity and biodegradation parameters (BP1 and BP2.10 17α.6 0.00 R2 = 0. 99 .95 API API 40 30 20 10 0 0.50 40 30 20 10 0 0. 6.2 R2 = 0.8 (Pr+Ph)/(n-C17+n-C18) 1.4 0. [203]) showing API to by controlled by biodegradation rather than any other factor such as mixing.05 0.

0 1.5 Pr/n -C17 Fig.3 δDsats vs.4 1. Pr/n-C17 plot shows straight relationship that increase in biodegradation is accompanied by enrichment in deuterium of saturated fractions.3).6 0. It has been shown that Pr/n-C17 is a good indicator to show the affects of biodegradation on Potwar Basin crude oils (Chapter 5.7 0.9 1.2. This revealed that lighter isotopes of saturated fractions are preferentially removed by microbes and remaining saturated fractions become enriched in deuterium (D) and this is in agreement with previous study [202]. 100 .1). That means with increase in biodegradation the δD of saturated fractions become isotopically heavy. section 5.3 1. Table 5.8 0. A straight relationship between variables shows that with increase in biodegradation indicated by increase in Pr/n-C17 is accompanied by increase in δD i.1 1. 6.2.6.6).2 Bulk Hydrogen Isotopic Compositions of Saturated Fractions A progressive change in δD values of bulk hydrogen isotopes of saturated fractions of crude oils has been observed (Chapter 5. δD of saturated fractions move to more positive. A cross plot of δDsats vs Pr/n-C17 is used to show the affect of minor biodegradation on δD of saturated fractions (Fig.e. 6.2 1. -120 biodegredation enrichemnt in D -130 δD(‰) sats -140 -150 -160 0.

Table 6.213].2. The HMW n-alkanes (>n-C22) are less affected by minor biodegradation and 101 . 6.2) show less negative (heavy) values for stable hydrogen isotopes of LMW n-alkanes.4.210-212]). [209] the D/H fractionation that occurs between water is ca. These studies have shown that hydrogen isotopic exchange occurs more readily for isoprenoids that contain tertiary carbon centers.3 Compound Specific Hydrogen Isotopic Compositions of nAlkanes and Isoprenoids Table 6.g. nonBiodegraded crude oils (Pindori-4 and Missakeswal-1. Similar differences have been reported for relatively ‘immature’ sediments dating from recent to Devonian (e. The LMW n-alkanes (n-C14 to n-C22) show a significant enrichment in D with increasing level of biodegradation. This leads to the fact that isoprenoid lipids are being depleted in deuterium relative to n-alkyl lipids in organisms. 158‰ and ca.2) show more negative (lighter) values while minor biodegraded crude oils (Rajian-3A and Minwal-1. one in the LMW region and other in the HMW region of the plot (Fig. These results are also consistent with respect to 13C enrichment observed for LMW n-alkanes in previous biodegradation studies [214]. Pr and Ph) are depleted in D relative to n-alkanes by up to about 80‰.6. Two different profiles are clearly visible across the n-alkanes δD plots. [197.4a). The δD compositions for individual n-alkanes from the same suit of oils are shown in Fig. Based on extant studies by Sessions et al. 235‰ for alkyl and isoprenoid lipids. The δD values for Pr and Ph are generally similar for all crude oils. whereby isoprenoid alkanes (e. With rising maturity. respectively. Table 6. This shows nonbiodegraded oils contained isotopically lighter compounds compare to the minor biodegraded oils. thermal maturity appears to have influence on this trend. However.2 shows δD values for n-alkanes and isoprenoids (Pr and Ph) in a suit of crude oils ranging from non-biodegraded to minor biodegraded samples. via a mechanism involving carbocation-like intermediates.g. 6. Pr and Ph become enriched in D. whereas the δD values for n-alkanes generally remain constant until a very high maturity level is reached [197.

Table 6. 102 . Pr Phytane.2 δD(‰)* values of n-alkanes and isoprenoids from Potwar Basin oils Sample n-alkanes\name P14 Pindori-4 P2 Missakeswal-1 P7 Kal-2 P5 Rajian-3A P11 Minwal-1 n-C14 n-C15 n-C16 n-C17 n-C18 n-C19 n-C20 n-C21 n-C22 n-C23 n-C24 n-C25 n-C26 n-C27 n-C28 n-C29 -151 -159 -157 -164 -165 -164 -160 -161 -154 -150 -148 -141 -133 -135 -132 -135 -151 -159 -154 -149 -152 7 -165 -169 -166 -168 -169 -167 -166 -165 -163 -168 -150 -153 -126 -123 -127 -129 -155 -166 -165 -157 -161 5 -130 -130 -132 -137 -135 -138 -133 -135 -141 -132 -130 -128 -126 -123 -122 -117 -131 -135 -157 -152 -155 -20 -129 -129 -133 -139 -140 -141 -135 -126 -129 -123 -117 -119 -116 -117 -115 -118 -127 -132 -142 -141 -142 -10 -119 -124 -122 -125 -126 -128 -128 -135 -135 -138 -135 -135 -132 -126 -118 -118 -128 -127 -157 -168 -162 -35 Aver n-C14-29 Aver n-C14-22 Pristane. Ph Aver. (Pr + Ph) Difference (∆δ) (Pr+Ph).(n-C14-22) *: δD (‰) with respect of VSMOW with in standard deviation of 5‰.

(a) n-C14 to n-C29 nalkanes (b) significant effect of biodegradation is observed in n-alkanes.4 The δD (‰) distribution of n-alkanes from Potwar oils. 6. 103 .-100 (a) -120 Pindori-4 Misakeswal-1 Kal-2 δD ‰ -140 -160 Rajian-3A Minwal-1 -180 n-C14 n-C18 n-C22 n-Alkanes n-C26 n-C29 -100 n-C14 to n-C22 (b) Pindori-4 Misakeswal-1 -120 δD ‰ -140 -160 Kal-2 Rajian-3A Minwal-1 -180 n-C14 n-C16 n-C18 n-alkanes n-C20 n-C22 Fig. nC14 to n-C22.

Pr and Ph are consistent with trends reported for non-biodegraded oils [197]. On the other hand.2). Pindori-4 (Table 6.e. The δD values for the isoprenoids (Pr and Ph) are fairly similar for all the oils and therefore do not appear to have been affected by biodegradation. the largest ∆δ offset (35‰) and lowest API value is observed for the Minwal-1 oil. whereby molecules containing the lighter isotope (i.86 and R2 = 0. the order of difference being consistent with that reported for microbes. The average δD values for the n-alkanes were calculated for n-C14 to n-C22 (Table 6. leading to enrichment in D for the residual components.their δD values are probably representative of the original OM source for n-alkanes. n-alkanes [202]. A difference in δD values between isoprenoids and n-alkanes represented as ∆δ. which is the most biodegraded oil of the suite.5 and shows a good correlation (R2 = 0. It appears that the n-alkanes have been fractionated during biodegradation. Interestingly the oils show a large ∆δ offset between the n-alkanes and isoprenoids. The δD of isoprenoids (average of Pr and Ph) are shown in Table 6. Using molecular parameters to assess light to moderate biodegradation levels of oils is difficult because components are removed in a quasi-stepwise fashion. isoprenoids/ n-alkanes). The plots of ∆δ against API values and Pr/n-C17 is shown in Fig.67. These oils were shown to be the most biodegraded on the basis of molecular compositional differences (API gravity. together with molecular parameters can be used to assess low biodegradation levels (2-3) of petroleum.2) since these compounds are most affected by biodegradation. The other oils fall between these two end-members. For the least biodegraded oil. i.e.2). H) are preferentially consumed. respectively) also consistent with an increase in biodegradation as these parameters decrease and increase. This study shows that δD differences for n-alkanes and isoprenoids.2. has been calculated by subtracting the average δD of LMW n-alkanes from the average δD of Pr and Ph (Table 6. respectively. 6. 104 . high API gravity and the similar δD values for n-alkanes.

7 0.9 1.2 1. 6.10 ∆δD isoprenoids-n. (a) API gravity.4 Fig.1 1.alkanes (‰) 0 -10 -20 -30 -40 10 15 20 25 API 30 35 40 (a) 45 10 ∆δD isoprenoids-n. and (b) Pr/n-C17 105 .3 (b) 1.5 Plot of δD(‰) difference between LMW n-alkanes (n-C14 .6 0.n-C22) and isoprenoids vs.alkanes (‰) 0 -10 -20 -30 -40 0.8 0.0 Pr/n -C17 1.

1 Effects of Biodegradation on PAHs Alkylnaphthalenes The biodegradation susceptibility of PAHs and their alkyl analogous is often more complicated to discuss than that of aliphatic hydrocarbons.2.and 1.2.6. It has been reported that the 2.3-DMN appear to be the highly resistant to the biodegradation. Certain aromatic hydrocarbons isomers are more affected towards biodegradation than others [15.7-DMN and 1. Minwal-1. Combination of mass chromatograms from aromatic fractions for the dimethyl.7) relates to the thermodynamic stability of the isomers.7-DMNs indicate similar susceptibility towards biodegradation. 6. The 1. DMN. 6. 6. The sequence of susceptibility to the biodegradation for DMNs (Fig.2.and 2.6. 1.7.naphthalenes (TeMNs) of selected least to most biodegraded samples are shown in Fig.isomers are significantly altered in DMNs and the 1.6.4-TMN and 1. 6. Methylnaphthalenes (MNs) appear to be the highly susceptible alkylnaphthalenes based on their decrease in relative intensities compared to other alkylnaphthalenes biodegradation increases.2.and 2.6c).6).7.6a and b).6.5-TMN 106 . A significant depletion in the 2-MN isomer relative to the 1-MN isomer is observed with rise in levels of biodegradation (Fig.6) at the higher biodegradation levels. It indicates DMNs are more depleted by biodegradation than TMNs and TMNs show more depletion to biodegradation than TeMNs. This biodegradation susceptibility sequence between alkylnaphthalenes (DMNs. In highly biodegraded sample from the set of oils (level-3.6.6. the 2. Biodegradation susceptibilities of aromatic hydrocarbons have been reported by laboratory simulation and reservoir studies [see 45].7-. the 2. 6.3. 6.6-DMN is more susceptible to biodegradation than similar isomer i. For TMN isomers.7-DMN (Figs. Similar trends can also be seen for other higher alkylnaphthalenes i. 2. similar biodegradation affects to the DMNs observed (Fig.41.7). TMN and TeMN isomers (Fig. With in the DMNs.6).(TMNs) and tetramethyl.3. Fig.43]. 6.4 6. TMNs and TeMNs) showed similar trends reported in previous results [41].(DMNs). 6. The depletion in aromatic hydrocarbons can be seen from the relative intensities of various aromatic compounds by biodegradation identified in the aromatic fractions (Fig.e.isomers from TMNs indicate to be more depleted to biodegradation than the 1.4. trimethyl.e.

6. trimethylnaphthalenes.4.2.2.7+ 1. TMNs.4.3.5 1.7 1.4.DMNs m/z: 156 1.7 1.4 1.3.2.3.5. DMNs.3 1. 107 .6.3.6 (b) P5-Rajian (c) P11-Minwal 40 42 Relative retention time (min) 44 46 48 50 52 Fig.7 1.6 TMNs m/z: 170 1.6 2.2.2.6 1.4.7 1.7 1.2.2.7 (a) P2-Missakeswal 1.3.6 Biodegradation susceptibility for alkylnaphthalene distributions (m/z 156+170+184.6 1. tetramethylnaphthalenes.2.6.3.6. Numbers on each peak refer to respective alkylnaphthalene isomer and highlighted peaks show isomer components most affected by rising biodegradation.2.7 1.6 TeMNs m/z: 184 2.3.6 1.7 1.7 1.7 1.5 2.3.3.4+2.3. dimethylnaphthalenes. 6.2.2.6 1.2 1.5 +1.6 2.5.6.5 1.5.7 1.7 1.2.3 1. TeMNs).

2.3.7+1.7>1.3.6.2.3.7+1.7~2.6+1.9+4.5>1.7>1.5)-TMNs.6.6+3.5>2.4.4 TeMNs 1.6.5.8~1.6+1.7~1.2.2 >~1. [38] for TMNr (1.2.7>2.7>2.3.4+2.7>1.2.10>1.2.2.6+2.9+4.2.4.2.4.3.2.6>1.6+1.5.6~1. 108 .7 TMNs 1.3+1.6+1.2.5 Most Susceptible Least Susceptible PMNr TMNr TeMNr Fig.2.7>>2.7>1.2.3~1.5.6.3+3.6>1.7> 1.10+1.2.6.9~1.MNs 2>1 DMNs 2.10+3.3.6~1. 6.7 MPs 2>3>9~1 DMPs 2.2.3.7/1.2.7/1.7 Order of susceptibility of alkylnaphthalenes and alkylphenanthrenes to microbial attack in the Potwar Basin crude oils (cf. Ternary plot was plotted using similar conditions for analysis and identifications as reported by van Aarssen et al. Numbers refer to positions of methyl substituents. [15]).4.5.7>1.3.2.7+1.5)-TeMNs and PMNr (1.3.6>2.5.9+1.6.6)-PMNs.2~2.6>1.3.5. TeMNr (1.3.5~1.2.7~1.3.4.3.5~1.3.3.5.7+(1.6.4.3.7/1.5>1.3>1.

3.& 1.2-DMN).3. TMN biodegradation ratio (TNBR: 1. the order of most to least biodegradation susceptibility for the TMNs is 1. up to about a level of 3.2.3.7-TeMN isomer.3.6-DMN/1. [41] reported a significant abundance of the 1. However.7-TMN) and TeMN biodegradation ratio (TeNBR: 1.6). These observations indicate biodegradation level for the Potwar oils to be at a minor level of biodegradation. TMN biodegradation ratio (TBR:1.3. For the Potwar Basin oil samples. generally TMNs show a decrease in relative intensity with rising biodegradation (Figs.3. The most resistant TeMN isomer in the Potwar Basin oils to biodegradation is the 1.7TeMN/1.4. In the Potwar Basin oils.3. They were designated those ratios by different names. Fisher et al.3.4-TMN) and TeMN biodegradation ratio (TeBR: 1.6-.6-TMN as being the highly susceptible isomer to biodegradation from reservoirs studies. most of the isomers are not altered during biodegradation with out few exceptions.5. Fisher et al.7-TeMN) (Table 6. 6.2.3. [41]. [42] reported the 2.3.7.5.6-TMN in a minor biodegraded oil while Huang et al. The exception of the 1.> 1. consistent with the data reported by Fisher et al. Although these alkylnaphthalene isomers are 109 .5-TMN isomers.3.6.3.6. slight differences in the relative intensities of some the TeMNs peaks are showing changed with rise in the biodegradation (Fig.5-DMN).6-TMN/1.7-TeMN isomer and the least resistant the 1. [41] proposed different polymethylnaphthalene ratios to determine the biodegradation level in a number of coastal sediments. 6.6b and c).2.and 1.7.7TeMN/1. DMN biodegradation ratio (DBR: 1.isomers (Fig.6.7. In light of this biodegradation sequence we are proposing different methylnaphthalenes biodegradation ratios (MBRs) to determine the low level biodegradation particularly in oil samples.3).7-TMN/1.5.6-DMN/1.7). It is noteworthy to observe that isomers which are structurally similar were applied in these Biodegradation Ratios (BRs) from every alkylnaphthalenes. These MBRs ratios were calculated by dividing the area of the most susceptible isomer from respective methyl naphthalenes to the least susceptible methyl naphthalene isomer and are shown in Table 6. It contains DMN biodegradation ratio (DNBR: 1.6.3.2. the effect of biodegradation appears to be light.6. With in TeMNs. 6.6-TeMN) indicating affective assessment for biodegradation samples up to about level 6 of biodegradation. The susceptibility sequence to the biodegradation of various isomers of naphthalene is reported in Fig.

3.3 Biodegradation ratios (BR) and alkylnaphthalenes ternary plot ratios.77 0.70 n.4 1.0 0.80 0.9 3.7-TeMN / 1.8 0.3.d.3. 1. 0.5)-trimethylnaphthalenes [38] e TeMNr: (1.70 0.3 1.49 0.47 n.6 1.7-TMN c TeNBR: tetramethylnaphthalene biodegradation ratio.2.d.6.5.6.4 2.85 0.2.3.5)-tetramethylnaphthalenes [38] f PMNr: (1.6 0.71 0.2.5.46 TeMNr e PMNr f 0.57 0. Level* 0 0 1 2 2 3 3 DNBRa 6.5.3.3.3.9 3.3 2.2 2. n.2.60 0.4 5. 0.2-DMN b TNBR: trimethylnaphthalene biodegradation ratio.7+(1.5.7+1.d.8 4.7+1.2. Oil # P14 P2 P13 P7 P5 P10 P11 P12 Name Pindori-4 Missakeswal-1 Turkwal-1 Kal-2 Rajian-3A Chaknaurang-1A Minwal-1 Biodeg.5 5.6 3.7 / 1.81 0.82 0.1 4.7-TeMN d TMNr: (1.7 5.6.6)-pentamethylnaphthalenes [38] n.6+1.4. a DNBR: dimethylnaphthalene biodegradation ratio.59 0.2.51 0.79 0.4 n.6-DMN / 1.: not determined 110 .1 0.3.5.1 2. 1.Table 6.64 n.7 / 1.0 4.d.8 TNBRb TeNBRc 5.7 / 1. 3 Joyamir-4 4. *: from Table 5.7-TMN / 1.5. 0.39 n.d.d. 1.3.d.4.9 3.2.4 TMNrd 0.

4 6.6 0.7) TNBR (1.60 0.0 4.5 0.0 1.4 0.3.0 5. 111 .8 Pr/n-C17 1.4 (TeNBR (1.40 Fig.0 DNBR (1.40 0.6. Pr/n-C17 showed a good correlation.80 Pr/n-C17 1.0 3.0 0.5.6/1.00 1.5 2.3.0 1.7) 2.2 1. 6. TNBR and TeNBR is observed.20 1.7.0 0. A significant decrease in DNBR.8 Polymethylnaphthalenes biodegradation ratios vs.5 1.0 2.0 0.3.6 0.0 1.2 1.7/1.0 3.0 0.8 Pr/n-C17 1.0 1.2.2) 5.0 6.4 0.7/1.0 4.

0.7).3. the most resistant. It has been shown that alkylnaphthalene ratios (TMNr.2. 6. 6.3.6-TeMN and 1. Table 6. The alkylnaphthalene ratios for the Potwar Basin oils (TMNr.5-TMN and for the TeMNr isomers 1. 6. 6. Hence.4. c.9.6. The isomers which appear to have a higher resistance to biodegradation have greater steric hindrance than those with less resistance to biodegradation.structurally similar they tend to show a significant difference in susceptibility to biodegradation (Figs. biodegradation led to a decrease in the TMNr and TeMNr values (Fig. biodegradation and mixing of oils. 0. based on the distribution of alkylnaphthalenes. 6. Similar results are observed for TNBR and TeNBR [41].44. TeMNr and PMNr. TNBR. It shows that increase in alkylation on aromatic rings results in the decrease in susceptibility to biodegradation which is consistent with previous studies [14. TeMNr and PMNr.88..7TMN > 1.5.7-TeMN > 1.8).9) that indicates MPs showed less resistance to biodegradation than the DMPs.f. see Fig. 0.8).83. The order of susceptibility to biodegradation for the isomers used in TMNr is 1.6-DMN isomer has the methyl groups positioned well apart.2. 6. [38] developed a ternary diagram to illustrate the effect of maturity.2. has methyl substitutions on adjacent carbon atoms.2-DMN isomer. The relative intensity of the MPs compare to the DMPs is decreases with increase in biodegradation (Fig. while the least resistant 1.192]. 6.2 Alkylphenanthrenes The affects of biodegradation on alkylphenanthrenes were reported using variations in the distribution of methylphenanthrenes (MPs) and dimethylphenanthrenes (DMPs).5-TeMN (Fig. [38]) were plotted in a ternary diagram (Fig.96). TeNBR.7 for definitions) affected by biodegradation plot away from the maturity centre of the ternary plot.6.3.7).3.7). the 1.2.41. These results support a low level of biodegradation for the Potwar Basin oils.7 and 6. For example. 112 . Van Aarssen et al. Combined representative chromatograms for the MPs and the DMPs from nonbiodegraded to minor biodegraded oil samples are shown in Fig. Each plot shows a good correlation with Pr/n-C17 (R2 for DNBR. 6. The plots were drawn between these biodegradation ratios and Pr/n-C17 (Fig.

9+1.3+2. 113 .6 2.5+2.6 3.9 A combined chromatogram of MPs and DMPs (m/z: 192 + 206) shows decrease in relative intensity with in increase in biodegradations. The numbers on peaks indicate the respective alkyl substituted isomer of phenanthrene and highlighted peaks show significant depletion as move to more biodegraded sample.8 1.9+4.7 2. 6.5+2.2 (b) P5:Rajian-3A Relative intensity (c) P11:Minwal-1 59 61 63 Relative retention time (min) 65 Fig.7 1.9+4.10+ 3.9+3.MPs m/z: 192 2 9 3 1 DMPs m/z: 206 1.10 1.3 1.10 (a) P2:Missakeswal-1 2.

6. the susceptibility to the biodegradation of the individual isomers is less clear due to large number of possible isomers and coelution of different substitution isomers on common stationary phases (Fig. A 114 . High Pr/n-C17 and Ph/n-C18 values and low API gravity values of some of the oils are consistent with relatively low levels of biodegradation up to level 3.7-DMP.10-DMPs) peak observed degraded relative to following peak representing the 2. 6.5+2.7-DMP was the most refractory isomer to the biodegradation. The relative intensity of the 9-MP increases with increase in biodegradation as moved from top to bottom in Fig.6+3.5-DMPs and the 2.For the MPs isomers. 2.7. 6.6-DMPs isomers which are most resistant to biodegradation indicated by continuous increase in relative intensity with increase in biodegradation (Fig. 6. 6.9+3.9). The 2.9 while relative intensity of the 2MP and 3-MP isomers decreases. 6.9c) the four coeluted isomers (1.9). it is observed that the 2-MP isomer is less resistant to biodegradation while the 9-MP and 1-MP isomers show higher resistance to biodegradation.9+1. For the DMPs isomers. The δD values for the LMW n-alkanes relative to the isoprenoids were found to be enriched in D because of the removal of D-depleted LMW n-alkanes.10+3. The ∆δ between the n-alkanes and isoprenoids of the most biodegraded oil was found to be as much as 35‰. 6. In minor biodegraded oil sample (Fig. CONCLUSIONS The δD values of selected aliphatic hydrocarbons (n-alkanes and isoprenoids) in eight crude oils of similar thermal maturity from the Potwar Basin.7) is consistent with field study of Chinese biodegraded oils [43] while contradiction is observed from laboratory biodegradation study [128] where 2. But rate of depletion for each peak is found considerable and most to least susceptible order for DMPs is given in Fig. Pakistan have been measured. There is no indication of mixing.9). It shows that affects of minor biodegradation (up to level 3) on the MP and DMP isomers are not severe and only slight depletion is observed across the biodegradation sequences (Fig.3-DMP isomers are depleted faster than from all DMPs isomers as move from nonbiodegraded to minor biodegraded oil samples (Fig.3+2. The susceptibility order for DMPs (Fig. based on various known molecular parameters.9). 6.

2). Trimethylnaphthalene biodegradation ratio (TNBR: 1.3.5.7) showed significant variation in values with increase in biodegradation indicate a valuable parameters for the assessment of low level of biodegradation.3.6. The affects of biodegradation on methyl and dimethylphenanthrenes showed that with increase in alkylation of phenanthrene decrease in biodegradation extent is observed in Potwar Basin crude oils. ____ 115 .e.7) and Tetramethylnaphthalene biodegradation ratio (TeNBR: 1. dimethylnaphthalene Biodegradation ratio (DNBR: 1.6/1.7/1.3.significant change in the alkylnaphthalene and alkylphenanthrene distributions is used to assess the affects of biodegradation on individual isomers.2. Different biodegradation ratios were successfully purposed i.7/1.

the abundances of these compounds (DBT.7 GEOSYNTHESIS OF HETEROCYCLIC AROMATIC HYDROCARBONS AND FLUORENES BY CARBON CATALYSIS ABSTRACT Laboratory experiments have shown that activated carbon catalyses the reactions of biphenyls (BPs) with surface adsorbed reactants that incorporate S. DBF. These data tends to point towards a common precursor perhaps lignin phenols of land plants. carbazole (C. DBT. DBF and BP) show similar concentration profiles throughout the Kohat Basin sediments suggesting that share a common source. dibenzofuran (DBF. Coupling of phenols leads to BP. N or methylene forming some common constituents of sedimentary OM namely. O. XXV). A relationship between the % abundance of the hetero element in kerogen and the abundance of the related heterocyclic compound in the associated soluble organic matter supports the hypothesis that these reactions occur in nature. Furthermore. XXVI) and fluorene (F. More specific supporting evidence was obtained from the good correlation observed between methyl and dimethyl isomers of the reactant BPs and the methyl and dimethyl isomers of the proposed product heterocyclics compounds. which has been demonstrated in our laboratory experiments to be the source of C. It is suggested that these heterocyclic aromatic hydrocarbons distributions reported for sediments and crude oils from the Kohat Basin (Pakistan) and Carnarvon Basin (Australia) are the result of a catalytic reactions of compounds with BP ring systems and surface adsorbed species of the hetero element on the surface of carbonaceous material. XXVIII). dibenzothiophene (DBT. 116 . XXVII). and F.Chapter . These compounds also correlate well with changes in the paleoredox conditions.

The common members of this group include.131].217]. Relative abundances of DBFs and DBTs have been reported in different depositional environments where marine carbonates show higher amounts of DBT while freshwater/lacustrine sediments show higher amounts of DBFs [12-13].131. It is convenient for the purposes of this study to include the fluorenes (Fs) in this group although in this case it is carbon which forms the third ring. These compounds comprise a BP cyclic ring system with incorporation of a hetero-atom forming a third five-membered ring.51. BP is formed through phenol coupling. In the latter study. lignin phenols. [215] reported a high relative abundance of DBT. A brief overview of these suggestions now follows. The high abundances of DBF and alkylated DBFs in coals led to the suggestion of their relationship with oxidative degradation [54] and their terrestrial origin from lower vascular plants.216].7. The changes in relative abundances of benzothiophenes (BTs) and DBTs has been the basis for proposed thermal maturity indicators for OM [52. dibenzothiophenes (DBTs). Their abundances coincide with a shift in δ34S of pyrite as well as with the disappearance of the major vegetation types occurring during the Permian/Triassic mass extinction event. Fenton et al.165. the compounds have been suggested to be derived from the same precursor i. dibenzofurans (DBFs) and carbazoles (Cs). source organic facies [6. DBT and DBF have been suggested to have formed through reaction of BP with S and O species [215].1 INTRODUCTION Heterocyclic aromatic compounds occur widely in sediments and petroleum [6. It is require to evaluate that all these compounds show similar arrangements of structure except difference in heteroatoms. The difference in distribution of DBF and alkylated DBFs has also been reported changes in lithology and thermal maturity [36. The mechanism of formation of these structurally similar compounds has not been reported.e. Pyrrolic N containing compounds in 117 .215].50-51. DBF and BP in a Permian/Triassic section from East Greenland. thermal maturity [37.56]. and migration effects [57].55]. fungi and lichens [6]. although their abundance in sediments and crude oils has been related to depositional environments [12.12.

Evidence that these conversions have also occurred in sediments is provided by relative abundance data showing precursor product relationship between BPs and the heterocyclic compounds in crude oils and sediments reported from the Kohat Basin (Pakistan). Furthermore. Distribution of heterocyclic aromatic hydrocarbons were reported from the Carnarvon Basin. Cs and Fs is shown to occur in laboratory experiments through carbon surface reactions to introduce a third ring in BPs. The formation of DBTs. 7. These contrasting concentrations and the relative distributions of heterocyclic aromatic hydrocarbons in sediments and crude oils may be due to lack of knowledge about the source and mechanism of formation of these compounds. In this chapter.2 RESULTS AND DISCUSSION Evidence that the solid–state carbonaceous material promotes chemical reactions in sediments has been suggested from data obtained from hydrogen exchange 118 . DBFs. abundances of DBT. BP.216]. precursor product relationship between BPs and heterocyclics.e. C and DBF throughout the Kohat Basin (Pakistan) sediments have been measured and compared with δ34S of pyrite minerals and pristane to phytane (Pr/Ph) ratio to establish their relationship with the paleoeredox conditions. The source of pyrrolic N has been reported as facies dependent and concentration of both Cs and benzocarbazoles (BCs) increases with rise in thermal maturity [50-51. Paleoredox conditions appear to play a role in the formation of these components and the availability of the hetero atom to undergo carbon surface catalysis. The geochemical significance of Fs is not well known except those reported in a few oil correlation studies [12-13] while alkylated Fs are not yet reported in any from of sedimentary OM. While contrasting results have been reported from Canadian oils indicating thermal maturity and depositional environment show no effect on the distribution of Cs [56]. number of evidence reported for the geosynthesis of heterocyclics aromatic hydrocarbons. Australia crude oils to show the global feature of this hypothesis i. Less work has been done on occurrence and distribution of Cs in sedimentary OM.petroleum have been suggested as indicators of migration [57].

3. 7. Distribution association is observed between heterocyclics and BPs in sediments and crude oils revealed that kerogen is catalysing such reactions in sedimentary OM. 1(b) shows a chromatogram indicating formation of DBF.1) of the reaction products from heating experiments with activated carbon at 300 °C in deactivated. The carbon catalysed formation of DBT from reaction of BP and elemental S under these reaction conditions is shown in Fig. 1(d).1a. This experiment was carried out after sealing the reaction tube without evacuation to provide a source of O contained in air. GC-MS analysis of the reaction products under these reaction conditions with coal is shown in Fig.reactions between hydrocarbons [81]. 7. Clearly the S species in the presence of coal 119 . The reaction of 1.2a.2. This surface reaction extend by providing sources of reactive O. A set of these experiments have also been carried out replacing activated carbon with crushed coal. The reaction product contained both aminobiphenyl and C as shown in Fig. 7. N and C for reaction with BP. 7. Fig. Blank experiments without carbon (Fig. evacuated glass tubes indicate significant concentrations of each of the compounds of interest in the reaction products. Here data and results are reported from laboratory experiments showing reactions of S. The reaction was repeated by replacing activated carbon with sub-bituminous coal and again a significant abundance of DBT was observed (see below). Mass chromatograms (Fig.1 blanks) showed no significant products and activated carbon when heated alone gave no products. Reaction of BP with surface N was made possible by using sodium azide [218]. 1(c). The surface O was provided to the activated carbon by molecular oxygen [84]. O.4.tetramethylbenzene with BP under the same reaction conditions that resulted in formation of the heterocyclic products from O and N donors produced F and MBP isomers as shown in Fig. 7. N and C species on carbonaceous surfaces with BPs form the heterocyclic and F ring systems.2.1 Laboratory Experiments on Activated Carbon Laboratory experiments have shown that carbon surfaces catalyse the reaction between BP and surface reactants.

1. S. Oxygen (Air) O c) AC.4-tetramethylbenzene. TMB MBPs 4 2 28 3 32 36 40 28 32 36 40 Relative retention times Fig.a) AC. BP. Each blank experiment was identical in composition. MBPs. activated carbon.2. 7. temperature and time but without activated carbon. sulfur. methylbiphenyls. AC. TMB. biphenyl. BP. S Blanks S b) AC.3. BP. Samples were heated at 300 °C for 16 hr. 120 .1 Total ion chromatograms (TIC) of extracts from laboratory heating experiments. sodium azide NH2 H N d) AC. BP . BP.

1. Similar type of reaction was repeated where N species reacted with BP at a reaction temperature of 270 °C.1 Probable mechanism of geosynthesis reactions Catalysis by carbon surfaces is a known process [84.reacted with BP to produce DBT.2b). 121 .and 4. This surface reaction at higher reaction temperatures favours the formation of the heterocyclic compound with the methyl substituent adjacent to the heteroatom.99] and formation of active adsorbed surface reactants involves free radical reactions. GC-MS chromatograms of experiment extract showed the presence of 4-MDBT and 2-MDBT (Fig.MBP respectively.3). In this section possible reaction intermediate and pathways for the formation of heterocyclic aromatic hydrocarbons and fluorenes are reported with laboratory experiments results as evidenced obtained from carbon catalyses surface reactions. At low heating temperatures the 2-MDBT isomer showed higher abundance while with increase in heating temperature of reaction produced higher concentration of 4-MDBT. A similar experiment using activated carbon with 3-MBP was carried at different heating temperatures from 200 °C to 300 °C. The reaction has inserted S into the BP ring system without isomerization of the methyl group suggesting that 1-MDBT and 3-MDBT would be formed from reaction of 2. The systematic change in the relative abundances of product with increase in reaction temperature suggests that the position of the methyl substituent influences the reaction energy of activation. 7. 7. Blank experiments without activated carbon gave no significant MDBTs. 7. The preferential position of S addition to the BP system is an important feature of the process that can also be recognized in the formation of DBTs under natural conditions in sediments. Since carbon surfaces have low polarity but are electrical conductors the reactions they facilitate are more likely to involve radical rather than ionic intermediates. The chromatogram of the reaction products showed significant C compared with that from the blank experiment (Fig. These results indicate that carbonaceous surfaces other than activated carbon facilitate these reactions.2.

S. sulfur. 7. sodium azide 2-aminobiphenyl Carbazole Blank 28 30 32 34 36 38 Relative retention time (min) Fig. biphenyl.S Dibenzothiophene Blank b) Coal.2 TICs of extracts from laboratory heating experiments at temperature 270 °C for16 hr. BP. 122 . Each blank experiment was identical in composition. BP.BP a) Coal. temperature and time but without coal. BP.

3 Mass chromatograms (m/z: 198) of the extract of heating experiments of 3MBP with elemental S in the presence of active carbon at different temperatures.5 Relative retention time 40.5 39.0 39. 7. 123 .m/z :198 S 2-MDBT S 4-MDBT 200°C 225°C 250°C 300°C 38.0 Fig.

A similar set of radical processes appear to be responsible for formation of DBF from BP and adsorbed oxygen. 7. 7.6 shows the relationships between the concentrations of the BP and the heterocyclic aromatic hydrocarbons and F in these sediments.2. DBT. A similar distribution of these products resulted when the TMB was substituted with nonyl amine (Fig.It is interesting to observe that both methylation of BP and methylene substitution of BP to yield MBP isomers and F are present in extract of laboratory reaction of BP and TMB (Fig. C) with deuteriated phenanthrene and reported in Table 7.2. The proposed reaction sequence for formation of these compounds is shown in Fig. 7.2.4c) indicating that the reactive methylene species can be formed on the solid carbon surface by methylene abstraction from different compound types. F. Pakistan have been analysed for heterocyclic aromatic hydrocarbons. 7. 7. C and F support the interpretation that BP is related to the formation of this group of compounds by its reaction with a species containing the hetero element contained in the kerogen.4b).1 Parent compounds A sequence of sediments from the Kohat Basin. DBF. 7. DBF. The formation of C from BP could similarly involve a nitrogen radical species such as nitrene [220] by direct insertion or via 2-aminobiphenyl (Fig.1. Formation of DBT. 7. 7. This formation of MBPs and F from BP could involve surface carbenoid (or carbene) species [219]. The quantitative measurements were performed by comparing peak areas of compounds (BP. The abundance of O and S species vary significantly with depositional environments and 124 .5.2 Distribution of Heterocyclic Aromatic Hydrocarbon in Sediments and Crude Oils In order to asses the likelihood that the precursor-product relationships observed in the laboratory experiments have also occurred in sedimentary OM relative abundances of the parent compounds (non-alkylated) and their proposed products have been examined in sediments and crude oils. Fig. Both the parent (unsubstituted) and methyl substituted isomers of these compounds are common constituents in sediments and crude oils.a) or acetonitrile (Fig.1c).

BP. 125 . methylbiphenyls. 300 °C and 16 hr. nonyl amine Fluorene b) AC. BP. activated carbon. BP. heating temperature and duration was same for all experiments i.4-tetramethylbenzene. 1. Acetonitrile Fluorene 28 30 32 34 Relative retention time Fig. AC.3. TMB. TMB Fluorene c) AC.BP MBPs 324- a) AC.2.e. biphenyl. MBPs. 7.4 TICs of extract of heating experiments of BP with activated carbon using different alkyl precursor compounds. BP.

AC. F.F CH3 DBT S SH AC :CH2 AC S BP O2 (Air) AC OH DBF O ? AC :NH2 (NaN3) NH2 H N C Fig. BP. activated carbon. DBF. biphenyl. dibenzothiophene. fluorene. 7. carbazole. C. DBT. dibenzofuran.5 Purposed reaction pathways on activated carbon for formation of heterocyclic aromatic compounds and F from BP. 126 . S: sulfur.

23 0.d.80 1.27 Concentration (µg/g TOC) DBT 8.14 0. fluorene S: sulfur.51 n.d.12 0. 7.3 n.28 n.66 6.39 N 0.4 1.Table 7. 0.11 0.89 0. F. N: nitrogen -: below detection limit n. 10.03 BP.d.: not determined 127 .1 n.14 Elemental composition (%) S 4.23 0.87 0.25 0.67 1.7 1.33 0.12 0.78 0.10 C 0.22 1. C.d.33 1.26 1.1 Concentrations of compounds and elemental kerogen composition for Kohat Basin sediments.05 0.19 0.d.01 0.05 0.47 0. <0.74 3.d. DBT.28 0. carbazole. 27.18 0.35 7. O: oxygen.75 14.31 DBF 0.1 n.37 n.50 0.68 3.19 0.10 n.52 2.38 0.49 0.7 O 12. dibenzothiophene.3 2.37 3.81 19.29 0.52 2.31 1.12 0. 0.d.07 0.06 2. Samples No S1 S2 S3 S5 S7 S8 S10 S12 S13 S14 Depth 4290-92 4310-15 4345-70 4510-12 4650-52 4680-82 4710-12 4834-50 4860-62 4940-42 BP 2. 1.01 n.11 n.53 11.19 F 1. 0. 0.88 1. dibenzofuran.d.71 0.d.d.80 0.01 0. DBF. biphenyl.51 0.

Fan et al.77-79]. O. DBF and F in a large suit of crude oils and source rocks from different sedimentary environments.e. They have concluded that the relative abundance of DBF and F was higher in freshwater environments while DBT was higher in marine environments. 128 . respectively. [12] reported distribution relationship between DBT. 7. DBF. It has been reported that freshwaterlacustrine oils showed higher abundance of DBFs than DBTs [6].171].7. The results suggest a probable relationship between the solid state abundance of the hetero atom in the kerogen and the organic compound formed from it after reaction with BP (or a related precursor).1. %O vs DBF and %N vs C is shown in Fig. O. These results showed that insertion reactions are going on in sedimentary environments where kerogen surface heteroatoms and methylene species reacted with BPs to synthesize heterocyclics aromatic hydrocarbons and F respectively. The abundance of S in marine and carbonate-evaporate environments and less abundance of S (hence more O) in freshwater-lacustrine environments could be related in this scenario to that the formation of heterocyclic aromatic hydrocarbons depend on the nature of kerogen surface species.abundant DBTs have been proposed to differentiate between marine and carbonateevaporate crude oils and sediments [167. The plots indicate clear relationship that increase in %age of S. Plots of the % elemental composition of the kerogen for the element that matches the hetero atom in each of the compounds i. Abundant BP has been reported in kerogen bound structures [221] and similarly BP acids and alcohols have been found in abundance in kerogen degradation study from Moroccon Timahdit oil shale [222]. C. The elemental composition (%) of kerogen for S. and N was determined from similar suite of sediments of Kohat Basin Pakistan and reported in Table 7. Insertion and chemical reaction of heteroatomic species with biological precursors has been observed in various stages of sedimentary OM [65. N increases the concentrations of DBT. %S vs DBT.

20 18 16 Concentrations (µg/g TOC 14 12 10 8 6 4 2 0 0 1 2 3 4 5 6 Concentration, Biphenyl (µg/g TOC) F R = 0.76 R = 0.97 7
2 2

DBT

R = 0.95

2

DBF 8

Fig. 7.6

Relationship of reactant (BP)-product (DBT, DBF and F) for Kohat Basin sediments (data given in Table 7.1).

129

10 Conc. DBT (µg/g TOC) 8 6 4 2 0 0 1 2 3 4 5 Elemental S (%)

0.6 Conc. DBF (µg/g TOC) 0.5 0.4 0.3 0.2 0.1 0.0 0 5 10 15 Elemental O (%) 20 25 30

0.4 Conc, C (µg/g TOC) 0.3 0.2 0.1 0.0 0.0 0.1 0.2 Elemental N (%) 0.3 0.4

Fig. 7.7 Relationship between compounds in SOM and the N, S, and O concentration of kerogen from each sample (data given in Table 7.1).

130

7.2.2.2 Methylated homologous of heterocyclics and Fs
In order to facilitate easy recognition of heterocyclic compounds with substituents on similar positions in the carbon ring system to the BP structural systems Table 7.2 has been included to show these relationships for both methyl and dimethyl compounds. The representative mass chromatograms in Fig. 7.8 obtained from the aromatic fraction of Kohat Basin sediment (Depth, 4345 m) show the relative abundances of MBPs, MDBT, MDBFs, MCs and MFs. The thermal maturity of the sample is immature to early oil generation window as indicated by C32 hopane and C29 sterane isomerization ratios (0.43 and 0.43, respectively) and Tmax value (431 °C). The most abundant methyl substituted isomers from DBTs (4-MDBT), DBFs (4-MDBF), Cs (1-MC) and Fs (1-MF) show structure association with most abundant methylbiphenyl (3-MBP). Similarly the least abundant methyl substituted isomers from each compound class i.e. 1-MDBT, 1-MDBF, 4-MC, and 4-MF show structure association with least abundant MBP isomer i.e. 2- (Fig. 7.8; Table 7.2). The compounds related with BP in a reactant-product sense are indicated by symbols in Fig. 7.8. It is noteworthy that the relative abundance results for methyl isomers of the BP reactant and the products indicate that the hetero atomic elements (S, O, N) and methylene insertion occurred into MBPs in sediments to produce corresponding methyl homologous of DBT, DBF, C and F, respectively. Keumi et al. [223] reported the positional reactivity for DBF with different species and showed that the reactivity of position 4 is minimum as less as 5% of all possible four substitution positions in DBF (1, 2, 3 and 4). In contrast, the 4MDBF is the most abundant isomer from MDBFs in sediments (Fig. 7.8b) indicates MDBFs are formed from MBPs by insertion of O species. While there is some evidence for methylation of the aromatic rings during these surface catalysed reactions the majority of methyl heterocycles are derived from the methyl substituted BPs rather than by methylation of the parent heterocyclic compounds.

131

4 1. 3.5 2.8.4 1.4' 2.5 3. 2.2 Ring position relationships between BP and related heterocyclic compounds and Fs.4 2. 3 2 4.7.8.6* 1.3 3.5.3 1.7 1.4 *: after rotation of phenyl ring along single bond 132 .4 4.7 Cs & Fs 4 1.5 3. 1.3.5* 1.3' 3. 1.4' DBTs & DBFs 1 4.6* 1.7 3.8.3 3. 1.6.3 1. 2. 2.2' 2.4' 4. 3' 4' 2' 1' 5' 6' 1 6 2 3 5 4 8 7 9 1 2 6 X 5 6 7 Z 4 3 2 1 3 4 5 8 9 X: S = DBTs O = DBFs Z: NH = Cs CH2 = Fs BPs 2 3 4 2.6.4 2.6* 3.7 1. 2 3 1.Table 7. 2.6.3' 2.2 2. 3.4 2. 2.5 3.2.4 2.6 2.9 1.

(a) m/z: 198

4-MDBT

(b) m/z : 182 4-MDBF

3+2-MDBT 1-MDBT

3+2-MDBF 1-MDBF

(c) m/z :168

3-MBP

4-MBP

2-MBP

1-MC

(d) m/z: 181

(d) m/z : 180

1-MF

3-MF 2-MC 3-MC 4-MC 9-MF 2-MF 4-MF

Relative retention times

Fig. 7.8

Representative ion chromatograms show relative distributions of MDBTs (198), MDBFs (m/z: 182), MBPs (m/z: 168), MCs (m/z: 181) and MFs (m/z: 180) from the Kohat Basin, Pakistan sediment (Depth, 4345 m). Symbols relate precursor-product compounds.

133

These relationships between methyl substituted BPs and methyl homologous of DBT, DBF, C and F are also a feature of crude oils. Distribution of these compounds in the crude oils from two different basins of the world (Pakistan and Australia) is also reported (Fig. 7.9) along with sediments to illustrate the global features of carbon catalyses formation of heterocyclic aromatics hydrocarbons. Quantitative Relationship between MBPs and MDBTs in Sediments The quantitative measurements were performed for MBPs and MDBTs isomers from Kohat Basin sediments and reported in Table 7.3. The absolute abundance relationship between the corresponding individual isomers of MBPs and MDBTs in sediments is shown in Fig. 7.10a. The concentration of associated isomers of MBPs is plotted against associated MDBTs isomers. It is observed that the concentration of corresponding isomers increase together. The most abundant 4-MDBT concentration increases with increase in concentration of 3-MBP. Similarly, the least abundant 1MDBT concentration showed similar increase in abundance with 2-MBP. The good straight line relationships (R2, 0.98) indicate that the MDBTs showed product precursor link to the MBPs in sediments. Moreover, the ratios between methyl substituted BP and DBT to the parent compounds from the suite of sediment and crude oils are shown in Table 7.3 and is shown in Fig. 7.10b. It is Interesting to observe that both ratios showed an excellent linkage between their values. Where MBPs/BP ratio increases the MDBTs/DBT ratio decreases and vice versa. It shows that the methyl substituted DBT isomers are formed from methyl substituted BP isomers rather than methyl substitution of parent compounds i.e. DBT and BP respectively. Similarly, the MBPs/BP and MDBTs/DBT ratios for crude oils (Table 7.3) are also in same of range of sediments. The significant abundance of DBTs in sediments from range of low to medium maturity [4] and the relative distribution of MDBTs vary with OM type. The results from Kohat Basin sediments are consistence that the geosynthesis of MDBTs occurred by surface reactions where bonded S still present on the kerogen surface.

134

a) Upper Indus Basin, Pakistan 3MBPs

b) Carnarvon Basin, Australia 3-

4421MFs 2-

1-

32949-

324-

MDBFs 13+243+241-

1-

MCs 1323244-

Relative retention time

Fig. 7.9 Distributions of MBPs and methyl homologues of DBF, C and F in crude oils from two different basins. a) Chaknaurang, Upper Indus Basin, Pakistan; b) Barrow, Carnarvon Basin, NW Australia. MBPs (m/z 168), MFs (m/z 180), MDBFs (m/z 182) and MCs (m/z 181). Symbols relate precursor-product compounds.

135

24 0.69 0.03 0.96 3.35 1.20 - 3-+2MDBT 6.1 2.10 0.9 1.91 0.6 2.65 2.5 4.16 - 4MDBT 7.61 0.95 1.9 2.13 0.29 0.18 0.38 0.Table 7.00 0.39 1.63 20.03 - Samples No S3 S4 S5 S6 S8 S9 S10 S11 S12 S13 S14 P19 P20 P21 P22 Depth (m) 4345-70 4410-40 4510-12 4534-60 4680-82 4690-92 4710-12 4741-42 4834-50 4860-62 4940-42 Concentration (µg/g TOC) 2MBP 0.7 1.45 0.5 4.3 1.31 0.14 - MBPs/ BP 2.87 3.06 0.12 0.2 0.35 0.52 0.MBP 2.35 8.08 0.73 0.7 1.03 0.1 MDBTs / DBT 2.05 0.26 1.MBP 1.03 1.25 0.9 1.22 1.80 1.67 0.11 0.3 Concentration and compound ratios of sediments and crude Oils Compound ratios 1-MDBT 3.23 0.59 2.00 0.0 5.30 0.28 1.4 0.6 3.5 2.53 0.99 2.1 0.0 3.7 0.55 1.53 0.42 2.1 2.05 1.89 4.0 -: not determined 136 .1 0.4 3.95 0.3 3.01 0.1 4.02 0.91 2.02 0.68 9.1 2.00 - 3.4 1.97 0.1 1.22 - 4.42 0.59 16.2 2.01 0.00 0.40 0.4 3.

7.98 10 0 0 1 2 3 4 5 6 7 8 9 10 Methylbiphenyls (µg/g TOC) 6 5 4 Ratio 3 2 1 0 (b) MDBT/DBT MBP/BP 4345 4410 4510 4534 4680 4690 4710 4741 4834 4860 4940 Depth (m) Fig. 137 .10 Relationship between MBPs and MDBTs in Kohat Basin sediments. a) absolute concentration plot shows association between individual isomers of MBPs and MDBTs.98 2-MBP vs1-MDBT R = 0.25 Methyldibenzothiophenes (µg/g TOC) MBiPhs vs MDBTs 20 4-MBP vs 2+3-MDBT 15 R = 0. b) plot shows ratio of MBPs and MDBTs to the parent BP and DBT in sediment samples.98 5 2 2 3-MBP vs 4-MDBT 2 R = 0.

and 3.and 3. At a lower level of relative abundance the 3.4-.and 3. 7.and 3.11).6.could form two DMDBT isomer additional to the high abundance 3.3′.4.and 4.2.225] and probably reflects a strong preference for substitution of the sulfur reactive species at ring position 138 .7.7.and 2. neither isomer has been reported in geochemical samples [181. The relationships between DMBP isomers and isomers of DMDBT. a) DMBPs vs DMDBTs Dimethyl homologues of DBT and BP have been showed a structure relationship in natural sedimentary OM and comparison of substitution pattern between BP and DBT structural system is shown in Table 7.8.2. The two most abundant DMBP isomers 3. Although a number of the DMDBT isomers with this substitution pattern showed co-elution it is apparent that the abundance of this group relative to the 4.4′. 7.isomers.6.2. The relative distributions of DMBPs and DMDBTs in representative sediment sample are shown in Fig.6. Data is available for DMBPs and DMCs [49.6. These are 2.substituted biphenyls (Fig.3 Dimethyl homologous of heterocyclics and Fs The product-precursor relationship can also be extended to the compounds with two methyl substituents.2).as the most abundant.4-DMBP isomers have a similar lower relative abundance pair of DMDBT isomers namely 2. It is interesting that the two most abundant DMBP isomers namely 3.and 4.and 3.7-DMF.isomers are in a similar proportion to the set of 2.substituted biphenyls relative to the 3.11. DMC and DMF are described from sediments and crude oils in following sections.6DMDBT isomers discussed above.3′have the corresponding structural DMDBT isomers 3.6.4′. This approach is however limited by availability of GC-MS data to enable reliable identification of isomers.224] however no data is available for DMFs or DMDBFs although I have been able to obtain an authentic sample of 1. It is interesting that the set of DMBPs with a substituents in position 2 have a corresponding set of DMDBT isomers with substituents in position 1 (Table 7.5.

11 Relative distribution of DMBPs and DMDBTs in Kohat Basin sediments (depth.6 2.6 2-E 3. 4680 m).2).4 2. Symbols relate precursor-product compounds.3 4.4 4-E 3.4 1.3' 2.3.4' m/z:182 Dimethylbiphenyls 3.7.4+1.6' 4.9 Relative retention times Fig.3' 2.2' 2.4' 3.3 3.2+1.5 3-E 2.7 1. Numbers on peaks indicate dimethyl substituted isomers of BP and DBT (Table 7.8 2.6 2.4' m/z:212 Dimethyldibenzothiophenes 1.4+2. 139 .6+1.5 3.

In 3. 1. This is again the case for preferential formation of 1. In both samples the two most abundant DMBP isomers 3. These relationships between methyl and dimethyl substituted BPs and DBTs is a common feature of crude oils. Again the symbols indicate relationships between BP isomers and the product DBT isomers derived from them.6-DMC the co-product from 3.11) the relative abundances of isomers indicates a reactant-product relationship consistent with that discussed above for the sediment samples b) DMBPs vs DMCs and DMFs DMCs and DMFs have been showed a structure relationship with DMBPs in natural sedimentary OM and comparison of substitution pattern between C.3`-DMBP and.8 and 7.3′.6-DMC is the next most abundant isomer. 7. Some preference for the position of substitution into the BP ring system is indicated by the relative abundances of reaction products. The relationships between DMBP isomers and isomers of DMC and DMF apparent in the chromatograms shown in Fig. 7. like 2. It is a co-product from 3. 7.have 1.3-DMC from 3. 140 .2.13 for a sediment extract from the Kohat Basin.4′.adjacent to the methyl substituents. F and BP structural system is shown in Table 7. it has a lower abundance than the alternative product with a methyl at position 1 indicating the preference for substitution of the hetero atom adjacent to a methyl substituent.2.12 shows the distribution of these compounds in the crude oils from Pakistan and Australia.6DMDBT isomer.8and 1. for comparison of related substitution patterns in BP and the heterocyclic compounds).and 3.DMCs as the two most abundant DMC isomers (refer to Table 7.7. Fig. Again this relationship is consistent with a carbon catalysed derivation of the DMCs from DMBPs.4`-DMBP. While the peak patterns are a little different to those from the sediment extract (Fig.2-DMC rather than 2.3′-DMBP isomer the phenyl ring rotation across the single bond followed by sulfur insertion is the probable source for the 2.4-DMBP. Pakistan and the Griffin crude oil from Australia.

4 2.6' 2. Pakistan.6 1.6+1. Australia.4+1. 141 .5 2. Pakistan 3 MBPs 4 MDBTs b) Carnarvon Basin. b) Wanaea.4' 3.8 3.3' 4.4 1.3+ 3.4 2.6 1.9 2.4 DMDBTs 4. DMBPs (m/z 182).6 2.6 3.4+2.3 3.6' 4.4 2.3' DMBPs 3.2+1.4' 3.12 Relative distributions of methyl and dimethyl biphenyls and dibenzothiophenes in crude oils from two different basins.8 1. Symbols relate precursor-product compounds. Carnarvan Basin.4' 3.3 3.4' 2.4' 2.4+1.3 2.7 1.4 3.2' 2. MDBTs (m/z 198) and DMDBTs (m/z 212).5 4.7.7 1. MBPs (m/z 168).9 Reletive retention time Fig.6+1.2' 2.4+2.2+1.3' 3.6 2.4' 3. Kohat Basin.5 2. a) Mela-1.3' 3.5 2.a) Kohat Basin. Australia 3 MBPs 4 MDBTs 4 4 3+2 1 2 2 3+2 1 3.6 2.

Kohat Basin, Pakistan 3,3'

3,4'

Carnarvon Basin, Australia DMBPs 3,3' 3,4'

2,5 3-E 2,2' 2,3' 2,4+2,4' 2,3

3,5


4,4'

3,4

2,5

3,5 3-E 4,4'

∆ 3,4

2,2' 2,6' DMCs

2,3' 2,4+2,4'

2,3

1,7 1,8 1,6 1,3 1,5+3-E 1,4+4-E

1,8 1,6

1,7

1,5+3-E 1,4+4-E


2,7+1,2 2,6 2,4 2,5

1,3

2,7 2,6 1,2

2,4

2,5

1,8 1,3

1,7 1,6 X

DMFs

1,8 1,3 1,7 1,6

1,9 3,9 2,9 4,9

EF 3,9 2,9

1,9 4,9

EF

X

Relative retention times

Fig. 7.13 Relative distribution of DMBPs (m/z: 182), DMCs (m/z: 195) and DMFs (m/z: 194) in the Kohat Basin sediment (Depth, 4940 m) and the Carnarvon Basin Griffin crude oil. Numbers on peaks indicate dimethyl substituted isomers. Symbols show precursorproduct relationships (Table 3).

142

In the case of DMFs only the 1,7- isomer has been identified using an authentic sample. The other peak assignments have been made assuming that the effect of changing the position of ring substitution of methyl groups on Cs has the same effect on retention time as that for DBFs and can be used to predict the retention time of the DMF isomers relative to the 1,7-DMF reference compound. Again the relationships in relative abundance of these isomers to those of DMBP support the proposed formation relationship. The relative abundance of DMFs showed two set of dimethyl isomers where one set showed tentatively identified 1,8-, 1,3- and 1,6- isomers including 1,7- isomer identified using authentic standard while second set show lower abundance collectively mark as X (Fig. 7.13). It can be seen that the 1,7- and 1,8-DMF isomers from both sediment and oil sample indicate higher abundance show a structure association with most abundant DMBP isomer, 3,4′- and 3,3′-. However, it is noteworthy that the small relative abundance difference between 3,4′-DMBP isomer with 3,3′-DMBP isomer in sediment sample could be related to the similar relative abundance difference of corresponding structure associated dimethyl isomers of F, i.e. 1,7- and 1,8- respectively (Fig. 7.13). While in case of oil sample this observation is reversed where 3,3′-DMBP isomer is relatively higher than 3,4′-DMBP isomer showed same difference in relative abundance of corresponding dimethyl isomers of F i.e. 1,8-DMF isomer is higher than 1,7-DMF isomer (Fig. 7.13). Similarly, next abundant 1,3-DMF showed structure and relative abundance relationship with next abundant DMBPs isomer, 3,4′-. The relative abundance of second set of dimethyl isomers of F indicated by X could be related to the dimethyl isomers of BP having lower abundance i.e. 3,4-, 4,4′- (c.f. Table 7.2). The relative abundance results between structure associated isomer of DMBPs with DMCs and DMFs revealed that the hetero-atomic element (N) and methylene insertion occurred into DMBPs in sediments and crude oils to produce corresponding dimethyl homologous of C and F, respectively.

143

7.2.3 Paleoredox Conditions and Heterocyclics Formation
Fig. 7.14 displays the abundances of DBT, DBF, C and BP, Pr/Ph and δ34S with depth for the Kohat Basin sediments. Since all the aromatic components tend to show similar abundance profiles with depth suggests to indicate a common precursor. Given that both the Carnarvon Basin crude oil and Kohat Basin sediments contain Type III kerogen (terrestrial-derived OM) the most likely natural product precursor for BP is thus suggested to be lignin phenol. A similar observation was made by Fenton et al. [215]. Lignin is a co-polymer comprised of phenyl–propenyl alcohols [226] and it is likely that these phenolic compounds could be the precursor for BP, and BP is thus intermediate source of DBT, DBF, C and F. However, other natural product precursor(s) can not be fully excluded for BP precursor. δ34S of pyrite in the Kohat Basin samples support changes in the paleoredox conditions of the water column. δ34S vary from –6.5 to -31.1 ‰. The δ34S results (-17.9 to -31.1 ‰) are mostly in the range of expected for periodic fluctuating dysoxic/euxinic depositional conditions [121,215]. These trends reflect the variations in the isotopic composition of seawater sulfate and imply a change in the sulfur cycle and a relative increase in the fraction of sulfur buried as pyrite. The sample with a δ34S of -6.5 ‰ is where C shows a maximum concentration and this result can not be explained. The exact source of the N present in C is unknown, but the availability of a specific N source is key here. The other aromatic compounds, BP, DBT and DBF, show a similar abundance profile with depth as observed by Fenton et al [215]. The redox conditions during this period of time (based on δ34S of pyrite and Pr/Ph) would favour the formation of DBF, DBT from BP. Anoxic/euxinic conditions are periodic, therefore it is not unexpected to observe similar abundance profiles of DBT, DBF and BP with depth. The samples will reflect an average of the seasonal redox conditions spanning several millions of years.

144

6 0. C and Pr/Ph with depth in Kohat Basin sediments Pakistan.δ S (‰) -35 4200 4300 4400 4500 4600 4700 4800 4900 5000 -25 -15 34 Dibenzothiophene (µg/g TOC) -5 0 5 10 15 20 Dibezofuran (µg/g TOC) 0 0. Depth (m) 145 .7 Fig 7.5 2 0 Biphenyl (µg/g TOC) 2 4 6 8 Carbazole (µg/g TOC) 0 0.5 1 0. δ34S(‰) of pyrite against concentrations of DBT.14. BP.4 Pr/Ph 0. DBF.5 1 1.3 0.5 0.

the most likely natural product precursor is lignin phenol. O. DBF.5 to -31. DBF. A similar abundances of DBT.CONCLUSIONS DBT. Given that the Kohat Basin sediments contain Type III kerogen. together with Pr/Ph and δ34S of pyrite for the Kohat Basin sediments of various depths suggest that these compounds share a similar precursor. Evidence that similar reactions occur in sediments was shown by enhanced formation of the heterocyclic compounds relative to biphenyls when the appropriate hetero element was present in the kerogen. C and F. Methyl substituted BPs (both mono and dimethyl) were shown to have an isomer abundance profile similar to that predicted for methylated heterocyclics (and Fs). the intermediate precursor for DBT. δ34S of pyrite of the sediments vary from –6. C and F have been shown to form by reactions of BP with surface active S. Phenol coupling can lead to BP. More specific evidence for a reactant-product relationship between BPs and heterocyclics (and Fs) was obtained from a comparison of the methylated compounds in sediments and crude oil. DBF and BP. _____ 146 .1 ‰. N and methylene species on carbon surfaces when heated at 300 °C. reflecting periodic fluctuations in the redox (anoxic/euxinic) depositional conditions.

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21-secohopane (Tetracyclic terpanes) IX 170 .10-trimethyltridecane IV nor-Pristane V Pristane VI Phytane 1 2 6 10 14 VII 22 27 32 37 VIII Tricyclic terpanes (Cheilanthanes) C24. 17.Appendix Isopreniods 2.6-diemthyundecane I nor-Farnesane Farnesane II III 2.6.

21α(H) shown XII C27 17α(H)-22.29. C34 tetrakishomohopane = C6H13. 17α(H). 30-norhopane (C29 hopane) = CH3. C32 bishomohopane = C4H9. C31 moretane 17β(H).29. C31 homohopane = C3H7.30-trisnorhopane (Tm) XIII C27 18α(H)-22.30-trisnorneohopane (Ts) XIV C30. C35 pentakishomohopane S and R isomers at C22. C33 trishomohopane = C5H11. 17α(H)-diahopane XV C29. C30 moretane = C2H5. 18α(H)-30-norneohopane (C29Ts) 171 . C30 hopane = C2H5.Hopanes 19 12 1 2 3 23 4 25 10 5 24 11 9 26 8 7 6 27 13 14 18 28 15 17 16 20 21 22 29 30 X X X = H. C29 moretane = CH3.21β(H) shown Y XI Y = H.

c S and R isomers at C20. 13β(H). X=CH3. 5α(H). b = C2H5. X= CH3. a C20 TA . C28. b = C2H5. C27-sterane. C28-sterane. Y=CH3 c C22 TA . X=CH3. C27-sterane. Y=C8H17 h 172 . X=CH3.17α(H) R = H. C27. Y=C6H13 f C27 TA . a = CH3. f 14β(H). X=CH3.Steranes and diasteranes R 21 18 11 1 2 3 4 5 6 19 10 9 8 7 12 13 14 17 16 15 20 22 23 24 25 26 27 XVI R = H. C29-sterane.17α(H) 4 5 3 14 7 12 2 1 8 7 6 5 4 9 10 3 11 2 Adamantane 6 Diamantane 1 8 XIX XVIII X Y 10 9 13 XX Triaromatic steroids (TA) C19 TA. X=H.17β(H) R XVI I Diasteranes R = H. C29-sterane. X=CH3. Y=H. C28-sterane. Y=C7H15 g C28 TA . Y=C5H11 e C26 TA . a = CH3.14α(H). e = C2H5. Y=C2H5 d C25 TA . X=CH3. Y=H b C21 TA . d = CH3. C29 c S and R isomers at C20.

Retene 4 5 6 6' 5' 4' Biphenyl XXII Naphthalene XXIII 1 1' 2' 3' 3 2 7 6 8 1 á â2 4 3 XXI 5 3 2 4 6 7 8 5 1 10 9 Phenanthrene XXIV 3 2 1 3 4 2 3 O5 4 NH 9 5 6 6 7 9 8 1 2 1 4 S5 9 8 7 6 7 8 XXVI Dibenzofuran XXV 2 4 Carbazole 3 1 Dibenzothiophene XXVII 9 5 6 7 Fluorene XXVIII --173 8 .

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