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Dr. SAMPEI, Yoshikazu Professor, Department of Geoscience, Faculty of Science and Engineering, Shimane University, E-mail:email@example.com
1. Fundamentals of Organic Geochemistry 2. Origin and Formation of Petroleum 3. Maturity 4. Migration and Trap 5. Source Rock Evaluation 6. Oil-Source Rock Correlation and Biodegradation 7. Modeling
“ Petroleum Formation and Occurrence ”
“ The Biomarker Guide ”
“ Introduction to Organic Geochemistry ” .
jp (19)Organic nitrogen and oxygen compounds (20)Biogenic methane (6)Biodegradation of n-alkane (7)Biodegradation stage (8)Biodegradation effect on sulfur&nitrogen contents and API 3. SAMPEI. Migration and Trap ----------------------------------------------(46) 1. E-mail:sampei@riko. Department of Geoscience. Shimane University.shimane-u. (8)Non-biomarker maturity indicators in postmature zone (9)Respond range of maturity parameter (10)Origin of methane 7. Modeling ----------------------------------------------------------(80) (1)Changes in %Ro under different heating rate (2)Computer simulations based on kinetics of isomerization (3)Data set of kinetic parmeters (4)Simulation results 8.ac. Origin and Formation of Petroleum (1)Kerogen Type (2)Depositional environment of kerogen type (3)Caracterization of Kerogen: bulk composition (4)Kerogen formation: classical and diagenetic path (5)Kerogen formation: new concept (6)HI and OI (7)Van Krevelen diagram and HI-OI (8)Rock Eval (9)Interpretation of Rock Eval (10)HI and H/C (11)Petroleum system (12)Crude oils characterization (13)Crude oils characterization 2 (14)Hydrocarbon compositions (15)Terpanes (16)Terpanes (17)Aromatics (18)Organic sulfur compounds --------------------------(16) (1)Standard evaluation sheet for source rock potential (2)Source rock generative potential (3)TOC and S2 of shale (4)Controlling factors of TOC (5)S2-TOC plot (6)Lacustrine source rock evaluation (7)Biomarker as organic source indicator (8)Biomarker as organic source indicator (9)Age control of the C28/C29 steranes ratio (10)Oxic-anoxic proxy (11)Depositional environment indicator (12)Origin indicator (13)Depositional indicator (14)Origin indicator 2 (15)Origin indicator 3 (16)Porphyrin (17)Souce rock potential and environmental change 6.Contents Organic Geochemistry of Petroleum System Dr. Faculty of Science and Engineering. Source Rock Evaluation -----------------------------------------(55) 2. Oil-Source Rock Correlation and biodegradation (1)Tool for oil-source rock correlation (2)Correlation by n-alkane (3)Correlation by steranes and hopanes (4)Correlation by steranes (5)Confidence of oil-source rock correlation ---------(72) . Yoshikazu Professor. Fundamentals of Organic Geochemistry ------------------------(4) (1)Components of oil (2)Biomarker (3)Labeling system (4)Symbols of chemical structure (5)Modifiers on chemical structure (6)Stereo-isomer (7)Optical isomer (8)Racemization (9)Important analytical equipment : GC (10)Important analytical equipment : GC/MS (11)Representative GC/MS result: Selected ion chromatogram (12)Representative GC/MS result: Full scan and mass chromatogram (1)Primary migration and secondary migration (2)Porosity and fluid pressurek (3)Porosity and permeability of reservoir rock (4)Microfracturing system in primary migration (5)Diffusion-controlled processes in primary migration (6)Molecular solution in water (7)Molecular solution in gas (8)Complex system for oil accumulation (9)Preferential expulsion 5. Maturity ------------------------------------------------------------(36) (1)Diagenetic compositional changes in hydrocarbon (2)Diagenetic change in chemical structure of kerogen (3)Vitrinite Reflectance (4)Maturity indicator of biomarker (5)GC/MS SIM chromatogram of oil (6)Relationship between two biomarker maturity indicators 1 (7)Relationship between two biomarker maturity indicators 2. Reference ---------------------------------------------------------(84) Contents 4.
Fundamentals of Organic Geochemistry 1-(1) Components of oil Asphaltens: Higher molecular weight (500-1500) NOS/polar compound. use to concentrate e. Urea adduction: Small molecules become adducted by urea crystal (NH2CONH2).g. soluble in n-C6H8 or n-C5H10 Molecular sieve: Separation based on molecular size by e. zeolite. small molecules become trapped in the crystal lattice. Tissot and Welte (1984) .1. steranes.g. insoluble in n-C6H8 or n-C5H10 Resins: Higher molecular weight (less than 500) NOS/polar compound. soluble in CS2.
Steranes Hopanes Peters and Moldowan (1993) . Maturity. Correlation between oils and source rock. Depositional environment.1-(2) Biomarker Useful tool to know: Origin of organic matter.
1-(3) Labeling system Three-dimensional structure To know: Maturity (Origin) Peters and Moldowan (1993) .
1-(4) Symbols of chemical structure To depict the stereochemistry of atoms Single bond: on the sheet plane Light gray bond and white circle: directe into page •¨ the alpha (α) position (The opposite side is beta (β) ) = Stereochemistry Peters and Moldowan (1993) .
Des-A: loss of A from structure.1-(5) Modifiers structure on chemical Homo-: one additional carbon on sturucture. Neo-: methyl shifted from C18 to C17 on hopane. S: asymmetric carbon that obeys convention in a anti-clockwise direction Peters and Moldowan (1993) . Iso-: methyl shifted on structure. R: asymmetric carbon that obeys convention in a clockwise direction. bis=di tris=tri tetrakis=tetra pentakis=penta hexakis=hexa Nor-: one less carbon on structure.
Peters and Moldowan (1993) . Important concept to understand maturity indicators of biomarker Changes to the mirror-image structure by heated condition (These two are so called “enantiomers”) These substituents form chiral molecule. Chiral molecule: The name is given to a substituent with an asymmetric carbon at which optical isomers may occur.1-(6) Stereo-isomer.
“•| “ Peters and Moldowan (1993) “levo- .1-(7) Optical isomer The stereo-isomer shown in the previous page is an optical isomer. Clockwise direction “dextrorotatory” “R (rectus or dextral)” or. “D” or. which can perform a rotatory polarization. “L” or. “+” Anti-clockwise direction rotatory” “S (sinister)” or.
17α(H)-sterane The ratio of 20S/(20S+20R) rises from 0 to about 0. 14α.1-(8) Racemization: Interconversion of enatiomers is called racemization. 17α(H)-sterane changes to the geological epimer 20S-C29 5α. Peters and Moldowan (1993) .55. 14α. Epimer Enantiomer Enentiomorph Antimer The biological epimer 20R-C29-5α. 1986).520. seifert and Moldowan.5 (equilibrium at 0.
1994). Capillary column is used to separate components of oils and rock extracts.1-(9) Important analytical equipment : GC GC: The separation of mixtures of compounds by partition between a mobile gas phase and stationary liquid phase is called gas chromatography (Miles. . Peters and Moldowan (1993) .
Shimane Univ. Peters and Moldowan (1993)
1-(10) GC/MS The tandem system of GC linked to a mass spectrometer; the most powerful analytical technique in modern organic geochemistry. Organic compounds •¨ separated •¨ transfered to the ionizing chamber •¨ accelerated •¨ detected in the electron multiplier Positive ions of mass/charge ratio (m/z) are impinge on the detector.
Analitical time: 1 or 2 hours GC temp.: about 40 to 300 ºC.
1-(11) Representative GC/MS result: Selected ion monitoring (SIM) is often used. With 70eV electron impact (EI) ionization SIM is very sensitive.
Steranes and hopanes have specific fragment ions m/z=217 and m/z=191, respectively. These two ions are commonly used as routine biomarker analyses.
Peters and Moldowan (1993)
1-(12) Full scan + mass chromatogram
“Full scan ” condition is not so sensitive. But “Full scan ” gives a detail information to know organic structure of unknown compound. The detail information is “mass chromatogram”. Major fragment ion & Mokecular ion
Peters and Moldowan (1993)
Representative GC/MS chart for steranes m/z=217 m/z=217 5 C27 sterane 20R (cholestane) 9 C sterane 20R 28 (ergostane) 13 6 7 8 11 10 C29 sterane 20R (stigmastane) 12 15 14 16 Diacholestane 20R 4 3 2 1 17 18 Unpublished data (Akita-oil) .
17α(H)-24-norcholestane 20S 5α.14β.17α(H)-cholestane 20S 5α.17α (H)-24-ethylcholestane 20R 5α.14α.14α.14α.17α (H)-24-n-propylcholestane 20R carbon number 27 27 26 26 27 27 27 27 28 28 28 28 29 29 29 29 30 30 .17β (H)-24-ethylcholestane 20S 5α.17α (H)-diacholestane 20S 5α.17β (H)-24-methylcholestane 20S 5α.14α.14α.17β (H)-24-methylcholestane 20R 5α.17β (H)-24-ethylcholestane 20R 5α. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 A B C D E F G H I J K L M N O P Q R Name 13β.17α (H)-diacholestane 20R 13β.14α.17α (H)-24-ethylcholestane 20S 5α.14β.14α.14α.14β.14β.17α(H)-cholestane 20R 5α.14β.14α.17α (H)-24-n-propylcholestane 20R 5α.14β.17α(H)-24-norcholestane 20R 5α.17β (H)-cholestane 20R 5α.Peak No.14α.17α (H)-24-methylcholestane 20S 5α.17β (H)-cholestane 20S 5α.17α (H)-24-methylcholestane 20R 5α.
Representative GC/MS chart for hopanes C30Hopane m/z=191 C31Homohopane (S.R) C33 (S.R) C34 (S.R) Tm C32(S.R) 35 Ts Peters and Moldowan (1993) 36:Oleanane 31:Gammacerane .R) C (S.
Peters and Moldowan (1993) .
Precursors of steranes Cholesterol H O H O Stigmasterol 24ƒ¿ -ethylcholesta-5.22E-dien-3ƒÀ -ol .
especially marine.As macerals (morphology) 2. Type II (oil prone): herbaceous comparatively hydrogen-rich.04) and appear to begin to generate oil at lower thermal exposure Shimazaki (1986) . preserved in sedimentary rocks Type I (very oil prone): amorphous hydrogen-rich. Origin and Formation of Petroleum 2-(1) Kerogen Type Kerogen: Insoluble. higher plants Type IV (inertinite) •FWoody&coaly oxidized and hydrogen-very-poor Type II-S : amorphous unusually high organic sulfur about 8-14% (atomic S/C>0. suboxic. especially lacustrine. Type-I phytoplankton in II III Type III (gas prone):Woody&coaly hydrogen-poor & poly-aromatic. algal in anaerobic.
Structural characteristics of Kerogen Killops and Killops (2005) .
2-(2) Depositional environment of kerogen type Type I: stratified freshwater lakes Type II: silled. deep-water basins on continental slope and rise outer shelf O2-minimum layer under upwelling Type III: lagoonal. deltaic and coastal swamps basins of restricted circulation on continental shelves Type I Type III Type II 500-2500m Type III Type II without supply of clay Peters and Moldowan (1993) .
7 and low O/C about 0. Tissot and Welte (1984) .2-(3) Bulk composition: Van Krevelen diagram Immature type I : high H/C about 1.2.9 and high O/C about 0.1 Immature type III : low H/C about 0.05. Immature type II : medium H/C about 1.3 and medium O/C about 0.
2-(4) Kerogen formation: classical and diagenetic path Living organisms are composed of: Lignins Carbo-hydrates Proteins Lipids Macro-molecules to Sugars Amino acids Fatty acids Polymerized to Humic acid Kerogen Tissot and Welte (1984) .
Structural characteristics of Lignin Killops and Killops (1993) lignin conifer wood broadleaf wood .
proteins and lipids are to humic substances. Killops and Killops (2005) Anoxic marine without Fe •¨ hydrogen sulfides •¨ organic sulfur •¨ sulfur rich oil . carbohydrates.2-(5) Kerogen formation: new concept Bio-macromolecules as lignins.
(2005) .2-(6) Rock Eval HI and OI Rock Eval hydrogen index (HI: mgHC/gTOC) and oxygen index (OI: mhCO2/gTOC) is simulating the Van Krevelen diagram. HI = S2/TOC Example: S2=4(mgHC/gRock) TOC=2(%) HI = 4/(2/100) = 200 (mgHC/gC) Peters et al. Immature type I: high HI 900 and low OI 20 Immature type II: medium HI 500 and medium O/C 50 Immature type III: low HI 100 and high OI 100.
0.9 100 0.3.2-(7) Correlation between Van Krevelen diagram and modified Van Krevelen diagram.1 50 III 0.6. HI 800.05 20 II 1. (2005) .2 200 Peters et al. O/C OI 0. Type I H/C 1. 500.
Tissot and Welte (1984) .2-(8) Rock Eval Anhydrous pyrolysis Institute Francais Petrole (IFP) Shimane Univ. du About 100mg of pulverized source rock sample Hydrocarbon detected by FID (flame ionizetion detector) CO2 detected by TCD (thermal conductivity detector) Shimane Univ.
2-(9) Interpretation of Rock Eval First at 300ºC: the peak area S1 Second at 300-550ºC(25 ºC /min) : the peak area S2 Carbon dioxide up to a temp. of 390ºC: the peak area S3 HI: S2/TOC OI: S3/TOC Tmax: ºC <435 ºC (immature) 435 to 460 ºC (mature) >460 ºC (post mature) Tissot and Welte (1984) .
0036OI + 0.0017HI + 0.3 C6H6 •F H/C=1 C10H8 •F H/C=0.71 2-(10) HI and H/C Quantitative relationship H/C = 0.Whelan (1993) and Thompson-rizer C20H42 •F H/C=2.8 C14H10 •F H/C=0.05.5 O/C = 0.1 C12H18 •F H/C=1. .
2-(11) Petroleum system Anoxic condition: kerogen survives oxidation Humic macro-molecule ( in diagenesis ) Hydrocarbon ( in catagenesis ) Gas ( in metagenesis ) Heated with increasing depth to release CO2 and H2O Peters et al. (2005) .
Biodegradation Oxydation Water-washing 2-(12) Ternary diagram of oils Paraffins Naphthenes Aromatics (&NOS) Tissot and Welte (1984) Non-degradaded: Paraffins&aromatics Degradaded: heavy oils. aromatics &NOS and much sulfur >1 % .
decomposed in the catagenetic Thermal maturation Tissot and Welte (1984) .Biodegradation Oxydation Water-washing Biodegradation only 2-(13) “Alteration”: Biodegradation+ water washing: Paraffins&Naphth enes decrease. produced in the early diagenesis. Maturation: aromatics+ asphaltenes decrease. Aromatics: absent in recent sediments.
Soxhlet extraction (Shimane Univ. molecular weight and absorption affinity alkanes (n-alkane) iso-alkane Cycloalkanes mono-aromatics di-aromatics poly-aromatics organic sulfur compounds organic nitrogen compounds organic oxygen compounds.2-(14) Hydrocarbon compositions Tissot and Welte (1984) Based on boiling temperature.) .
(2005) .2-(15)a Terpanes Sesterterpanes (C25): Acyclic Tricyclic tetracyclic head Isoprene unit: building block for terpenoids diatom Peters et al.
(2005) .2-(15)b Terpanes Triterpanes (C30): Acyclic Tricyclic Peters et al.
(2005) .2-(16)a Steranes Peters et al. (2005) Peters et al.
2-(16)b Hopanes Peters et al. (2005) .
2-(17) Aromatics Peters et al. (2005) .
(2005) .2-(18)a Organic sulfur compounds Peters et al.
(2005) .2-(18)b Organic sulfur compounds low matured high sulfur oil Peters et al.
(2005) . (2005) Peters et al.2-(18)a Organic nitrogen compounds pH control Neutral nitrogen Basic nitrogen Peters et al.
2-(18)b Organic oxygen compounds Mainly due to biodegradation 1 2 DPEP –––(maturation)–––> Etio Peters et al. (2005) .
Chlorophyl-a 1 2 .
Eubacteria: CH3COOH2 ---> CH4 + CO2 Archaebacteria: CO2+4H2 ---> CH4 + 2H2O . (2005) Methane formation Early stage of diagenesis by methanogenic bacteria (methanogens) after working sulfatereducing bacteria Deltaic and coastal swamps: Activity of methanogenic bacteria is high because of abundance in organic acid (mainly acetate.2-(20) Biogenic methane Peters et al. indicating oxic condition) and absence of sulfate-reducing bacteria.
Metagenesis (High molecular weight nalkanes decrease by thermal degradation. Maturity 3-(1) Production decomposition hydrocarbon and of Diagenesis. Tissot and Welte (1984) .) Peak of oils at about 2500m: an average on Mesozoic and Paleozoic source rocks The depth changes due to type of kerogen. Catagenesis.3. burial history and geothermal gradient.
Tissot and Welte (1984) . “Infrared spectra” Aliphatic bonds C-H (2920 and 2855 cm-1).3-(2) Diagenetic change in chemical structure of kerogen Characterized based on some common fanctional groups. CH2 (1375cm-1) CH3 (1455 and 1375 cm-1) Aromatic bonds C-H (930-700 cm-1) C=C (1630 cm-1) Ketones. acid and esters C=O (1710 cm-1) These peaks decrease with increasing diagenesis mostly by temperature.
Rmin Measured on the polished vitrinite with oil at 546nm incident light under microscope Abbreviations: Ro (o: in oil). 450.0 435.5. 510 Based on the change in the reflectance of polished virinite particles Increase with increasing time and temperature (by progressive aromatization) Rmax. 2. %Ro. 470.TypeIII&Humic coals 3-(3) Vitrinite reflectance Very popular maturation indicator Tissot and Welte (1984) Ro (%): Tmax (•Ž ): 0.0. Rm (m: mean). . 1. 1.5.
0. (2005) .6 homohopanes average equilibrium ratios C31. 1987) Peters et al.59 (Zumberge. and C35 are 0. C32. 0.58. 0.62 and 0. C33.3-(4) Maturity indicator of biomarker 22R and 22S C31-35 homohopanes 20R and 20S C29 sterane C31 or C32 homohopanes 22S/(22S+22R) ratio: 0 to about 0. C34.55.60.
Peters et al.29. (2005) The less stable Tm decreases relative to Ts with increasing maturity.30-trisnorhopane) and less stable than Ts. (2005) .29.3-(5) GC/MS SIM of oils thermal with Biomarker: broken by cracking and aromatization 17α-hopane decreases increasing maturity Peters et al. Ts is C27 18α-trisnorhopane (18α-22.30-trisnorhopane) and Tm is C27 17α-trisnorhopane (17α22. C27 hopanes Ts/Tm. The C19-C29 tiricyclic terpanes can be used as fingerprint.
.3-(6) Maturity parameters The ratio of 20S/(20S+20R)C29-steranes: a good linear correlation with ßß(ßß+αα)C29-steranes αα means: C29.14α.71. (2005) 20R or 20S 17α or 17ß 14α or 14ß ßß(ßß+αα)-C29-steranes: From near-zero to about 0.67-0. 1986). seifert and Moldowan. 17α(H)-sterane ßß means: C29. 17ß (H)-sterane Peters et al.7 (equilibrium at 0.14ß.
Each maturity value does not indicate the exactly same stage of maturity under a different heating rate condition. Peters et al. (2005) . In high maturity: Hopane isomerization increases more showly than sterane.3-(7) Different isomerization rate (diagenesis to catagenesis) In low maturity: Hopane isomerization increases faster than sterane.
(1994) Ro=0.79*MPI-3-0.6). MPI-3 Sampei et al.4-1.Peters et al. Radke (1988) and Farrington et al (1988) Based on the thermodynamic stability. . Methylphenanthrene index (MPI): Radke et al (1982).30 (Ro=0. (2005) 3-(8) Aromatic compounds are useful as a maturity indicator in postmature zone. ß-position is more stable than α-position.
8 and 0. Ts/(Ts+Tm): up to 1.4 in %Ro (Dia/(Dia+Reg) steranes have a disadvantage that is influenced by depositional environment and clay catalyst and Ts/(Ts+Tm) depends on source. (2005) 3-(9) Range of maturity parameter 20S/(20S+20R) steranes.55 in %Ro Dia/(Dia+Reg) steranes. . 22S/(22S+22R) hopanes: up to 0. DPEP:deoxo-phylloerythro-ethiprophyrin.Peters et al.) MA: mono-aromatic steroid TA: triaromatic steroid Etio: Etio-porphyrin is thermally derived from DPEP.
Tissot and Welte (1984) .3-(10) Origin of methane biogenic or thermogenic Cross plots of δ13C to methane/total hydrocarbon (C1/ΣCn) Biogenic methane δ13C about -60 to -80 ‰ vs PDB very high C1/ΣCn more than 0. δ13C value of methane increase with increasing maturity by thermal cracking up to -20 ‰ vs PDB.97 Thermogenic methane δ13C more than -50 ‰ vs PDB low C1/ΣCn down to 0.6.
Migration and Trap 4-(1) Primary migration: Migrate up or down to such a porous and permeable carrier rock as sand stone The driving force is an internal pressure due to inorganic and organic transformations.4. Secondary migration: From the source rock through permeable rocks along faults and conduits to trap Great migration distance in the order of 100km unless special big unconformity Tissot and Welte (1984) .
4-(2) Porosity and fluid pressure Interrelationship of: Porosity of source rocks. Temperature. Fluid pressure. Tissot and Welte (1984) . Depth Primary migration efficiencies of between 5 and 80 % of available oil are believed.
4-(3) Porosity and permeability of reservoir rock Reservoir rocks require more than: 10 % (porosity) and 1 m-darcy (permeability). Tissot and Welte (1984) .
Tissot and Welte (1984) .4-(4) Microfracturing system in primary migration Many microfractures are produced by overburden pressure after petroleum generation in catagenetic stage. Then. the microfractures connect to initial fractures to migrate hydrocarbons.
fault. and interbedded siltstone lens.Tissot and Welte (1984) 4-(5) Diffusion-controlled processes in primary migration Hydrocarbons move independently from places of higher concentration to places of lower concentration. . important geological structures are: fractures. For this diffusion system.
High temperature increases water-solubility of hydrocarbon. Aromatic compounds are more water-soluble than n-alkane.Tissot and Welte (1984) 4-(6) Molecular solution in water One of possible transporting mechanism of petroleum during primary migration Generally low molecular weight hydrocarbons are more watersoluble than high molecular weight hydrocarbon. Molecular solution system in primary migration is important for low molecular weight hydrocarbon. water-solubility logarismically increases with decreasing carbon number. For n-alkane. .
4-(7) Molecular solution in gas Solubility of petroleum in gas increases with increasing pressure and temperature. Tissot and Welte (1984) .
4-(8) Complex system for oil accumulation Large faults make complex for oil trap system. Tissot and Welte (1984) . Major boundary fault acts as primary conduit for migration.
the more hydrocarbon is expelled. which is recognized by comparing n-alkane distribution of bitumens from thick and thin source rock formations.4-(9) Preferential expulsion Compositional fractionation sometimes occurs due to petroleum expulsion. according to the n-alkane distribution from the thick ones. The lighter molecular weight is. Tissot and Welte (1984) . Thin source rocks easily expelled light molecule nalkane.
Source Rock Evaluation 5-(1) Standard evaluation sheet for source rock potential TOC.S2 HI OI %Ro Tmax Biomarker compositions For considering: Kerogen type Depositional environment. (2005) . Hhydrocarbon potential Maturity Peters et al.5. Rock-Eval S1.
.5% of TOC and 2.5-(2) Source rock generative potential Peters and Moldowan (1993) To assess the source rock generative potential.5mgHC/g-rock is a poor source rock. More than 1% of TOC and 5mgHC/g-rock is a good source rock. the most basic parameters are TOC and S2. and less than 0.
Nevertheless. many shales are not so rick in TOC and S2. depositional environment.5%. (2005) Generally. We need to know thickness. age. continuity and maturity . are occasionally interbedded in the shales and sand. The peaks of TOC and S2 are sometimes about <1% and <2. respectively. very high TOC and S2 more than 5% and 20mgHC/g-rock.5-(3) TOC and S2 of shales Peters et al.
Over about 0. Ibach (1982) .1mm/y TOC decreases with increasing SD. Ibach (1982) Up to about 0.1mm/y TOC increases with increasing SD.5-(4) Controlling factors of TOC Primary productivity Oxic-anoxic condition Sedimentation rate Sedimentation rate is often a key.
Source rocks are sometimes plotted on the straight line with an intercept zero. On this diagram HI levels which show kerogen type are expressed as a linear line. indicating that the source rock had deposited under the same environment and composed of same type kerogen. Peters et al.5-(5) S2-TOC plot S2-TOC plot is a useful evaluation diagram for source rock. (2005) .
e. i. Type I kerogen may deposit under the condition with high sediment+water influx and high accommodation rate with high primary productivity in the balanced fill system Peters et al. in the fluvial system with over filled. (2005) .5-(6) Lacustrine evaluation source rock Coal deposits under the condition with high sediment+water influx and low accommodation rate.
(2005) Steranes and hopane distributions are good indicators for organic source.5-(7) Biomarker as organic source indicator Peters et al. .
C28-sterane is mainly from such specific plankton as diatom. Peters and Moldowan (1993) . C27-sterane is mainly from phyto-plankton. C29-sterane is mainly from land-plant.5-(8) Biomarker as organic source indicator 1 Ternary diagram of C27-C28C29-steranes shows origins of organic matter.
Because C28/C29 sterane ratios have changed during the last 600 Ma. The ratio from marine source rock with a little or no terrigenous organic matter input have increased from about 0.3 in 600Ma to 1. (2005) .5-(9) Age control of the C28/C29 steranes ratio Care should be paid for the interpretation of C28/C29 steranes ratio.3 in 100 Ma Peters et al.
High Pr/Ph ratios >3. 1993).0 indicate terrestrial organic matter input under oxic conditions and low values <0.6 typify anoxic (Peters and Moldowa.5-(10) Oxic-anoxic proxy 1 Oxic-anoxic proxy: pristine/phytane (Pr/Ph) ratio. Peters et al. (2005) .
commonly due to hypersalinity) Peters et al.5-(11) Depositional environment indicator condition 10*Gammacerane/(Gammacerane+Hopane) showing oxic-anoxic according to salinity stratification . (2005) . (water-colum stratification.
5-(12) Origin indicator Highly branched isoprenoids (HBI) are diatom markers (Jurassic to Tertiary) HBIs: series of C20. C25.C35 Peters et al. C30. (2005) .
(2005) 5-(13) Depositional indicator Isoprenoid thiophenes: Anoxic and iron-poor condition produce H2S by sulfate reducing bacteria Then H2S was incorporated into isoprenoids. .Peters et al.
5-(14) Origin indicator 2 Irregular isoprenoid hydrocarbon botryococcne (C34H70) is from Botryococcus braunii. A lacustrine alga accumurated into boghead coal and torbanite Peters et al. (2005) .
Oleanane/(Oleanane+C30hopan e) ratio: Highly specific for higher plant input Peters et al.5-(15) Origin indicator 3 Oreanane is from angiosperms or flowering plants nearly terrigenous mainly after Cretaceous age. (2005) .
concludes biologist David Winship Taylor of Indiana University Southeast. http://www. "Flowering plants may have originated during the Permian period. a species of gigantopterid unearthered in China in 1993. This drawing is a reconstruction of Vasovinea tianiia. daffodils and other flowering plants. an extinct plant group that lived some 250 million years ago. Gigantopterids: The oldest oleanane-producing seed plants. Gigantopterids. followed by firs. research professor of geological and environmental sciences. 2001 Geochemists find evidence that flowers may have evolved 250 million years ago When flowering plants appeared on Earth ? According to the fossil record.Stanford Report. But the chemical is absent in other seed plants. We based our findings on an organic compound called oleanane " says J. may be the oldest relatives of roses. conifers and several other varieties. Michael Moldowan.edu/dept/news/report/news/april4/acsflowers-44. between 290 and 245 million years ago. such as pines and gingkoes.html Mosses were the first plants to emerge on land some 425 million years ago. Fossilized deposits of gigantopterids contain oleanane – an organic chemical found in modern flowering plants but absent in pines and other seed plants. ginkgoes. Oleanane Oleanane is produced by many common flowering plants as a defense against insects. Artist: Hongqi Li/American Journal of Botany . April 4. fungi and various microbial invaders. flowering plants abruptly appeared out of nowhere about 130 million years ago.stanford.
Organometallic derivatives of the nucleus of the haemin or chlorophyll molecule. Iron and magnesium are bonded to these compounds. While, during diagenesis ion exchange takes place in the nucleus, and nickel and vanadium are substituted.
Peters et al. (2005)
5-(17) Souce rock potential and environmental change
During transgressive, TOC and HI are high, and terrigenous input and degradation are low.
Peters et al. (2005)
6. Oil-Source Rock Correlation and biodegradation 6-(1) Tool for oil-source rock correlation Oil-Oil correlation: n-alkane, aromatics, biomarker, isotope ratio Oil-Source rock: n-alkane, aromatics, biomarker, isotope ratio Oil-Gas: light n-alkane, isotope ratio Gas-Gas: light n-alkane, isotope ratio Gas-Source rock: n-alkane, isotope ratio
Tissot and Welte (1984)
6-(2) Correlation by n-alkane n-Alkane distribution is useful for correlation. Between bitumens from source rock and oils Curiale (1993) .
Care should be paied to the maturity. Curiale (1993) .6-(3) Correlation hopanes by steranes and Steranes and hopanes are the most useful fingerprints.
(2005) .6-(4) Correlation by steranes Comparing the ternary diagrams of sterane and diasterane Diasterane composition reflects rock faces such as clay stone. Peters et al.
the oil-source rock correlation may be known. The gas – source rock correlation is difficult under deltaic and coalforming condition Peters et al.6-(5) Confidence of oil-source rock correlation Under marine and lacustrine environment. (2005) .
Higher molecular n-alkanes are easily broken in the first stage of biodegradation Peters et al. (2005) .6-(6) Biodegradation of n-alkane n-Alkane is the most sensitive to biodegradation.
(2005) .6-(7) Biodegradation stage Hydrocarbon gases •¨ n-alkanes •¨ iso-alkanes •¨ isoprenoids •¨ aromatics •¨ poly-aromatics •¨ steranes&hopanes Peters et al.
1%.6-(8) Biodegradation effect on sulfur&nitrogen contents and API Sulfur and nitrogen contents decrease about 4 and 0. (2005) . respectively. While. API increases from about 8 to 30 Peters et al.6% to 1 and 0.
7.75 at 1-2ºC/Ma. %Ro=0. computer simulation is necessary for an accurate discussion Rullkotter (1993) . maturity of the peak of oil window decreases: %Ro=0. Modeling 7-(1) Changes in %Ro under different heating rate With increasing heating rate. Therefore.6 at 6ºC/Ma. %Ro=0.9 at <1ºC/Ma.
thermal conductivity of rock strata.63•~ 10-5 (Wm-2) .42•~ 10-5 (Wm-2) World average: 0.Geothermal gradient (•Ž /km) Depending upon 1. water movement World average:25•Ž /km 5•Ž /km: ex. heat flow 3. Walio oilfield in the Sarawati Basin. Andros Island in the Bahamas 90•Ž /km: ex. indonesia Heatflow(Q) Q=k•~ ƒ¢ T k:thermal conductivity ƒ¢ T:geothermal gradient 1 (HFU: heatflow unit) = 0. 2.
.. k 2 = Ae − E / R (T1 + ∆T ) .... k n = Ae − E / R (T1 + ( n −1) ∆T ) C1 = C 0 e − k1 ∆t .. A: pre-expornential factor.(2) dT =q dt k = ( ----------------------------------------------------------- (3) A T − E / RT e dT q ∫T 0 ------------------------------------------------------------------------------------------------- (4) (5) ART 2 − E / RT )e k=( qE RT RT 2 1 − 2 ( E ) + 6 ( E ) k1 = Ae − E / RT1 . (1986) C = C 0 e − kt k = Ae − E / RT (concentration chan ge) (A rrhenius equation) ∆T = q) ∆t . t: time.-Sampei-and Suzuki-(2005).⋅ ⋅ ⋅ ⋅ ⋅ ⋅ ⋅.987 cal/deg.⋅ ⋅ ⋅ ⋅ ⋅ ⋅ ⋅⋅..-------... (5) by Alexander et al. q: heatig rate... R: gas constant 1. k: rate constant...-------------------------. C0: initial concentration of kerogen.( 1 ) ----. Pre-exponential factor (A) C: concentration of kerogen.. E: activation energy. C 2 = C1e − k 2 ∆t . T: absolute temperature. C n = C n −1e − k n ∆t ------------------------ (6) (7) (8) ----------------------------------- C n = C 0 e − ( k 1 + k 2 + ⋅⋅⋅⋅⋅⋅ + k n ) ∆t -------------------------------------------------------- .7-(2) Kinetics of isomerization Activation energy (E).
7-(3) Data set of kinetic parmeters Sampei and Suzuki (2005) .
7-(4) Simulation results Sampei and Suzuki (2005) Sampei and Suzuki (2005) .
y by PRA software . Colombia Cretaceous Age m.Modeling of Burial History for the La Luna Formation(Well) La Cira 1625K well.
y by PRA software . Colombia Cretaceous Age m.La Cira 1625K well.
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