. Bogota 16-18" February 201Aun ewne Biogenic Gas Generation and Migration Processes Short Course Bogota, February 16'"-18", 2010 Contents . Introduction to Biogenic Gases . Biology and Metabolism of Methanogens . Chemical and Isotopic Composition . Modelling Biogenic Gas Generation . Expulsion and Migration . Unconventional Biogenic Gases o Solution gas o Secondary biogenic gas o Gas hydrates . Summary . References BGX1000Tutor biography Chris Clayton PhD ARSM, FGS geochem@e-clayton.com Chris was born in the UK more years ago than he cares to remember. Following a first degree in Geology at Imperial College, U London and the Institute of Geological Sciences Isotope Geology Unit. sity of London he completed a PhD in silica diagenesis and chert formation jointly at King’s College He joined the BP Research Centre in 1982 where he somehow became and organic geochemist. During this time he researched among other things, isotopic behaviour in the petroleum system, kerogen formation processes, biogenic gas generation and controls of petroleum seepage. Chris left BP at the end of 1992 and has since worked as an independent consultant in geochemistry and basin modelling to the petroleum, minerals and groundwater industries world wide. He now lives in the middle of nowhere in the heart of the English countryside near Worcester, « BGX100.0: Biogenic Gas Generation & Migration Processes ween |. Introduction to biogenic gases a What are they? a Why are they important? a Where are they? a What am I going to learn this week? ween What are biogenic gases? Natural gas, principally methane, formed in sediments as a direct result of microbial activity BGX100.1 LIBiogenic Gas Generation & Migration Processes wpepe@er Common misconceptions 2 Biogenic gases are a minor resource right? 3 Wrong: > 20% of known gas reserves 2 But they are quite small aren't they? 2 Nope! 2 ea Urengoy 286 tf 2 Young sediments only though? Next you'll be telling me that they aren't shallow 2 Correct! 2 Anonety 4,600 (15,000) 2 Butonly of local importance - surely? 3 Wrong - they're everywhere ween New developments a Petroleum industry 2 Growing realisation that biogenic gases are viable exploration targets 2 Gas hydrate exploitation 2 Coal bed methane o Environment 2 Methane more than 20x more potent than CO, as a greenhouse gas 2 Gas hydrate decomposition provides a feedback loop 4 waning 2 decomposition > methane > warming a Microbiology 2 Major new understanding BGX100.1 12Biogenic Gas Generation & Migration Processes wwen Where are they? But it may be swamped by thermogenic gas ‘gu 4 econ mae nro sas be Sacer Gas Gece Ota fe ; - WS \Vajor plays Play Reserves a 750 tef Shem (90% known reserves) “12 tef Poway, (15 tef in place) Plait 200 tef oe (735 tef in place Teen ah 200 bef Flegist) (85 tef in place) GoM 2 16teF Cook Inlet 1 tcf (6.5 tef yt) ‘Nigeria/Black Sea n Carpathian foredeep 7 tef (7 tet yt) ‘Trinidad n BGX100.1Biogenic Gas Generation & Migration Processes wweee What will happen in this course? 1. Introduction » Biology and Lots of lectures Metabolism Chemistry & Isotopes Basin Modelling Migration Case studies Practical exercises Aww Unconventional gases 2 Solution gas 2 Secondary methane 2 Gas hydrates 7. Summary ween Riles There is no timetable! We take whatever time we need Tf you don’t understand something — ASK You will not be alone Questions and interruptions are welcome Exercises are not tests Feel free to cheat BaxI001 1Biogenic Gas Generation & Migration Processes wawee 2. Biology & Metabolism of Methanogens What are they? Where do they live? How do they work? a What conditions do they need? oco wees Classification a Methanogenic (‘“methane-producing”) organisms are members of the Domain Archaea a Distinct from bacteria and (“higher organisms”) a Eucary a With bacteria, comprise the procaryotes cf multicelled eucaryotes (~ Eucarya) a Previously referred to as Archaebacteria a changed ¢. 1977 a Probably among the first organisms on Earth BGX100.0 21Biogenic Gas Generation & Migration Processes ween Key differences ‘Archaca a Structure 4 Archaea & Bacteria ~ single celled 4 Eucarya~ multi-celled Bacteria a Cell walls 4 Archaea ~ pscudopeptidoglyean or protein only 4 Bacteria —peptidoglyean 4 Eucarya plants: polysaccharides, animals: none, fungi: chitin a Cell membrane 44 Archaea ~ branched chain hydrocarbons linked to glycerol by ether linkages 2 Bacteria & Eucarya ~ straight chain fatty acids linked to glycerol by ether linkages a DNA 4 Archaea & Bacteria ~ chromosome is a single “circular” DNA molecule 4 Archaea also have circular DNA “replicons” 4 Archael gene organisation more like eucaryotic genes than bacterial Fo wwaeer Archacal classification a Two main phyla a Crenarchaeota o Euryarchaeota Many archaea are extremophiles a subdivided into classes a Halobacteria < high salinity 2 Methanobacteria 2 Methanococei 2 Methanopyti 2 Archeoglobi 2 Thermoplasmata bigh temperature 2 Thermococei < — a Some others proposed a Nanoarchaeota a sit le species a Korarchacota a known only from DNA BGX100.0 2awees Morphology a Typically a few microns 2 Olpto>15p a same as bacteria a Variable morphology a bacilli a cocci 2 spirilli a plate like a either unicellular, colonial or filamentous a Some are flagellate 2 gives motility Biogenic Gas Generation & Migration Processes 1oT 1mm Eucaryotes 10° 10° Procaryotes 2 PTH E wor Viruses 10° Proteins 10° nm Small molecules 10" Atoms ween Methanogens a Require anoxic, sulphate-free environments 4 outcompeted for substrates by sulphate reducing bacteria a animal intestines a swamps and marshes freshwater and stagnant 2 marine sediments below the sulphate reduction zone Ws ete. a often dominant organisms Formation of biogenic methane femaraton, CH:000H -€H4 + COs BGX100.0Biogenic Gas Generation & Migration Processes ween Microbial distribution in marine sediments Total microbial PLsingmi) Archaeal PL (9%) 1 100 1000 =o 50 100 .001 2 Microbes alive to >700m_ based on intact polar lipids oor: 2 Archaea dominant below ~20em 2 More recent work extends this to >1500m Subseafloor depth im) 100. 1,000. waeee Methanogen metabolism ‘Two main methanogenic processes operate: 1. Carbon dioxide reduction CO, + 4H, & CH, + 2H,0 Acetate fermentation CH,COOH © CH, + CO, Used to be thought that CO, reduction was dominant in marine environment and fermentation was dominant in freshwater environments. “Supported” by 8D data. Now known to be more complicated Methanogens are the end member of a complex consortium of microbial processes BGX100.0 24Biogenic Gas Generation & Migration Processes ween! Microbial ecosystem complex microbial community Methanogens are the end member of a ‘And have a complex biochemistry of their own a wees Energy yield — various substrates CO; reduction Reactants Products AG*(KJ/mol CH4) ‘COxg) * 4HA9) - CHag) + 2H20 1308 (1) 4HCOO™ (aq) + 4H” = CHAg) + 3CO49) + 240 144.5 (2) CO4(g) + 2CH,CH.OH(aq) + CHalg) + 2CH;COO™(aq) + 2H,0 41115 @) ‘COx(g) + 4CHsCHOHCHaq) (CHalg) + 4CHsCOCH3(aq) + 2H20- 7 4) Methyl reduction Reactants: Products AG*(KJ/mol CH4) 4CH,OHiaq) 3CHag) + COxA9) + 240 106.5 (5) (CH;OH(aq) + HA) CHAg) + HO 1125 (6) 4CHNH;"(aq) + 2420 - 3CHi(g) + COx(g) + 4NH,"(aq) “76.6 7) 2{CH) NA + 240 “30H con ani 3 {ACH + 6H,0 SCH, + 300;¢ NK" *% & CHCOCOOH +05H:0 © 1280H, + 17800, 6 4 (CHyCOO (aq) + H” CHalg) + COAG) “36.8 (11) BGX100.0 AG* standard free energy change at pH 7.0 25Biogenic Gas Generation & Migration Processes ween Methanogenesis controls a Substrates a COyhydrogen or acetate a Other nutrients 2 @g. nitrogen, phosphate et problem sd trace concentrations 2 available locally from mineral diagenesis a Temperature tolerance a Salinity tolerance a pH tolerance ween Where does substrate come from? 2 Used to be assumed that other organisms produced CO, and H Key paper: Wellsbury er al. (1997) Heated coastal sediments to ~100°C Stimulated acetate (x10°) formation which increased methanogenesis Matches profile in cores from Atlantic ocean Suggested that this is biological acetate generation, 2 decreases fens 60°C 2 Parkes et al (2007) repeated experiments using irradiated controls to prove biological origin of wees VIL howe 1 ag sah, cts sch BGX100.0 26Biogenic Gas Generation & Migration Processes ween Organic carbon supply a Source of substrate a Recent organics or protokerogen a anything will do, but a temperate climate, terrestrial organic matter best 2 rich in carbohydrates a No known limit on TOC a but need enough to generate a free gas phase 2 typically 0.5-1% weeee Temperature control — individual species 10, & Collation of published ‘methanogen temperature ranges g & Relative activity of CH, production poe prise He Sem chenyer 0 10 290 SD 7 BD Semen ie Bovey Temperature°C Key points: a All species less efficient at low temperature and high temperature 2 Optimum temperature varies with species ‘4 notable optimum around 35-40°C Just about anything possible BUT these are individual species a methanogens are only the end member of a consortium BGX100.0 27. Biogenic Gas Generation & Migraticn Processes ween Temperature control — microbial consortium 06 ‘ D: ‘sudash Incubation of organic-rich slurries © 1omdepth © ae depth — average 10418 os Spiked samples showed same effect, implying true biological 04 03 02 Relative generation rate (normalised) on ° ir Temperature °C Better representation of real world J wpe@ee Temperature controls a Optimum temperature around 35-40°C a Implies an optimum burial rate/thermal gradient a Too slow: organics reduced before methanogen optimum a Too fast/hot: methanogens cooked before they finish their work adinerese ata tm BGX100.0Biogenic Gas Generation & Migration Processes wawee Salinity a OK in fresh water a methanogenesis in lakes and glacial tills (Illinois) a Common in marine sediments at depth (35+ ppt) a Should be an upper limit a obligate halophilic methanogenesis found to occur up to 12% salt (Perez-Filiol etal, 1985) 2 but only for CO,/H, pathway 2 limit not known for acetate pathway ween pil control a Optimum thought to be c. 6.5-7.5 but exceptions exist a Methobacterium strain AZ 6.6-7.4 (Zehnnder & Wubrmann, 1977) a M. mobilis 5.9-7.7 (Paynter & Hungaie,1968) a M. arbophilicum 6.4-8.6 (Zeikus & Henning, 1975) a M. thermoautotrophicum 6.0-8.8 (Zeikus & Wolfe, 1972) a Common in peat bogs a usually pH around 5.5 a Methanotrophy exists below pH 1 (Pol erat., 2007) a also archaea so possibly also some methanogenesis at this pH a Methanogenesis also observed in alkaline hot springs (Ward, 1978) a pH8&s a 30-71°C BGX100.0 29Biogenic Gas Generation & Migration Processes ween Key Plays a Deep sea fans 2 Sedimentation rates are typically very high a Geothermal gradients are low a Source shales and reservoir sands are intimately associated 2 Organic matter is usually terrestrially dominated a Deltas. 2 High sedimentation rates a Low geothermal gradients a. Terrestrial organic matter a Coastal Plains. 2 Lower than optimum burial rates but a Very extensive 2 Organic matter terrestrially dominated BGX100.0 210Biogenic Gas Generation & Migration Processes wees 3. Chemical and Isotopic Composition a How do we recognise biogenic gas? a How do we deal with mixtures of biogenic gas and thermal gas? ween Hydrocarbon chemistry of biogenic gas 7 All biogenic gases very dry “0 Archaea can only produce methane and traces of ethane/propane under normal ‘circumstances Rare excepti ° 85 sto ms 350 "960 acxi000 atwees ODP leg 201 Toate oy cae) tf fepate ey) J | % | < ie . Peru margin eruise :* . ] Largely dedicated to microbiology * Biogenic Gas Generation & Migration Processes = cot 0 © 2 {emane. propane) (moth) wes mostly adsorbed Ac entrations kept low due to deep sul kes fermertation of higher ween Higher Hydrocarbon Generation ‘Two main methanogenic processes operate: Carbon dioxide reduction CO, + 4H, & CH, + 2H,0 No mechanism to form higher hydrocarbons Fermentation pathway CH,COOH © CH, + CO, (acetate) C,H,COOH © C,H, + CO, (propionate) C\H,COOH & C,H, + CO, (butyrate) Potential to form ethane and propane True mechanism probably more complicated Baxiono Distribution of VFAS i typical marine sediments Acetate most aburdant Also most energetically favourable to fermentBiogenic Gas Generation & Migration Processes wees Also demonstrated in Laboratory 4 Anoxic estuarine sediments a thane oy hse 4 “ Incubated in laboratory ‘Methane concentrations ~ 10" x ethane concentration etname (emoves/Tu8e) * wetmame Garoces/ 1086) \ $a $9 eale ween Inorganic components « Acetate fermentation: CH,COOH = CH, + CO, produces 50/50. CO, and CH, ‘Carbon dioxide reduction: CO, +4, =* CH, + 21,0 reduces COs and generates CH, ° 3 1S BY asa0350030 Pe wo Me we m0 20 m5" 4 te’ => €0,£0, +04, Nines CH) BGXION0 33Biogenic Gas Generation & Migrtion Processes wees Influence of solubility Solubity rm StP/) 123 4s s ‘Hydrostatic conditions: i 3 E = i 5 caves & se = zon sso ines ie "i e rowan discharging water wee Carbon isotope ratios u Three forms of carbon: a @C,3C, 4C: different numbers of neutrons a 'C radioactive, °C & C stable all have same chemical properties additional source of nitrogen eS > Cee a 3C to ?C ratios vary because reaction rates vary for each molecular mass Reanpte = Reandard 1000%o standard “del” R=PCmC standard for carbon is PDB) Calira estonder. BGXIO00 a4 “per mil”Biogenic Gas Generation & Migration Processes wees Carbon isotope ratio — biogenic methane 120 1 Grciatantt Tl Freshwater lakes and swamps TB Marine sediments 100 80 60 40 ‘Thermogenic gases 20 «95-90 -80 -70 -60 -50 -40 -30 -20 waeee 5'°C of associated CO, associated with CO, reduction 2 1 Glacial it co, cH, Freshwater lakes . and swamps 1m Marine sediments = x» oval 40% a 6 65 %e @ 40 %6 ‘6 20% ——. 7 . 60% 15% 5 m}20 16-12 8 -4 0 4 8 12 16 20 abe le ex, Rayleigh fractionation 55 %e If dominated by CO, reduction, CH, and CO, isotopes will track ceach other Bax10n0 a5Biogenic Gas Generation & Migration Processes wees Example Rayleigh curve 1 09 «08 «07 GOS ok 82k f(L-extent of conversion) wees Data from DSDP cores ss ” ne er Rie tof arin as posi e Pr ee area : Pe 7 = os i 2 i- Rl bk Seem o track eachother at sallow depth: a F " implies high propeton of CO, eduction = a Diverge at greater deh: dominantly fermentation pathway a = eh ite ai ech ‘tees ‘Cpe ey te Soe pe ee a a ey a oy ™ = = = : oc) E Cayenne saximao 46Biogenic Gas Generation & Migration Processes waves 5!°C of higher hydrocarbons ‘Considerable conflict in the literature Many publications cite very light values for ethane and propane Possibly an analytical effect Needs more work! 300 4, (red) 4, (blue) 4, (green) 400 00 800 04 o ween Hydrogen isotope ratios - 5D Originally interpre ‘CO, reduction (he entation (light) vs. y group) But 2. Fermentation produces CO, as well as CH, a CH,COOH & CH, + CO, 4 this CO, then reduced 2 partial overprinting of fermentation signal 2 Laboratory labelling studies show that acetate itself can exchange hydrogen Jo to 4 dere ea, 1956 eiicawatierenciny a. Dill exchange in methyl group CO,+4H, — CH,+2#,0 2 probably result of enzyme complex carbon monoxide ~~ chydrogenase and subsequent methyl group Equilibrium with water ren KY ~ 2 eS PAIS — nm, «K) AS Me k" faster than k!? -20 %e 4 —e — kinetic isotope fractionation 40 B5C of gas depends on: 0 89C of procaine —=_. a «kinetic fractionation factor (k'Yk"") 2 extent of generation “35 %eBiogenic Gas Generation & Migration Processes ween Rayleigh fractionation 1 09 08 oF 06 05 04 03 02 01 09 Fraction remaining (ducctse\ gos gererv loa index), wpep@es Isotope interpretation diagrams With suitable calibration of & and determining 3!°C of precursor relative to bulk kerogen Can construct interpretation diagrams for 6'C in gas components As a function of both source and maturity BGx100.0 30Biogenic Gas Generation & Migration Processes wees Methanc-Wetness crossplot Wee Australian coal gases BGXI000 aurwpapee (US) Gulf of Mexico 8c methane wre source Biogenic Gas Generation & Migration Processes os 07 ayscs wpeee Texas/Louisiana detail Bax100.0 ‘8c methane wrt source merelor de kermogen 4 borgenre Amoyer prshindeded 4 onhyosded Jrendt ose Jenmogenie oa os os o7 os 09 capeers 32Biogenic Gas Generation & Migration Processes Wee GoM methane isotope ratios Wee GoM ethane isotope ratios Extensive Cracking ‘Moderate Cracking Lage thons bags noe CPC indicu lermogente BGxI000 3BBiogenic Gas Generation & Migration Processes wee@e@e Isotope distribution diagram Methane Ethane Propane Butane BGxI000 34wees Effect of gas mixing a. Gases of same maturity Biogenie Gas Generation & Migration Processes b.More mature non-associated gas ae a 20 20 f son, 30 30 - Le 40 0 2 / leone’ “ aecpaict-tsane / ae somarectsd- 2080 ey «o methane ethane propane butane methane ethane propane butane weee@em Draugen Field - NOCS ae 45 a Two groups of gases implies significant barrier in field a Lower group pure Spekk source a Upper group contains 10-20% coal gas BGXI000 aus from Are Fm. Implications: 2 gas flushing a deasphalting may produce tar matBiogenic Gas Generation & Migration Processes Alternative methods (Some good, some not so good!) wees Schoell diagrams 1% methane “300-250-200 “150-100 “65 | oC methane, propane, & i 25 BGxI000 36Biogenic Gas Generation & Migration Processes wemee BGR empirical correlation - beware! 20 Only works for the a kerogen 5!°C from which it was derived 204 Kerogens of different g 88C will give different = 9 answers io as 4 40 : T T = Ld T 40 35 30 “25 -20 °C propane wees Chung natural gas plot Vo " 00 2k 20. C-C-C-C-C-C-R oe C-C-C-C-C-R ms c-C-C-C-R C-C-C-R C-C-R * A a b Mass balance: “° ONC, = [ONC + (1) 8hC, 1/0 ” rearranging: 44 oe Cateeco rete BBC, = -Im HNC, -8C, ) FOC, 46 : But assumes isotopic homogeneity of gas precursors lzieare ethane methane npantare BGx1000 30?Biogenic Gas Generation & Migration Processes wwe James (1983) diagram Calculated isotopic equilibrium fractionation factors as function of temperature ‘Then re-normalised to field data using LOM maturity scale Gives isotopic separations as function of maturity wae James diagram Lom 6 4 0 2 4 6 18 T T T T T T methane 10% ethane Rewsrvt F LOM scale offset propane. by 2 units butane

> &y ot ee 30 RY a ey oY \ -40 3 § z 48 = -50 Ss “60 Po Dried 1 AField 2 “ © Field 3 -70 + 0 o1 02 038 O4 OF 06 O07 08 09 1 an Campo » S Ce 36/ ee OCLs ass. in| SP Ces: asl Boo C9Cx EIth- veneer Exercise | 8Biogenic Gas Generation & Migration Processes Macuspana Basin background ‘The Macuspana Basin is a partly onshore, partly offshore basin with 13 producing fields, all in the onshore part. ‘These have produced 5.2 tef gas to date with remaining reserves estimated at 1.8 tef. Gas is produced from deep water marine turbidites in reservoirs of Miocene to Pliocene age, down to 2600m. Lower Pliocene shales are believed to be the main source rocks. Geothermal gradients range from 20- 27°C/km with a maximum reservoir ‘temperature so far encountered of 75°C. Blo. stratigraphic ~ manners lubes jubigrmnaes ohio obs obigevina mepethes ae orice Glebe apna olahna lanl ar Speco nese F580 —claturctaia manert = F520 Prertatin glamor FHC Clobigerma opens FS Matine fooding surface“ Upwarfing LUNG Urcontority \ Upware-coarsenng [Elemis [caress [—] se Exercise 1Biogenic Gas Generation & Migration Processes Souree Rock (Lithology) ‘Tarooian (8h, Lst) Cretaceous (8h, Lt) Paleocene sn) Eocene (8) Oligocene (8) UM Niccene (Sn) UMiocene (sn) L Pliocene (sm) ‘TOC (samples) TOC (average) wt wth 0.50.4.61 (221) 0.59-4.79 (139) 051.387 (73) 051-159 (311) 0.50-2.56 (239) 0.50-1.70 (407) 050-275 (147) 0.80.1.47 (59) * TOC =Total Organic Carton HL= Hydrogen Index Korogon Types: Type Iil= Hi 75-200; Type Will = #11 200-400: Type Il = 1 400-7001 Exercise | 085 Be 0.88 =a 75-791 175-800 87-843 63.771 75-644 71484 70-551 meta Kerogen Type Basedon Hi 100,10 "a, ‘ua, ‘a, 1 ‘un, vi wat, vu wa, Early mature to mature (420-478) Immature to mature (421-472) Immature to mature (423-456) Immature to mature (418-448) Immature to mature (421-445) Immature to early mature (423-442) Immature (415-432) Immature (413.432). Biogenic Gas Generation & Migration Processes wawee 4. Modelling biogenic gas generation a How can we estimate volumes of biogenic gas? a Can we build this into basin models? a Biogenix® software @aeee The new order 2 Revolution in microbiology happening quietly in the background 2. Direct evidence of deep biosphere 5 live organisms isolated from >1500m in marine sediments a Acetate fermentation looks to be most important 4 conflict with earlier hydrogen isotope studies which suggest CO, reduetion dominant 2 Substrate supply to methanogens appears to be temperature controlled 4s thermal activation and biological breakdown of protokerogen a Substrate is limited and availability is kinetically controlled Amenable to modelling Can we build this into conventional basin models? aGxi000 “a. Biogenic Gas Generation & Migration Processes: wees What do we know? 2 Microbial consortium which produces CH, has a set sliewies © Geol temperature tolerance i fom 2 CH, step involves availability of substrate 7 a Principally acetate ont a Organisms are starved 7 2 Substrate is produced by microbial processes i 2 But depends on “softening up” of protokerogen | 4 2 ar main aan aca j a Implies an inorganic structural rearrangement in kerogen ‘ a Kinetic process von 2 Notall of protokerogen is available to convert to a acetate Bonn pobndadeds il edo yaa eo lenceria ncn How can we build this into conventional basin models? “Cae @eweae Modelling the process 9 Need to understand: 2 Volumetries How much kerogen gets converted «@ Substrate generation 4 Chemical kinetie approach How much is reactive? a Microbial conversion efficiency Volumetnis 4 Temperature control How fasts substrate generated? Substrate kinetics How much substrate Isconverted to methane? Microbial efficiency BGx1000 aBiogenic Gas Generation & Migration Processes wees Stage 1 - Volumetrics a During diagenesis, protokerogen loses carbon, hydrogen and oxygen a How much carbon is lost during diagenetic stage below sulphate reduction zone? 2 Can't rely on lab studies 4 Experiments not exhaustive 2 Two approaches: 4 Carbon/sulphur mass 4 Carbon/oxygen mass ba wees Volumetrics — C/S ratios Sulphur incorporated into kerogen and/or matrix (pyrite) during sulphate reduction Any subsequent change in C/S must be due to toss of carbon “fixed” below SRZ 5 = otter _ SS arse esa mie 20 iets Sis i z 10 Raisewell & Berner (1987) as looked at mean CIS ratios in black shales ° os 10 15 20 25 30 35 40 BGxI00.0 43Biogenic Gas Generation & Migration Processes wees Volumetrics: C/O ratios Organic matter > CO, + 4H, % CH, + 2H,0 Carbonoxygen lost in the atomic ratio CH,COOH & CH, + CO, (+ 4H, % CH, +2H,0) Carbon:oxygen lost in the atomic ratio 1:1 % carbon lost CO, reduction TABS Type Ik fermentation [SRO CO, reduction 4.9-6.0 fermentation [ERED ef. 21.5 % from C/S ratios Type II omc ween Stages of modelling Type: 24 Type i How much is active? How fast is substrate generated? Substiate kinetics How much substrate is converted to methane? Microbial efficiency BGxI000 aBiogenic Gas Generation & Migration Processes WOH Stage 2 — How fast is substrate generated? 2 Key paper: Wellsbury et al. (1997) Heated coastal sediments to ~100°C ‘Stimulated acetate (x10°) formation which increased methanogenesis. Matches profile in cores from Atlantic ocean Suggested that this is biological acetate generation 2 Parkes ea (2007) iat contol to prove bilagcal conta ‘Same process observed in natural environment wees Substrate generation 2 a Comparison of lab and natural data do not match 2 Implies a heating rate effect 2 Nota pure biological control 2 Repeated experiments show that source of acetate is limited a Progressively exhausted 2 Lot in common with conventional kinetics 2 Comparable to conventional petroleum generation 4 Can be modelled using Arrhenius approach aGxi000 45Biogenic Gas Generation & Migration Processes Waee Reaction kinetics dc c's agp sinensis Based on first order reaction: ——— ieopen dt oo aC Rewriting equation; ——= KC dt kis the rate constant _E——_Tistwoktetroponte defined by Armheniusas: k= Ae *F 4s equeney ft Eis actaton ‘pends an pe of bods bokon Ifwe know A and E we can predict the extent of reaction as a function of time and temperature Kerogen is complex - numerous reactions are involved need a range of activation energies WH8H What conventional kinetics to use? a Parkes* team work suggests feedstock generated as organic acids (espe. acetate) a Supported by PhD work at Potsdam (Vieth ef al., 2008 and GRC presentation) 2 Published kinetics for acetate 2 Braun ea. (1992) 2 Knauss ef al (1997), 2 stuggest temperatures too high for methanogens to use 2 BUT, Wellsbury ef al. (1997) say that acetate is rapidly broken down to CO a Therefore use CO, kinetics as proxy 1 Semthing happens othe kerogen 2 But what CO, kinetics? 2 Numerous options. “pence BOxI000 46sr i eri a WaeH CO, kinetics a Burnham & Sweeny (1989) Industry standard 2 But not based on truly immature kerogen a Schoell - Pokur coals a Boom Clay 2 Deniau et al. (2005) 2 Lorant et al. (2008) 2 evisod Kinetics using diferent A foreach 2 beter simulation of early CO, burst 2 Tie impact on CH, generation i oe I How much substrate Is converted to methane? ‘Microbial ficiency BGxIO00 a7Biogenic Gas Generation & Migration Processes Wweee Stage 3 -Microbial efficiency . \ \4 i methanogen temperature ranges oa 02 { 3040S . 0 2 Relative activity of CH, production Temperature°C Key points: 2 All species less efficient at low temperature and high temperature 2 Optimum temperature varies with species ‘4 notable optimum around 35-40°C 4 Justabout anything possible a BUT these are individual species 2 methanogens are only the end member of a consortium @ea@ee Temperature control - microbial consortium 06 os pases Incubation of organiich i iccach slurries. 0s © amdepth average 10+18m | Spiked samples showed same effect, implying true a biological temperature sensitivity 03 02 Relative generation rate (normalised) on ° er ne a a a ne |) Temperature C Bax100.0 48Biogenic Gas Generation & Migration Processes Wwee Microbial temperature control Modelled as combination of two normal distributions aso teens ¢ ete ns Smee : ee i ee @ ‘normal distribution 2 ag owner 3 5 a0 g & 020 3 ® o10 an a a ae ee a a a) temperature (*C) umed that at optimum efficiency microbes can convert all available substrate Wweee Stages of modelling Type I: Type I How much is reactive? Volumetrics How fast i substrate generated? Substrate kinetics How much substrate is converted to methane? Microbial efficiency Baxi00.0 419Biogenic Gas Generation & Migration Processes @eee Correction for near surface losses «a Earliest methane bubbles out of system 4 “Ebulition” 2 or diffuses up 4 Re-oxidised at base of sulphate reduction zone a Need to correct for this 2 Base or SR zone ~ 12m for GoM ——. 2 No general rule 4 Usually take nominal 15m as max depth for \ ween Final modelling scheme substrate generation N COsresuton: CO, +r 4Hy «CHa + 20 microbial efficiency Baxi000 x ‘methane generation profile 410Biogenic Gas Generation & Migration Processes Weaee Methane speciation a Notall methane will be in the gas phase a Need to calculate a Adsorption effects a Apressure, temperature, TOC) a Dissolved gas content 2 Apressure, temperature, salinity, porosity) a Remainder in gas phase a PVT correction to get gas saturation in pores 2 Biogenix assumes ideal gas 2 Combined with Compaction curves to derive bulk density + Weee Adsorption effects Based on equation of Pepper & Corvi (1995). Gas believed to be adsorbed on kerogen. Defines adsorption coefficient acy, (g/gC) dcyy = 6.703 + 9.4e**log(P) — 6.2e**log(T) P = pressure (MPa) T= temperature (°C) BGx100.0 aulBiogenic Gas Generation & Migration Processes Ween Solubility Based on equation of Yamamoto et al. (1976) Defines the Bunsen solubility coefficient, b: In b= A, + A,(100/T) + A, In(T/100) + S(B, + B,(T/100) + B,(T/100)) ‘T= temperature (Kelvin) 'S= salinity (parts per thousand) wees Testing the model a All models are fiction unless tested or calibrated a Two tests a North Sea Tertiary 2 Seepage associated with pockmark complex 2. Gas log from nearby well log? 2 Can we reproduce gi a Hydrate ridge 2 ODP data 2 Lot of microbiology work (global warming) a Can we reproduce gas generation rates? Baxi000 412Biogenic Gas Generation & Migration Processes wean! North Sea: 15/25 pockmark complex Witer pth sy \ fA $s hy - : we Witeh Ground Fm. . Re coef (Coal Pit Fm, Boomer profile wpeee Hordaland/Nordland Group Sediments Upper Eocene -Pliovene (c. 5-40 Ma) Gas seeps Shallow marine deposition Minor coals Dominantly terrestrial organic matter Bulk TOC ~0.5-1% Inssitu flow rates (1990) 0.4 to 0.6 Vhr ©. 27 gas vents, 350 x 250m Individual vents vary, overall flux ? constant Net flux of ¢, 0.44 m*STP/m"/yr 2 Methane 4 >95% (no higher hydrocarbons) a BNC -72810-78.6 %e a 8D. -23810-247 %e a No detectable 4C (> 30 000 years) 2 Carbon dioxide 2 047-1.36% 2 BEC 194 10-34.5 %e BaxI00.0 43Biogenic Gas Generation & Migration Processes wean Model results Fraction of potential/Bacterial efficiency 0 02 04 06 08 10 = 7 me 2 es v.08 3 Subauate geneton i Ieee el re aa Ceneraton ate Ty) ween Modelled gas saturation nent cto ss) z i : ‘1000 : é 00. x00 BGXI000 4sBiogenic Gas Generation & Migration Processes Wwaeee Measured rates of methane generation coca ates Very wide range ~ BUT All measured by inoculation of sediment samples in the laboratory Reflects maximum possible that organisms are capable of tes Not valid if natural environment is 1" 1 > tos OY? starved Methane generation ate tomvanty) Is there a better way? wweee Hydrate ridge, ODP Leg 204 2 Lot of interest related to global warming and hydrate exploration 2 Lot of microbiology 2 Inssitu methane generation rates > Related potential generation rate of individual organisms (0.06 fino ay ‘hase on la neubation) to total cell biomass in setiment 2 “lower end estimate” of 6x10-° nmol/gm/day for bulk sediment (4 samples), [BHT 17°C] ‘Much lower than laboratory estimates (10°) Expected rate if natural ecosystem is starved pt BGxIONO 4sBiogenic Gas Generation & Migration Processes Ween Model vs. measured rates Modelled rate site 1244 a einen astninte \ x XX ‘Seems to confirm that methanogens are starved Colwell et a, ‘minimum bulk rate @aee Comparison with Blake Ridge Higher rates at Blake Ridge = i higher TOC near surface ==> (300m) ~ similar TOC below this, | higher geothermal gradient hole goes deeper BGXION0 4.16Biogenic Gas Generation & Migration Processes Weee Biogenix software Tetanae mrttennno ree te, Pets et pe mesma WEE Sadie ban Ses, Eber Eaieon = eS eee in nents ieee et se aroun +" gost mien ncn ro wees Numerous input options Data Input and options eeaanine 1s Ero Eee eae ap 00) om rane eptiooe sai progr tng = cane prey roan ea gronaree OC a con pa ne = ‘se Sarena mee (VN) Sis rose a f pt btes TOY? == sat ode renemets m rterontrecrn ty CE] agen tases FE 4 2 van sys |" Can inp bared TOC Sr ealculte this neocon be ee et nytt rate “tet ned Caton he he BoxI009 407We Biogenix status a Current version is v3.1.2 a Available in house in Bogota a Version 3.2 in preparation a Beta version available a needs final testing 4 can select depth range to model a wider range of lithologies 4 better pressure modelling a slightly modified volumetrics 3 modified interface enhanced graphies a Needs final addition 2 Output page for input into Zetaware’s Trinity 2 Discussions under way over format 418 Biogenic Gas Generation & Migration Processes WaeIee Basic parameters can also be changed == BsBiogenic Gas Generation & Migration Processes Exercise 2 - Angostino-Porto Garibaldi Gas Field, Po Valley, Italy In this exercise we will us the Biogenix program to look at the generation profile in one of the Porto Garibaldi wells. You are provided with the following information: 1. Simplified summary of stratigraphy and average TOC data for each interval TOC. 2. Temperature data for this and nearby fields from which to determine the average geothermal gradient. |<) s? 3. Pliocene burial history diagram for the near by Gallare 4 well from which to determine average \ Vv |g sedimentation rate. The well is located offshore in 5m of water. Sea water salinity is maintained throughout the sediment column (i. salinity gradient = 0). Use the hybrid bacterial model Questions 1. At what depth would you expect the maximum gas concentrations? (2109 4 or? STP /mn? roc) 2, What maximum gas saturations are reached in the pore spaces? &y? 9.9 “/+ ef pore spoces my ea 00 2° Soo ck 3. AM um depth, how much free gas is present in Ikm! of sediment (Iscf = 0.0283m')? 9,0. 27 ogee oe 190 ket] we Play around With Some of the option on the Main Input page to get a feel for how different inputs affect the results. For example, how do things change with a higher geothermal gradient, or if the sequence were all at hydrostatic pressure? Oey lect = Free ges = Sm /m 20054 —-G, 01D} @ 36 0' 009.0, | 65/ 4 i ‘ Ka? 109m? 0,0060 (0,001) = 94G0' 0 2 45/ Nis" < 138 5 109m? 2h, 8 x10"scF $0 bef. Exercise 2Exercise 2 Depth below sea floor % TOC in shales Recent change of scale 0.8 0.8 0.6 Middle-Late Pliocene 0.8 0.6 v e & g 12 a ui Biogenic Gas Generation & Migration Processes [EEE] song sik E==] Silty shale Organic matter type II/Ill 0.2% Type III TOC in all sand intervalsBiogenic Gas Generation & Migration Processes Background information Production of biogenic gas in the Po Valley is from deep water turbidites, deposited during the Plio-Pleistocen the Alpine foredeep. Deeper thermogenic gases are produced from Mesozoic strata and locally some mixing occurs. In this tectonic setting, the Plio-Pleistocene basin has a characteristically high sedimentation rate and low geothermal found as deep as 4,600m (Antonello field). gradient so biogenic ga: Source rocks are redeposited muds within the turbidite sequence. Associated hemipelagic deposits have only about 20% of the TOC terrestrial and 20% marine organic matter although the TOC distributions have been simplified somewhat for the benefit of this exercise. The gases are sealed intraformationally, often by very thin mudstone cap rocks ( Cretaceous |" Fiore FCT Jurassic Get Tema snr una Northern Apennine Foreiand (Po Basin) avers voneceee omen _ RAVENNA PORTO CORSM PORTO GARISALON @) rover were — am rower iene — EF 46, Exercise 2Exercise 2 Depth (m) 500 1000 1500 2000 2500 3000 3500 4500 5000 Biogenic Gas Generation & Migration Processes Porto Costin W. . \, Porto Ganibatai = Dosso degli Ange “Mt . ‘Anemone ‘Antonella gb . ‘Antonella -+ + 10 2 30 40 S50 60 70 80 ‘Temperature (°C) 3Biogenic Gas Generation & Migration Processes Time (Myop) 10 3 1000 = 3 3 oo 1500 g 200 ? é 20 3 Exercise 2Biogenic Gas Generation & Migration Processes ween 5. Expulsion and migration a How does gas get out of source? a Does it go up or down? a How much is lost during migration? Waeeet Principles of migration - basics a Need a minimum gas saturation for migration to occur 2 Gas-filled pores must be interconnected 2 Theoretical minimum is about 10% saturation 4 Based on close packed spheres a. True value may be a bit higher in mudrocks 4 Greater tortuosity of pore network 4 Poorly constrained experimentally a Only 2-3% gas saturation required for seismic response Baxi00.0 stBiogenic Gas Generation & Migration Processes waeeet Principles of migration - directions ao Need a minimum gas saturation for migration to occur 2 Gas-filled pores must be interconnected 2 Theoretical minimum is about 10% saturation 4 Based on close packed spheres a True value may be a bit higher in mudrocks 4 Greater tortuosity of pore network ed experimentally 2 Only 2-3% gas saturation required for seismic response 4 Poorly constra a Gas will migrate in response to a gradient in fluid potential a Not necessarily a pressure gradient 4 Although t tay help in hydrodynamic environments a Gas potential depends on: a Water potential 2 Buoyancy 2. Capillary potential wees Fluid potential emer deny Fluids move from regions of ale a high fluid potential to regions For water: of lower fluid potential rae = P -PeBe" =U N.B. NOT high pressure to low pore “overpressure pemanire pressure hydrostatic copay resistance pressure ayneoep , For gas: BGXIO0O ©, = ©, ~ pyge + 2y/1C058 g buoyancy SAP oc ange 4) potential % (@) I rock is water-wet, = 0°, coyps= | 52Biogenic Gas Generation & Migration Processes Waee Buoyancy (P,) ®, i wy Oe* 2y/r.cosB In the absence of overpressure gradients (A, = 0) and a homogeneous lithology (A®.= 0) migration force will be vertically upwards or vertical vector of this if carrier bed is tilted Magnitude of force depends on z, the column height Need a minimum height of continuous gas phase to squeeze out of pores through narrower pore throats Calculations suggest em scale icrieal peeaariGtceriporersiriinihimiaoned % ween Capillary potential (®,) 5 = Pw PgB2 + 2y/ncosp a Depends on: 2 Interfacial tension between gas and water, y 2 Aten a Contact angle 6 2 =O irpores are water wet a Pore throat radius, r 2 Inverse relationship ‘288 composition) 4 Smaller pores give g 4 Can influence expulsion in fining coarsening sequences BGxI000 33 ABiogenic Gas Generation & Migration Processes wees Overpressure (P,) jas ®, ~@)- p.g2 + 2y/rcosp Overpressure: 2 Often referred to as the water potential: &, =P-p,gz=U 2 Builds up in shales 2 Dissipated in permeable beds 9 lateral pressure transmission 2 influences: 2 primary expulsion depth 2 sealing efficiency 2 compaction 2 pars hydrostatic 9.81°108 Pam 0433 psiift Waa Causes of overpressure a Compaction disequilibrium 2. Shales deposited too fast to de-water a Kerogen conversion (()-20)%» of above per 1 vols TOC) 2 Not relevant for biogenic gas! a Aquathermal expansion (« |()" compaction effect) a Clay diagenesis (c. 1% compaction effect except in rare cases) 2 eg. smectite > illite BaxI000 sfBiogenic Gas Generation & Migration Processes ween F {fect of deposition rate on overpressure Pure shale sequence 2000 Depth (m) g 4000 5000 $ sed. rate m/Ma jp >> op 250 6000 T T T T + 0 10-20 30 40 50 60 Overpressure (MPa) wees Lateral pressure transmission surface Low OP High OP Overpressure 2 builds up in shales a dispersed in sandstones aaxt000 55Biogenic Gas Generation & Migration Processes: weet | ateral pressure transmission - effects sense overpressure Isolated horizontal sandstone normally pressured sandstone pressure communication updip pressure communication downdip BGxI000 56Biogenic Gas Generation & Migration Processes ween! North Sea Brent province Overpressure (MPa) 0 1 2 3 4 50 6 = & & Modelled OP Isolated horizontal sands GE Allincommunication - sealed in Hydrostatic - all connected to sea floor All connected to sands dows dip Wwaeee Downwards gas expulsion pore pressure geneous shale’ buoyancy exceeds overpressure gradient —* upwards expulsion Y bed inp overpressure grant execeds buoyancy commmnication = downwards expulsion ‘pdp Limit: ~100m for gas aaxi000 57Biogenic Gas Generation & Migration Processes ween Ideal closed system low «————————__ pore pressure ——————————> high upsip equal «overpressure, ———————— equal. 7ysPncin high «<——_———_——__telative overpressure |——————+ low weaeee Secondary migration principles No overpressure to worry about For gas to migrate: ia capillary resistance (0, — 2,)gh > 2y|— OD crag ny 3 id. Zone oeson 1 so yj | ose Toe t - buoyancy (bu PB (oe pa).g.h Rearranged: h> Need a minimum height of gas to force it through the pore throats Same as expulsion from source interval Bax1000 58Biogenic Gas Generation & Migration Processes ween Heights of petroleum (m) for vertical migration Petroleum density Pore radius (m) kgm) 10° mm) 100.1 mm) 10540 um) 200 0004 038 3.75 300 0.04 043 429 400 005 050 500 500 0.06 0.60 6.00 600 0.08 oa 7.50 700 0.10 1.00 100 800 os 150 150 64. = 1000 kam? ry wweawee Implications Baxs0n0 For a typical gas, must be in the order of Sm to invade 10u pores but to invade pores of radius | mm, only 5 mm is required This indicates that gas must migrate as a series of stringers of significant height, rather than as discrete bubbles Gas will invade widest pore network first, then divert if it suddenly reaches narrow throats, leading to a dendritic network, and isolated abandoned stringers This will lead to migration losses... 39Biogenic Gas Generation & Migration Processes Wwaeeae Migration losses 2 Poorly constrained for gas a Foroil: 2 Volumetric calculations suggest that losses are typically in the order of about 2% of the total pore volume of the carrier bed for siliciclastic beds (13%) 2 Decreases to perhaps only 0.5% for limestones 2 May beas high as 10% for karstified sediments although these estimates are poorly constrained by data. wpapees Rationalisation a Two scales of focussing a field studies suggest flowing petroleum is focussed into coarser sand bodies 4 typically about 10% ofthe total sand body 2 experimental core studies suggest about 20% of the pores occupied by petroleum a 10% x 20% = 2% 2 Carbonates may incur smaller losses because they have a wider range of pore sizes at a given locality and interconnected large pores (such as vuggy pores) occupy a smaller fraction of the total pore space 2 Karstification may create a narrower interconnected pore size distribution so high saturations are achieved. For gas, losses are PROBABLY smaller BUT augmented by solubility loses in ier BaxIon0 5.10Biogenic Gas Generation & Migration Processes wees Lateral or vertical migration a Vertical migration is promoted by 2 thick mudstone sequences 2 high sedimentation rates 2 active faulting 2 fault displacements >half sandstone thickness a Lateral migration is promoted by 2 continuous tilted stratigraphy a salt sheets 2 low sedimentation rates or regional hiatus a. little faulting or small displacements wees Hydrodynamics Gas volumes exsolved a Methane is highly soluble in water 2 Significant hydrodynamic effect on migration a Solubility increases at high pressure 2 Water flow to shallower depth (discharge) will exsolve gas «Particularly in orton a 2 Uplift (basin inversion) will exsolve gas ater iniially saturated at 200m, Probably contributory to West Siberia deposits 00 05 10 15 20 29 30 35 40 Exsoived volume ee STPee) aGx1000 suBiogenic Gas Generation & Migration Processes ween Western Siberia Messoyakha Aretik Gatch Yamburg Medvezh’ye 170tet 54.7 tet Zapolyarnoye 94.1 te Gubkin 125 tcf et Komosol 16.2 tef ‘Vengapur Vengayakha 103 tef ier Total reserves >770 tof weapee Western Siberia BGxIONO Large intracratonic basin Neocomian contains gas/oil/condensate Cenomanian ~ nearly all dry gas a Some 2derived from oil biodegradation 4 Recorts of dead oil in reservoir (Rovenskaya & Nemchenko, 1992) discussed later a No such evidence in most fields 4 Appear to be perfectly normal biogenic gas Reserves > 770 tef recoverable Why so huge? 52Biogenic Gas Generation & Migration Processes wawee VW. Siberia gases ° . 20 1000 +0 ae a 40 = ae . i =n = ™ 2-50 é £2000 z é 1 8 . £ . 3000 “ %5 100 . 4000 ao “0 "30" "20 8°C of methane waee West Siberia - palaecogeography 2 Cenomanian reservoir 2 coastal sediments alternating sand, shale and lignite 2 rapid transgression-regression cycles 2 Source rocks 2 Pokur Suite coals a Cenomanian burial 50m/my 2 estimated to have generated 500 tm (17,700 tef) a 20x discovered a Seal a thick Turonian shales BGxI000 513Biogenic Gas Generation & Migration Processes: ween Hydrology Geohistory Model Urengoy Area Note Miocene inversion Hydrology not thought to have changed appreciably since pre-uplift Uplift will cause exsolution of gas Slutty of methane gf) “oO mo © Temperatre(C) 8 8 Calculated volumes sufficient to fill Urengoy BaxI000 SiBiogenic Gas Generation & Migration Processes ween Urengoy Baxt0n0 low pem bare pone But still not easy to develop!Biogenic Gas Generation & Migration Processes Exercise 3 - Timing of biogenic gas migration wn example from the Black Sea coast to investigate when biogenic gas may have been In this exercise we will us expelled from the source rock. All relevant data are shown on the attached figure. Procedure 1. Construct a Bioogenix model for the situation at the End of the Eocene, You will find it helpful to paste some of the resulting figures into Powerpoint to compare with the results from stages 2 & 3. 2. Now modify your model for the situation at the end of the Oligocene, For this you will need to input a customised burial history. Again, copy the results to Powerpoint 3. Finally, modify your model to the present day situation. When do you think the sandstones were charged? Exercise 3500 4 1000 Depth (m) Exercise 3 Age (My) CL NEOGENE silts OLIGOCENE black shales 5] tse oe HI =/200) on tt limestone [Biogenic Gus Generation & Migration Processes Water depth/btm temperature Present day 0m/9°C Oligocene 200m/18°C Eocene 500m/15°C Geothermal gradient 28.3°C/km conglomerate band LWR EOCENE maris CRETACEOUS 4° MIDDLE-UPPER EOCENE marls with sandstones 0% Av TOC in marls 1.58% oe © Kengers hyo * -Biogenic Gas Generation & Migration Processes waeent 6. Unconventional biogenic gases a Solution gas a Secondary biogenic gas a Biodegraded oils a Coal bed methane a Gas hydrates Wwweee Solution gas a Methane has an appreciable solubility in water a Numerous examples of Commercial deposits produced as solution gases a Mostly small a Sometimes significant a Gas yield depends on: a Pressure a Temperature a Salinity aox1000 61Biogenic Gas Generation & Migration Processes ween Methane solubility Temperature “C Wee Suiydsci-ten’nengasu - Japan a All produced (initially) as solution gas a Previously 92% of gas production in Japan a Nigata gas field, North-western Honshii 2 600km? 2 10.5x10° » (37 bet) a Kant6 region, Tokyo 2 1000 km? 2 85,7810? m? (3 tet) a Reservoirs Recent-Miocene in age a Dominantly Plio-Pleistocene a Marine/lagoonal facies a >90% CHy, 5% CO, + N; (up to 40% in marginal regions) a Ethane < 0.04% in most cases BaXI000 62Biogenic Gas Generation & Migration Processes Wwweae Suiy dsci-ten’nengasu — Kanté gas region a Dissolved gas in Kazusa group seds Early Pliocene-Early Pleistocene 2 Thick marine sequence (2800m) 2 Fairly deep ocean basin a Sands silt and shales a Present in dense brines a Production started 1931 2 >300 wells by 1940 2 Down to 400m 2 Rotary drilling introduced 1939 2 Wells now reach 2000+ m 2 Gas sourced indigenously 2 in argillaceous units 2 d55C CH, -66 to -70% a Initial GWR ~ 3m3/m> a Reached >100 m'/m? during production 2 Depletion drive gives rise to gas cap: Wwaeee Suiy dsei-ten’nengasu — Kanté gas region a Dissolved gas in Kazusa group seds 2. present in dense brines a Strong meteoric water flow 2. fresh water cap 2 dense brine found in synclines! a Iodine important by-product BGxI000 63Biogenic Gas Generation & Migration Processes wean Secondary biogenic gas 7 Wi aio 2 Oils reservoired at < ~70°C prone to i | biodegradation | NTT 2 Aerobic degradation most destructive isons, a Also involve Sulphate reducing bacteria | . - es a By products include CO, and short chain Hisar. ~ fatty acids tl | 2 Amenable to methanogenesis in | A microenvironments ie ie 2 Secondary biogenic methane (Npuuldlin.”"* wer AC,,H,, + 30H,O > 49CH, + 15CO, | s6=-159660 K* NH,* PO,* Co Nil Peers — t+ Ta] oman das fommncul dupes, +H.) beogenmatuation [Biomass + CH, +O, ween Isotopic effect — North Sea gases Biodegradation 2 Dominantly CO, reduction 5 2 Results in Rayleigh effect 1 2 Residual CO, gets heavier as CH, gets lighter 5 wCCO, $5 50-45-4035 30-25 °C methane BGxI000 otBiogenic Gas Generation & Migration Processes ween! Process can be modelled CO, conversion to methane leaves residual CO, enriched in "C (Rayleigh fractionation) Ween West Siberia gases 3000 % % 100 methane 4000 ‘a0 Ta de goo) Some of Cenomanian gases in W Siberia may also be secondary gas : oes og. Messoyaka, Russkoye, Taz. All have degraded oil coating to detrital grains (API 17-19°) 2 Carbon isotope range -47.9 to 50.9% Distinctly different to other Cenoma n gas deposits 2 No traces of oil 4 Isotopically lighter BGx100.0 65Blogente Gas Generation & Migration Processes wees Coal bed methane a Many coals contain original thermogenic gas a Some contain early biogenic gas a Others appear to contain secondary biogenic gas a Sydney Basin, Australia a Work by CSIRO 2 Illionois Basin, USA 4 Work by ConocoPhillips a Recent attempts to enhance microbial 400 “300 "200 00 0 processes to increase yield SOCH yest ween Sydney Basin High-low volatile bituminous coals Mixing of biogenic gas with original thermogenic gas C2.% 68 24 1012 ry 9 ‘optimal tp for most methanogens ~38°c Boe So ° wet gas ° q Biogenic contribution confined to low temperature "°F BGXI000 66Biogenic Gas Generation & Migration Processes weaeet Sydney Basin cross section Meteoric water i Poogerc __ Thernagens Late-Early Permian ale Ferman coo measixes ‘Sowleg crna! ory Highest biogenic contribution found in recharge areas csr1.ct wawen Sydney Basin — CSIRO model Infiltration of meteoric water Introduction of igneous CO, (8) tate crinceo Late Cretaceous inversion Partial leakage of gas Original burial Generation of thermogenic gases Baxi000 67Biogenic Gas Generation & Migration Processes wees Illinovis Basin ILLINOIS ; INDIANA. wweee Isotopic ratios Balk of methane cle Derived fi Bax100.0 68Biogenic Gas Generation & Migration Processes Ween Microbial contribution More microbial CH, wea@ee Proposed degradation scheme © ‘ot polyaromates"” oe acetate ‘of carboxylic acids) ‘COOK of Sitroptic acetate ‘nda |, £0, ue Gy ; methanoge! oor, \ ; aw cil degradation”* Bax1000 9Biogenic Gas Generation & Migration Processes @ee8e Geological model me CENOZOIC Temp 8! [Paleogene INeo. Pleistocene Holocene | | Microbial a |CHy Depth 1.5 domly Duo -10 ler) 29) "mM ire 0.3km 15M 0.1km ‘Age 320 100 19 1 ot oot 0.001Ma ewes Gas hydrates a Also termed clathrates a Gas retained in ice-like solid crystal matrix a Cage-like structure retains gas inside 2 Different structures occlude different gases a Stable at high pressure and low temperature a Common on outer continental slopes and rises a Under permafrost regions a ex. West Siberia a Considerable interest a Vast potential resource a Drilling hazard 2 Global warming 2 May destabilise hydrates 42 Feedback loop since CH, is a greenhou aax100.0 610Ween Structures a Cage like structure a Three main structures known a Possibly more to be discovered a Type I (sI) most common (>95%) 2 Body a Can accommodate small molecules only 1 CH, Cally COs. HS et tered cubic Biogenic Gas Generation & Migration Processes a Accounts for nearly all biogenic gas hydrates a Type Il (SII) a Diamond lattice structure 2 Also accommodates propane and isobutane Type H (sH) 2 Can include higher hydrocarbons e 2 May be orange/tan coloured ween Hydration number a Water:gas ratio a sl about 5.75 a ~150m? CH,/m hydrate a Vastly higher than CH, solubility 2 0.045 viv at STP a Stable when lattice > 90% full 1 " 4 ne ge “8 628 ue eastysne(A) 995450, saver aous7 gesoeoccted 1a C2 wet wwwese 1 " H hhyraton No 575, S67 ser eawtysz0A) 895438 aovars aos ieee cece Hace wet woes. a Need anomalously high gas concentrations to form as of gas seepage intensive local biogenic methane production Bax100.0Biogenic Gas Generation & Migration Processes ween Morphology and size a Solid massive hydrates quite rare a Usually isolated nodules and occasional layers a Pore saturations usually low a Often a few percent a Sometimes up to 30-40% a Hydrate zone much thicker a Typically 1-30m a Lateral range a Often many 100s meters 2 sometimes kms wean Stability a0 : 000 HYDRATES STABLE - sooo E z : = seo 1 tee i ‘extrapolated — 3 2e00 & Engozes & site a fi Better |, Stan pie wate a 5 0 6 © 2% ‘Temperature (©) May intersect sea floor BOXT000 100. 204 [=] Presenter 04] Prat zone n-26) 70] El wien Fo i - je 7a 2. 0 od TOO oO ‘Assumed mnenu dentin Need high pressure/low temperature © ‘ vip z 0 — 5 i 10 we : : q i i de 2 E 0 ne i 500 “Temperate ©)Biogenic Gas Generation & Migration Processes ween Hydrates at sea floor 6000 000 - Most natural hydrates well Pot whhin stability 000 4000 & . —_Implies that hydrates do not é 3 ccupy entire stability zone g 3 occupy y ® 000 § 3 2 lust be gas-limites 8 ® Must be gas-limited i : 2000 F 1000 Temperature (©) BGx1000 osBiogenic Gas Generation & Migration Processes wwa@ee Structure stabilised by other components x o wo f. : j : | B10. : i : i j ™ After Sloan (1998) Ww. T T T a a a0 oa Temperate pin Implies that thermogenic gas hydrates and COyrch gus hydrates will be more stable wae Physical properties Property Seawater Ive st sti Density Tos 0917-092 Na Youngs modulus (268K/10"Pa) 95 B4 (est) BA (est) Poissons ratio: 0.33 053 Bulk Modul (2724) 56 Na Siar modsles (272K) 24 Na Velocity ratio (compsbese) 19s NA Linear thermal expansion (200K, K"') 56.10" 7.10" 2.10" Adiabatic bulk compression (273K, 10"'Pa) 2 14 (est) 14 (ost) Electric resistivity (Sm) 0310-1000 =150 NA Thermal conductivity 056 223 odsn02——sta002 Bax1000 Some properties differ significantly from water and ice Readily spotted on logs and seismic 6MBiogenic Gas Generation & Migration Processes WaaH Seismic response Usually visible as a Bottom Simulating Reflector (BSR) ssw 994 905 997 = Top of hydrate usually indistinet BSR represents base of hydrate zone Polarity reversal due to May be shallower tha arged sediments below hydrate limited waeeet Typical log response CALIPER se Lars NEUTRON at a o "10 ee) jes4m 4 y D R A T E 667m, 19 190 1000 MUD GAS om aGxi00.0 615Biogenic Gas Generation & Migration Processes Wee Rates of formation a Not known in detail a But much theoretical work u Main limiting factor is probably gas supply a Typically form over 10°-10° years a Destruction is geologically instantaneous a Hence worry about global warming BGx100.0 6.16Biogenic Gas Generation & Migration Processes Exercise 4 - Gas seeps from Papua New Guinea ‘The Aure Thrust Belt in Papua New Guinea is a mountainous tropical jungle terrain in which it is impossible to obtain geological and geochemical data by remote sensing or geophysical techniques. In addition, little source rock data have been obtained from outcrop or boreholes. Identification of the petroleum source system in the area therefore depends largely on information gathered from samples of natural petroleum seeps known to the indigenous people. The region is substantially uplifted so no present day generation of oil and gas from source rocks would be expected and any seepage identified is therefore likely to be from accumulations. ‘A total of 34 gas seeps, mostly from block PPL 30, were analysed for chemical composition and stable carbon isotope ratios of the gas components. Selected samples were analysed for the stable deuterium- hydrogen ratios of their methane component. Six of the gas seeps were associated with oils. For 24 of the seeps the associated waters were analysed for their chemical and isotopic composition. These gases are described in detail by Baylis er al, (1997, Marine Geology, 137, 109-120). What is the origin of these gases? Where would you propose taking out an exploration license? Gop s S%C Brogenve seyrerhrs iia, 5 onyance matter | SD below - 20% fo § Localed yn runs: Cony = Assocekd us th Fresh weer Aileollected in erusd bed s. C2 [7 f'"3e. Drogenre OD Ploure - 2407o0 deep water ancrent omamre matles © Salma wales. (o Low CO. ameantrhons Ae Kk cS _ Lh ot e- Thermogenre go? et IBC thermeyene assocaled wr thoil sec a methane 64 \ Orls bonodecsrde J. hssynocla Iron Ly Combom brow o-f brogence gos. _ COL very heavy tsoropic seyebae - Exercise 4 LBiogenic Gas Generation & Migration Processes (wa6210Ay) Mons 0 (vous) aad 01 anne: jw 0 ut Sones BIOS TE pouuuaiep ou - 00s conse coz ror vot a ° 85 ——_oveon prus 306 ve ooze once ae es ez so o €'98—ovesjon pras 306 te oor eee - oor ou Se ° £02 vero pra wos 608 2 ore osse 02. z9e zu ez ro ‘SB oueD}on pas Hot ors (09r 0e- ve zr z 70 esa peqsons 0+ - ‘ eet z : at vo. 1 soe une 326 62 ooze ovat otz: : : Gi ° ° 8 pequons Se6 se ooze oat or. vse 0 ° gi) ueson prs you s0B ce - - 0e- vor est 60 v EB uBDen prus 06 92 oss 09 we. Ty oe 6 20 $25 OuBDIen pry yo.+ seb Sz - - 07: ser om ra ° £98 ve>en pray se $e 0068 over ee: ot vu oe ro EB oueryen pray 506 2 cots ‘oct oe: ear eer a £0 EB oueDen pray S06 ce ose spe ote. se a © tt B18 CUED prus 526 ooze oases 00: of st co ° 838 ueyen pruy $96 02 eunows 086 ozo sze- zor- ve. 1 so zo £99 oueaton prus se6 et cocrt oor : ost w vo ° 82 ouerjon prs 526 at rat 989 : see : vor 80 ° 688 Oueon pr 526 ct 0068 aces : eet : fa st ° 318 veo pra 525 91 overt eee : ee en nm ° %—oueajon pus 25 st oer cots ore: A ra ot 8 54 oueaton pus 525 ot 090 902 Sze zor. cee oe zo Zo Se ouesjon pms 0 + S28 ET ‘002 op ove Por sot 60 10 TSB oueaton prus se 21 zanoxo : : eae ect ca v0 ° pean e611 : oce sz se eo o eos Fea son 526 of z € Fe ut ete eer ° oes 8 6 & o» : zz i : : 526 8 7 3 vse. ee vot soe o ess. og 20n 526 2 : - a : eat zo o ese ag Jon 526 9 : : oer : 61 © o a7 oa Jon 50 : rt : var 9 6 vee oa son a8 : at : eee ot ° re eq son 596 € = : ssi : sot +9. ° zee eq son 526 2 z € esr re : oa ca 6 as ag Jon 526 1 anos yous you sues = zo ena apuow —_uimpos at oem pete mN% = r0D% =a 19% sys uorDone9 aly dons “odes Exercise 4Biogenic Gas Generation & Migration Processes (Owen Stanloy ‘obduction zone Papuan foreland Ausvatia Exercise 4 3Exercise ¢ 8D of methane (per mil) 8'°C of carbon dioxide (per mil) Biogenic Gas Generation & Migration Processes erm 8!°C of methane (per mil) [2 sw jet uw? Flos ou 3 Btu Ch = liyh) lasksprc- — Norma| (st. b= Rayh lsof. 20 30 40 % carbon dioxideBrercise 4 Biogenic Gas Generation & Migration Processes = a 2 2 zB 2 3 S 5 2 § ‘6 rnon-associated ‘gases, cil associated gases 3'3C (per mil) DVT Assoc heh Methane Ethane Propane ButaneBiogenic Gas Generation & Migration Processes 12000 * sea water 10000 -8000 6000 sodium (mg/l) 0 5000 10000 15000 20000 chloride (mg/l) 5'°O water (%e SMOW) 0 5000 40000 15000 20000 chloride (mg/l) Exercise 4 6Biogenic Gas Generation & Migration Processes Sample 31 4 | | Sample 25 a Exercise 4 1Biogenic Gas Generation & Migration Processes waee 7. Course Summary a What have we learnt? a What conclusions can we draw? weawe@et Importance of biogenic gases a > 20% of known gas reserves a Can be huge a eg. Urengoy 286 tcf a Can be as old as Cretaceous a Rare Jurassic examples a Possible Devonian example a likely to be secondary gas a Can be deep a Antonello 4,600m (15,000 ft) a Widespread Baxi00.0 21Biogenic Gas Generation & Migraion Processes wees Microbial ecosystem Methanogens are the end member of a complex microbial community ‘And have a complex biochemisry of their own ween Mechanisms Methanogens (Archaea) are the end member of a complex consortium of microbial processes Two main methanogenic processes operate: 1. Carbon dioxide reduction CO, + 4H, & CH, + 2H,0 2. Acetate fermentation CH,COOH & CH, + CO, Used to be thought that CO, reduction was dominant in marine environment and fermentation was dominant in freshwater environments. Now know that deep gas is dominantly from acetate fermentation BGxI000 72Biogenic Gas Generation & Migration Processes ween Methanogenesis controls a Substrates a CO,/hydrogen or acetate a Other nutrients 2 eg. nitrogen, phosphate er rarely a problem a only need trace concentrations a available locally from a Temperature tolerance a Salinity tolerance a pH tolerance ral diagenesis Wwweee Where does substrate come from? 2 Used to be assumed that other organisms produced CO, and H, 2 Key paper: Wellsbury ef al. (1997) a Heated coastal sediments to ~100°C 2 Stimulated acetate (x 10°) formation which increased methanogenesis 2 Matches profile in cores from Atlantic ocean a Suggested that this is biological acetate generation BUT, sodo some inorganic reactions Parkes er al (2007) repeated experiments using irradiated controls to prove biological origin of acetate Acctte co. hes > ey oh ‘enone coenwisg" Mena” “tomes MS Baxi00.0 73Biogenic Gas Generation & Migration Processes ween Temperature controls a a Optimum temperature around 35-40°C Implies an optimum burial rate/thermal gradient a Too slow: organics reduced before methanogen optimum a Too fast/hot: methanogens cooked before they finish their work tan 1092) Gece ase er wwen Hydrocarbon chemistry of biogenic gas Bax1o00 10 All biogenic gases very dry “ Archaea can only produce methane and traces of ethane/propane under normal ‘circumstances ° 95 350 bs 30 960Biogenic Gas Generation & Migration Process wees Carbon isotope ratio — biogenic methane 120 Glacial drift [Gl Freshwater lakes and swamps Marine sediments 100 60 35°C methane n=544 40 ‘Thermogenic gases 20 0 <95-90 -80 -70 -60 -50 -40 -30 -20 wea@ee Hydrogen isotope ratios - 5D Originally interpreted as fermentation (light) vs CO, reduction (heavy group) But a. Fermentation produces CO, as well as CH, 4 CH,COOH # CH,+ CO, 2 this CO, then reduced 4 partial everprnting of fermentation signal 2 Laboratory labelling studies show that acetate itself can exchange hydrogen droge a ae a) 2 de Grafer a, 196 Eisbon taxiaa section 2 DIH exchange in methyl group Conta, CH, +240 4 probably result ofenzyme complex carbon monoxide a chydrogenase and subsequent methyl group Equilibrium with water detiydrogenation by tewahydromethanopterine o similar ‘Acetate fermentation enzyme CH,COOH CH, +CO; 4 Carbon not affected 2 a ‘8D more likely related to 6D of water Bax100.0 75Biogenic Gas Generation & Migration Processes ween Dealing with mixed gases a All potential source rocks will contain biogenic gas a Adsorbed gas a Dissolved gas a Free gas a Any thermogenic gas will be added to this a Result — expect gases of mixed origin a Strong biogenic component at low maturity Biogenic signature swamped at higher maturity Recognised with various gas interpretation figures epee Texas/Louisiana detail e on acsocate 0 - : i io? st iD 5 : a 4 20 : “0 50 + eters 04 os os o7 os 09 10 apes Bax1000 76wees Schoell diagrams Biogenic Gas Generation & Migration Processes {80 methane 300-250-2002 180-100 ore 8C methane, é wees Chung natural gas plot vn 7 co 2 oe okt eo C-C-C-C-C-C-R ag C-C-C-C-C-R ca C-C-C-C-R c-C-C-R C-C-R ” " 32 b Mass balance: * ONC, = BEC, + G1) dC, ]/n ~ rearranging: on BNC, = Wn ONC, -84C,) +9°C, 46. But assumes isotopic homogeneity of gas precursors Boxt0n0 27 Tsxcene etane methane pentaneBiogenic Gas Generation & Migration Processes Wee Carbon isotope ratios Pleistocene U. Pliocene M. Pliocene L. Pliocene Messinian M. Miocene Cretaceous Jurassic Triassic 8°C methane eee Must also consider biodegradation BM Cey (ed ‘Santa Barbara Basin ‘Methane Concentration (mt) Always worth measuring 8D on biogenie methanes BaxION0 78Biogenic Gas Generation & Migration Processes ween Volumetrics: C/O ratios Organic matter CO, + 4H, % CH, + 2H,0 Carbon:oxygen lost in the atomic ratio 1:2 CH,COOH & CH, + CO, (+41, % CH, + 21,0) Carbon:oxygen lost in the atomic ratio 1:1 % carbon lost CO, reduction —7.4-8.8 Type Il fermentation [OBO CO, reduction 4.9-6.0 ‘Type Ill: fermentation [IS238000) ‘ ef. 27.8% from CIS ratios Toes ses bh S Wweae Reaction kinetics dC “aC is change in concentration of reactive Based on first order reaction: -—«C kerogen dt «tos change in time Rewriting equation; == ic dt kis the rate constant LE defined by Archeniusas: k= Ae ®7 4s feueney factor is atvtion energy pend om peo ands bing rokon If we know A and E we can predict the extent of reaction as a function of time and temperature Kerogen is complex - numerous reactions are involved need a range of activation energies BGxI000 79Biogenic Gas Generation & Migration Processes @eaeee Microbial temperature control 0.60 050 0.30 0.20 ‘lative generation rate (normalised) 010 0.00 Modelled as combination of two normal distributions © Smdepth © romeepth © tamaepth average 10418 armaldtrbuton 1 raimalaetrbuton 2 togener Assumed that at optimum efficiency microbes can convert all available substrate 40 20 3) 4s temperature (°C) Wwaeee Stages of modelling BGxION0 ms Type: How much s reactive? Votumetncs How fasts substrate generated? Substrate kinetics oor much substrate isconverted to methane? ‘Microbial efficiency 710Biogenic Gas Generation & Migration Processes ween Final modelling scheme substrate generation microbial efficiency - Xx { ‘methane generation profile rman ‘Then allow for abetted a 2 disap Wweee Model vs. measured rates a: oe “ tot ton Zz ae — me Modeled ate site 124d _— ee _| , Seems to confirm that methanogens are starved Colwell eta 0 minimum bulk rate aGxio00 zuBiogenic Gas Generation & Migration Processes wean Biogenix software Data input and options roast 06 67 = anny a ig et sync wate wr Cnt ween Principles of migration - directions a Need a minimum gas saturation for migration to occur 2 Gas-filled pores must be interconnected 2 Theoretical minimum is about 10% saturation 2 Based on close packed spheres a True value may be a bit higher in mudrocks 2 Greater tortuosity of pore network Poorly constrained experimentally 2 Only 2 4 gas saturation required for seismic response a Gas will migrate in response to a gradient in fluid potential 2 Not necessarily a pressure gradient 2 Although that may help in hydrodynamic environments a Gas potential depends on: a Water potential 2 Buoyancy 2 Capillary potential Bax100.0 72Biogenic Gas Generation & Migration Processes ween Buoyancy (P,) oa p.87qigay/ r.cosp In the absence of overpressure gradients (A@,,= 0) and a homogeneous lithology (A®,= 0) migration force will be vertically upwards or vertical vector of this if carrier bed is tilted Magnitude of force depends on z, the column height Need a minimum height of continuous gas phase to squeeze out of pores through narrower pore throats Calculations suggest em scale Individual gas bubbles will not migrate out of a fine grained source rock wees Capillary potential (®) gp = Pw PBZ + QP» a Depends on: 2 Interfacial tension between gas and water, 7 4 temperature, gas composition) a Contact angle 6 o>0 4 = Oifpores are wi 2 Pore throat radius, r 4 Inverse relationship 4 Smaller pores give greater b, 4 Can influence expulsion in fining/coarsening 026, sequences 4 only operates over few meters aaxi00.0 213@eaeee Overpressure (P,,) Biogenic Gas Generation & Migration Processes 2, OD rage + Deco pressure Overpressure: 2 Often referred to as the water potential: @,=P—pygz=U lithostatie 2 Builds up in shales 2.27108 Palm _ 1 psilt 2 Dissipated in permeable beds 2 lateral pressure transmission depth hydrostatic 9.81108 Pam 0433 psilft wean Downwards gas expulsion influences: primary expulsion 2 sealing efficiency 2 compaction 2 porosity 2 ga satmation we pore pressure buoyancy exceeds Homogeneous shale: overpressure gradient —* equal ®, upwards expulsion rook v ted in presare commanicaton up dip », ~100m for gas BGXIO00 74 overpressure gradient exceeds buoyaney ‘=> downwards expulsionBiogenic Gas Generation & Migration Processes wwaeee Secondary migration loses a Fora typical gas, /r must be in the order of Sm to invade 10,1 pores but to invade pores of radius 1 mm, only 5 mm is required a This indicates that gas must migrate as a series of stringers of significant height, rather than as discrete bubbles a Gas will invade widest pore network first, then divert if it suddenly reaches narrow throats, leading to a dendritic network, and isolated abandoned stringers a This will lead to migration losses... ween Po Valley — generation/migration model Apennines Alps Po River Z [r= [EB] Biogenic methane Mz [FR] Thermogenicmethane pe: plrplestocene fs] Mio: Miocene Mixed origin @® voesors MZ:Mesozoic BaxI000 75Biogenic Gas Generation & Migration Processes wees Hydrodynamics Gas volumes exsotves a Methane is highly soluble in water ; oe a Significant hydrodynamic effect on Gone = 30cm migration = a Solubility increases at high pressure a Water flow to shallower depth (discharge) will exsolve gas 2 Particularly in foreland basins a Uplift (basin inversion) will exsolve gas wate nally snuratedat 2000m Wee Methane solubility Methane solubiity v/v STP BGxI0N0 716Biogenic Gas Generation & Migration Processes weaeee Suiy dsei-ten’nengasu — Kanto gas region 2 Dissolved gas in Kazusa group seds 2 present in dense brines a Strong meteoric water flow a fresh water cap a dense brine found in synclines! 2 Iodine important by-product wae Hydrology Salut of methane ks) oo 4% 3 0 9 60 7 6 9 100 Temperature) ot ae ‘anaing sear BaGxi00.0 77Biogenic Gas Generation & Migration Processes waeae Secondary biogenic gas 2 Oils reservoired at < ~70°C prone to : a . biodegradation j nae ; F a Aerobic degradation most destructive WigdallUlli. Alassio, 2 Also involve Sulphate reducing bacteria 7 we 2 By products include CO, and short chain Ha eltilllr = 4 ; fatty acids ii Lk ld 2 Amenable to methanogenesis in microcnvironments i el ane Y 4 Secondary biogenic methane li lil al AC, H,, + 30H,0 —* 49CH, + 15C0, | 36-5561 Kt NH," PO.” Co NiJ——_ from mineral hydra Narvents & ace elements +H, ] kerogen maturation ‘ol atomattion from mineral dlagenesis Biomass + CH, + CO, wees Coal bed methane a Many coals contain original thermogenic gas . . 20 a Some contain early biogenic gas _7 a Others appear to contain secondary 2 biogenic gas = a 3 a Sydney Basin, Australia 2 0 1 Work by CSIRO ay 2. Illionois Basin, USA 0 u Work by ConocoPhillips ° ao 0 a Recent attempts to enhance microbial 400 300 "200 100 processes to increase yield BD Chg vaom BGXIONO 78Biogenic Gas Generation & Migration Processes weeee Proposed degradation scheme © ‘ot polyaromatics ‘of carboxylic acids) So! oF cna methanogenesi a ~S demethy anaerobic“ ©: ation” and a ing cleavage tL “oo oll degradation” Ween Geological model Temp &q-~__ [Paleogene|Neo| [Holocene Microbial 60c | i Depth 1.5} | sem'ig Dae 10 | le29 | 17M | 1c 0.3km 1M ~ 0.1km Age 320 100 10 1 ot oo 0.001Ma Bex100.0 719eee Gas hydrates Cage like structure 2 Three main structures known 2 Possibly more to be discovered Type I (sI) most common (>95%) 2 Accounts for nearly all biogenic gas hydrates 2 Body centered cubic 2 Can accommodate small molecules only 4 CH, CH COs HLS et a Type II (sil) a Diamond lattice structure a Also accommodates propane and isobutane a Type H (sH) a Can include higher hydrocarbons a May be orange/tan coloured ween Natural hydrates Pressure (MPa) 1000 10 1s Temperature (6) 2 7.20 cavity ia) snes ocloses 5000 4000 3000 2000 Equivalent water depth (m) Biogenic Gas Generation & Migration Processes ) 1 0 4 “8 ra620 396439 aora7s aoe race wwtoee wires Most natural hydrates well within stability zone Implies that hydrates do not occupy entire stability zone Must be gas-limitedBiogenic Gas Generation & Migration Processes WHaH Seismic response Usually visible as a Bottom Simulating Reflector (BSR) z : i Top of hydrate usually indistinet BSR represents base of hydrate zone Polarity reversal due to gas charged sediments below hydrate May be shallower than expected if system is gas-limited weee Typical log response CALIPER sp lars NEUTRON " m ohm potest) 3 570" coo er [-—| 664m 4 Y D R A T E | © | e67m SONIC MUD GAS smooom om BGx100.0 720Biogenic Gas Generation & Migration Processes wees Source rocks a TOC> 0.5% is adequate to produce free gas -a Marine or freshwater or terrestrial 2 Temperate climate herbaceous vegetation is best 4 —+ cool climate 2 BUT anything will do a Rapid burial 2 Too slow: TOC lost near surface 2 Too quick: not enough time 2 Optimum: instantaneous burial to 40°C 2. Best observed: 200-700 m/my for typical basin waen Key Plays a Deep sea fans a Sedimentation rates are typically very high 2 Geothermal gradients are low 2 Source shales and reservoir sands are intimately associated 2 Organic matter is usually terrestrially dominated a Deltas. a High sedimentation rates 2 Low geothermal gradients 2 Terrestrial organic matter a Coastal Plains. Lower than optimum burial rates but a Very extensive 2 Organic matter terrestrially dominated BGxIO00 7122Biogenic Gas Generation & Migration Processes ween Geological controls of biogenic gas alitt i HERA ween Where next? a Biogenix being upgraded Interface with Trinity 4 Requires simplified algorithm a Microbiology research still ongoing a Expect more surprises a Petroleum industry as a whole now take biogenic gases seriously a Expect competition After that, it’s up to you! Baxi0n0 723Biogenic Gas Generation and Migration Processes 8. References Bakker, R.J. (1998) Improvements in clathrate modelling I: the H,O-CO,-CH,-N,-C,H, fluid system. Jn: Henriet, J.-P. & Mienert, J. (eds) Gas Hydrates: Relevance to World Margin Stability and Climate Change. Geological Society, London, Spec. Publ. 137, 75-105. Baylis, S.A., Cawley, S.J., Clayton, C.J. & Savell, M.A. (1997) The origin of unusual gas seeps from onshore Papua New Guinea. Marine Geology, 137, 109-120. Berner, U. & Faber, E. (1996) Empirical carbon isotope/maturity relationships for gases from algal kerogens and terrestrial organic matter, based on dry, open system pyrolysis. Org Geochem., 24(10/11), 947-55. Braun, R.L., Burnham. A.K. & Reynolds, J.G. (1992) Oil and gas evolution kinetics for oil shale and petroleum source rocks determined frpm pyrolysis-TQMS data at two heating rates. Energy & Fuels, 6, 468-474. Burnham, A.K. & Sweeney, J.J. (1989) A chemical kinetic model of vitrinite maturation and reflectance. Geochim. Cosmochim. Acta, 53, 2649-2657. Chung, H.M., Gormley, J.R. & Squires, R.M. (1988) Origin of gaseous hydrocarbons in subsurface environment: theoretical considerations of carbon isotope distribution. Chem. Geol. 71, 97-103. Clayton, C.J. (1991) Carbon isotope fractionation during natural gas generation from kerogen. Mar. Pet. Geology, 8, 232-240. Clayton, C.J. (1992) Source volumetrics of biogenic gas generation. In: Bacterial Gas (Ed. R. Vially), Editions Technip, Paris, 191-204. Clayton, CJ. (1994) Microbial & Organic Processes. In Parker, A & Sellwood, B.W, eds. Quantitative Diagenesis: Recent Developments and Applications to Reservoir Geology. NATO ASI Series, v.453, 125-160 Coleman, D.D., Risatti, J.B. & Schoell, M. (1981) Fractionation of carbon and hydrogen isotopes by methane-oxidising bacteria. Geochim. Cosmochim. Acta, 45, 1033-1037. Colwell, F.S., Boyd, S., Delwiche, M.E., Reed, D.W., Phelps, T.J. & Newby, D.T. (2008) Estimates of biogenic methane production rates in deep marine sediments at Hydrate Ridge, Cascadia margin. Appl. Environ. Microbiol., 74, 3444-3452. Cramer, B., Poelchau, H.S., Gerling, P., Lopatin, N.V. & Littke, R. (1999) Methane release from groundwater — the source of natural gas accumulations in northern West Siberia. Mar. Petrol. Geol., 16(3), 225-244. BaxI000 arBiogenic Gas Generation and Migration Processes Daniels, L. (1993) Biochemistry of methanogenesis. In: M. Kates, DJ. Kushner & A.T. Matheson (Eds.), The Biochemistry of Archaea (archaebacteria). Elsevier, New York, 41- 112. de Graaf, W., Wellsbury, P., Parkes, R.J. & Cappenberg, T.E. (1996) Comparison of acetate turnover in methanogenic and sulphate reducing sediments by radiolabeling and stabe isotope labelling and by use of specifi inhibitors: evidence for isotopic exchange. Appl. Environ. Microbiol, 62(5), 772-771. Deniau, 1, Behar. F., Largeau, C. De Canniere, P. Beaucaire, C. & Pitsch, H. (2005) Determination of kinetic parameters and simulation of early CO, production from the Boom Clay kerogen under low thermal stress. Appl. Geochem., 20, 2097-2107. EGI (2008) Energy and Geoscience Institute, University of Utah Report 2008-50501574 Grace, J.D. & Hart, G.E. (1986) Giant gas fields of northern West Siberia. AAPG Bull., 70(7), 830-852. Giirgey, K., Philp, P., Clayton, C., Emiroglu, H. & Siyako, M. (2005) Geochemical and isotopic approach to maturity/source/mixing estimations for natural gas and associated condensates in the Thrace Basin, NW Turkey. Appl. Geochem., 20, 2017-37, Hinricks, K.-U., Hayes, J.M., Bach, W., Spivak, A.J., Hmelo, L.R. Holm, N.G. Johnson, C.G. & Sylva, S.P. (2006) Biological formation of ethane and propane in the deep marine subsurface. Proc. Nat. Acad. Sci. USA, 103(40), 14684-14689. James, A.T. (1983) Correlation of natural gas by use of carbon isotopic distribution between hydrocarbon components. Amer. Assoc. Pet. Geol. Bull., 67, 1176-1191 Jones, D.M., Head., 1M., Gray, N.D., Adams, JJ., Rowan, A.K., Aitken, C.M., Bennett, B., Huang, H., Brown, A., Bowler, B.F.J., Oldenberg, T., Erdmann, M. & Larter, $.R. (2008) Crude-oil biodegradation via methanogenesis in subsurface petroleum reservoirs. Nature, 451, 176-180. Knauss, K.G., Copenhaven, S.A. Braun, R.L. & Burnham, A.K. (1997) Hydrous pyrolysis of New Albany and Phosphoria shales: production kinetics of carboxylic acids and light hydrocarbons and interactions between the inorganic and organic chemical systems. Org. Geachem., 27 (7-8), 417-496. Larter, $.R., Head, IM., Huang, H., Bennett, B., Jones, M., Aplin, A.C., Murray, A., Erdmann, M., Wilhelms, A. & Di Primio, R. (2005) Biodegradation, gas destruction and methane generation in deep subsurface petroleum reservoirs: an overview. Proc. 6” Petroleum Geology Conference, Geol Soc. Lomdon, 633-639. Lipp, J.S., Morono, Y., Inagaka, F & Hinrichs, K.-U. (2008) Significant contribution to Archaea to extant biomass in marine subsurface sediments. Nature, 454, 991-994. BGX1000 82Biogentc Gas Generation and Migration Processes Lorant, F., Largeau, C., Behar, F. & De Canniére, P. (2008) Improved kinetic modelling of the early generation of CO, from the Boom Clay kerogen. Implications for simulation of CO, production upon disposal of high activity nuclear waste. Org. Geochem., 39, 1294-1301. Marsden, S.S. & Kawai, K. (1965) “Suiydsei-ten’nengasu”, a special type of Japanese gas deposit. Bull. AAPG, 49(3), 286-295. Mattavelli, L., Ricchiuto, T., Grignani, D. & Schoell, M. (1983) Geochemistry and habitat of natural gases in Po Basin, northern Italy. AAPG Bull., 67(12), 2239-2254, Oremland, R.S. (1981) Microbial formation of ethane in anoxic estuarine sediments. Appl. Environ. Microb., 42(1), 122-129. Parkes, RJ., Wellsbury, P., Mather, LD., Cobb, SJ., Cragg, B.A., Hornibrook, ERC. & Horsfield, B. (2007) Temperature activation of organic matter and minerals during burial has the potential to sustain the deep biosphere over geological timescales. Org. Geochem., 38, 845-52. Parkes, R.J., Wellsbury, P., Mather, LD., Cobb, S.J., Cragg, B.A., Horsefield, B., Hornibrook, ERC & Maxwell, J.R. (2007) Temperature activation of organic matter and minerals during burial sustains the deep biosphere over geological time scales. Org. Geochem., 38, 845-852. Paynter , MJ.B.,& Hungate, R-E. (1968) Characterisation of Methanobacterium mobilis sp. n., isolated from the bovine rumen. L. Bacteriol., 95, 1943-1951. Pepper, A.S. & Corvi, PJ. (1995) Simple kinetic models of petroleum formation, Part III: modelling the open system. Mar. Petrol. Geol., 12, 417-52. Pol, A., Heijmans, K., Harhangi, H, Tedesco, D., Jetten, M.S.M. & den Camp, H.J.M. (2007) Methanotyrophy below pH by a new Verrucomicrobia species. Nature, 450, 874-878. Raisewell, R. & Berner, R.A. (1987) Organic carbon losses during burial and thermal maturation of normal marine shales. Geology, 15, 140-145. Rooney, M.A., Claypool, G.E. & Chung, HM. (1995) Modelling thermogenic gas generation using carbon isotope ratios on natural gas hydrocarbons. Chem. Geol. 126, 219-232. Rovenskaya, A.S. & Nemchenko,N.N. (1992) Prediction of hydrocarbons in the West Siberian Basin. BCREDP, 16, 285-318. Sandu, C. (2003) Time/temperature constraints on the generation of biogenic methane gas in natural gas, Japan. Org. Geochem., 26(5-6), 399-407. Schoell, M. (1980) The hydrogen and carbon isotopic composition of natural gases of various origins. Geochim. Cosmochim. Acta, 44, 649-662. BGx100.0 83Biogenic Gas Generation and Migration Processes Schoell, M. (1983a) Genetic characterisation of natural gases. Amer. Assoc. Pet. Geol. Bull., 67, 2225-2238. Schoell, M. (1983b) Isotope techniques for tracing migration of gases in sedimentary basins. J. geol Soc. London, 140, 415-422. Schonheit, P. 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