08/12/2004

Todays Lecture:
These powerpoint files were produced for the Earth History class at the Free University Berlin, Department of Geological Sciences The copyright for texts, graphical elements, and images lies with C. Heubeck, unless otherwise specified. Download, reproduction and redistribution of theses pages in any form is hereby permitted for private, personal, non-commercial, and class-related purposes use as long as the source is identified. Despite of my efforts, I cannot guarantee the completeness, correctness and actuality of the material. Prof. Christoph Heubeck Institut fr Geologische Wissenschaften Freie Universitt Berlin Malteserstr. 74-100 12249 Berlin GERMANY ph: ++49-(0)30-83870695 cheubeck@zedat.fu-berlin.de fax: ++49-(0)30-83870734 http://userpage.fu-berlin.de/~cheubeck/

Geochemistry, Maturation, and Migration

The origin of petroleum hydrocarbons

Todays Lecture:

The (organic) origin of hydrocarbons Geology of Source Rocks Geochemistry of source rocks; accumulation
and maturation

Note (1): Oil and gas are fundamentally incompatible with the solid and aqueous components of the lithosphere

Chemical composition of hydrocarbons Links and Literature

CaCO3

HCOH

H2O, CO2

Lectures Heubeck Geology FU Berlin

08/12/2004

The origin of petroleum hydrocarbons

The origin of petroleum hydrocarbons

Note (2): Hydrocarbons are a mere transition stage in C cycle: a stage in the strive towards products of lower energy.
Organic ?

Hydrocarbons

Anorganic ?
Deep origin: carbide + water = acetylene (C2H2), subsequent condensation Variation: Association with hydrothermal systems) Cosmic origin: Hadean petroleum rain

Geological association: Associated witth unaltered aquatic (marine, lacustrine) sediments Inferences: Similar to known biotic oils: Whale oil, fish oil Knowledge from mining: Gas and coal closely associated Analysis: Chemically similar to known components of life: proteins, fats, fatty acids Isotopes: Always very light C13

The origin of petroleum hydrocarbons

How much Carbon is there ?

Empirical Associations
marine sediments diatomaceous sediments and anoxic black shales, especially where migration can be shown to be short or nil. origin from phytoplankton (mostly diatoms), zooplankton (radiolaria, planktonic foraminifera etc.).
7.00E+19 6.00E+19 5.00E+19 4.00E+19 3.00E+19 2.00E+19

O2

O2

1.00E+19 0.00E+00 Igneous/mmc C Hydrosphere, biosphere Carbonates Total Organic carbon

Lectures Heubeck Geology FU Berlin

08/12/2004

Where is the organic carbon ?

Todays Lecture:

Dispersed in sedimentary rocks 97.51 % = 11000E15 kg

The (organic) origin of hydrocarbons Geology of Source Rocks Geochemistry of source rocks; accumulation
and maturation

Chemical composition of hydrocarbons

Petroleum in nonreservoir rocks 2.35% = 265 E 15 kg Petroleum in known reservoirs 0.01 % = 1E15 kg In coal and peat 0.13 % = 15E15 kg

Links and Literature

Petroleum accumulation is an extremely inefficient process: Only about 0.01 percent of TOC end up in known reservoirs !

Geology of Source Rocks

Which lithologies may form good source rocks ? Carbonates generally little OM but exceptions ! kerogens from carbonate OM dominantly sapropelic favorable environment for accumulation of HC (high productivity, no bioturbation, density stratification). rapid cementation preserves OM

Sandstones

Source Rock A unit of rock that has generated oil or gas in sufficient quantities to form commercial (migratable, significant) accumulations.
Shales
offshore mud, Chile

are abundant (~65-70% of all

sedimentary rocks)

are dominant in deeper, quiet-water

depositional environments (stagnation) highest initial porosity, highest initial fluid content high compactibility, potential for internal seals

Lectures Heubeck Geology FU Berlin

08/12/2004

Geology of Source Rocks: Shales A rich shaly source rock

is dark (high TOC) is laminated (varves?, benthic fauna absent) contains abundant (micro-)fossils: a primary
organic sediment

is rich in microfractures shows a pronounced fissility is phosphatic (many), uraniferous; commonly

sulfidic

may have common carbonaceous material

(but is not required).
TOC % of rock <0.5 Very poor 0.5 1 Poor 1-2 Fair 2-4 Good 4- -12 Very good > 12 Excellent

Outcrop of Los Monos Fm., old road to Cochabamba near Angostura, Prov. Santa Cruz, Bolivia

Accumulation of Hydrocarbons

Accumulation of Hydrocarbons

What conditions favor the production of plankton ?

cold water high supply of nutrients

What conditions favor the accumulation of plankton ? no vertical mixing, stratification oxygen deficiencies at water bottom warm water

Lectures Heubeck Geology FU Berlin

08/12/2004

What conditions favor the accumulation of plankton ? no vertical mixing, stratification oxygen deficiencies at water bottom warm water

Primary lack of oxygen Due to poorly circulating basin currents

Primary lack of oxygen Due to poorly circulating basin currents

Overwhelming of available normal oxygen levels Due to high organic production (how ? See above)

Primary lack of oxygen Black Sea Sapropel accumulation Stagnant basin

Better preservation !

http://www.npagroup.com/dataservices/imagegallery/blacksea.htm

Overwhelming of available normal oxygen levels Due to high organic production (how ? See above)

California sea-water temperature distribution

Map of Chlorophyll concentration

Upwelling region of cold, nutrient-rich deep water masses off Peru and Ecuador, winter 1979.

Los Angeles Region

http://daac.gsfc.nasa.gov/CAMPAIGN_D OCS/OCDST/ocean_color_from_space. html

http://oceanexplorer.noaa.gov/explorations/02quest/background/upwelling/media/fig2_map.html

Lectures Heubeck Geology FU Berlin

08/12/2004

When and where do good source rocks form ? At times of global oceanic anoxic events (OAEs) associated with sea level rises (transgressions)

When and where do good source rocks form ?

Late Devonian transgression(s): Canada (Exshaw

Shale and others), Wolga-Ural (Domanik Fm.), North Africa, southern US (Woodford Shale)

Jurassic and Cretaceous transgression(s):

Principal source rocks in Middle East, western Siberia, North Sea (Kimmeridgian shale), Venezuela (La Luna Fm.)

Oligo-Miocene transgression: California

(Monterey Fm.), Caucasus, Carpathians, Indonesia

http://odp.pangaea.de/publications/ 165_SR/chap_07/c7_4.htm

http://energy.er.usgs.gov/products/papers/World_oil/AAPG/bulletin/fig_01.htm

Significant Devonian Source Rocks

When and where do good source rocks form ?

Domanik Fm. Exshaw Shale

Woodford Shale

Los Monos Fm.

Lectures Heubeck Geology FU Berlin

08/12/2004

Conversion of OM to Petroleum

Todays Lecture:

How is the organic-rich sediment quickly removed from oxygen?

The (organic) origin of hydrocarbons Geology of Source Rocks Geochemistry of source rocks; accumulation
and maturation Chemical composition of hydrocarbons

Minimize bioturbation Generate anaerobic conditions (quiet, deep water lacking overturn with aerated water) Rapid fall-out (high sedimentation rate but beware of dilution) Prefer fine-grained sediment (lower perm, low in OC)

Links and Literature

http://www.baselinedgsi.com/services/rock-eval.asp

Principal Zone of Thermal Oil and Gas Formation

What happens in the kitchen ?

What happens in the kitchen ?

0 60 120

-50 deg C OM to kerogen (~0-1000 m)

Initial loss Breakdown and thermal cracking Cook-off Phase separation

The Cook (not Alfonso)

t ien rad al g rm the geo / km an Me eg C d 30

50

Temperature (deg C)

60

50 175 deg C kerogen monomers (~1000-6000 m) 2

Bacteria Temperature Time

The Recipe
K = A e (Ea/ RT)
The Kitchen

100

Principal temperature of oil formation 120 4

The Kitchen

150

Principal temperature of gas formation

where K = rate constant A = pre-exponential (frequency) factor, idenpendent of T Ea =activation energy of reaction R = universal gas constant T = Temperature in Kelvin

200

Lectures Heubeck Geology FU Berlin

08/12/2004

Coal to wood; OM to kerogen Dehydrogenation and simultaneous carbonization also in the process of forming coal from wood:
Source Material wood peat lignite bitumious coal anthracite H:C-ratio 1.464 1.308 1.044 0.768 < 0.324

Rank of coals; oil- and gas fields; rock diagenesis

Reflectance, Ro (%) 0.3 0.4 ASTM Brown coal and lignite White (1915) Fuller (1919) Fields of Heavy oils Sandstone Lithology sands generally saturated with fresh water

60 Temperature (deg C)

Subbituminous coal

0.5

Commercial Oil fields

Principal fields Of medium oils

soft sands, continuous and porous fairly continuous and open

120 0.6 0.7 1.0 Medium volatile 1.4 200 Low volatile 1.8 2.6 6.0 Semi-anthracite anthracite No commercial oil fields; gas fields may occur Oil deadline bituminous coal

Principal fields Of oil and gas Oil rare, high grade; gas common

Analogous transformation in the generation of petroleum:

Source Material avg. organisms fats, proteins, carbohydrates pyrobitumen (kerogen) carbon H:C-ratio 1.920 1.680 1.524 0.000

tight with some porous beds

No oil or gas with rare exceptions

Rocks tight and hard

After P.A. Hacquebard and J.R. Donaldson, Can. J. Earth Sci., 1970

Humic vs. Sapropelic OM

Van-Krevelen Diagram
The fundamental Van-Krevelen-Diagram,showing principal evolutionary paths followed by the different maceral groups
2

Sapropelic organic material Humic Organic material

http://www.laubag.de/Presse_Dienst/presse.htm

alginites

1.6

exinite: dinoflagellates, algal tissue, pollen, spores etc.

H:C-ratio

largely of carbohydrate-lignin
composition little protein high in nitrogen low in hydrogen (<5%) derived from terrestrial materials, associated with continental sediments thermal alteration yields gases and solids, little liquids

structureless vegetable mud or

slime

vitrinite

polymerized material of lipid and

protein derivsation

high hydrogen content (> 10%) aquatic sedimentary facies

(marine and lacustrine)

high volatile yieldd thermal alteration yields lipids,

waxes, gases

Inertinite / fusinite

0.2

0.3

0.4

O:C-ratio

Lectures Heubeck Geology FU Berlin

08/12/2004

Lithology of Source Rocks

Depositional Environments of Source Rocks

petroleum oil shales

2 0.7

Marine; zoo- and phytoplankton

1.6

sapropelites peats

1.6 1

Lacustrine, mixed sources

H:C-ratio

H:C-ratio

lignites

1.5

bituminous coals

2.0 VR 4.0 3

2.5

Terrigenous, higher land plants

peats

3.5

anthracites

4 TAI

oil gas
0.2 0.3 0.4

0.10

0.20

0.30

0.40

O:C-ratio

O:C-ratio

Van-Krevelen Diagram
Principal evolutionary paths followed by the different maceral groups

Van-Krevelen Diagram
Geochemistry of some well-known source rocks

2 0.7

2 0.7

1.6 1

1.6 1

H:C-ratio

H:C-ratio

Jurassic, Saudi Arabia

1 1.5

1.5

Eocene, Green River, USA Toarcian, France

2.5 3

2.0 VR 4.0 3

2.5

2.0 VR

Tertiary, Greenland

oil
3.5 4 TAI 0.2 0.3 0.4

4.0 3.5 4 TAI 0.2 0.3 0.4

oil gas

gas

O:C-ratio

O:C-ratio

Lectures Heubeck Geology FU Berlin

08/12/2004

The modified Van-Krevelen Diagram

Oxygen and hydrogen indices for samples from lower Aptian organic-rich horizons (OAE1a; Table T3) plotted on a modified van Krevelen diagram. The characteristics of organic-rich samples from Holes 1207B and 1213B, and from the Aptian at Holes 463 and 866A in the midPacific are also shown. Data for Sites 463 and 866A are compiled from Dean et al. (1981), Mlires et al. (1981), and Baudin et al. (1995). The size of the data points is proportional to organic carbon contents. The lines designated I, II and III represent the evolutionary trends with thermal maturation of the three major kerogen types (Tissot et al., 1974). OI = oxygen index.

Pyrolysis how does it work ?

Up to 550 deg C: HC by cracking: remaining HC generation potential

Ground and decarbonate sample Convert to CO2 by burning in controlled atmosphere

(helium, oxygen)

Detect and measure CO2, HC and oxygenated

components in a mass spectrometer
CO2 released from organic matter during pyrolysis

Free, already generated HC, volatized below 300 deg C

max T in deg C

0m Immature zone

1000

2000

Oil zone Wet gas zone 430 440 450 460 T(C)

3000 0 300 C 600 C

S1

S2

S3

Some typical pyrolysis patterns

Some typical pyrolysis patterns

S2 S2
0m 0m

S1
800 m 1000 Immature zone 1800 m 1000 Immature zone

S1
0 300 C 600 C

2000

Oil zone Wet gas zone 430 440 450 460 T(C) 0 300 C 600 C

2000

Oil zone Wet gas zone 430 440 450 460 T(C)

3000

3000

S3

S3

Lectures Heubeck Geology FU Berlin

08/12/2004

Some typical pyrolysis patterns

Some typical pyrolysis patterns

S1 S1 S2
2140 m 0m Immature zone 0m

1000

S2
2480 m

1000

Immature zone

2000

Oil zone Wet gas zone 430 440 450 460 T(C) 0 300 C 600 C

2000

Oil zone Wet gas zone 430 440 450 460 T(C)

3000 0 300 C 600 C

3000

S3

S3

Some typical pyrolysis patterns

Production Index

S1 : (S1+S2) Production Index PI, the indicator of thermal maturation. S1

0m Immature zone

How much of the available kerogen is available as HCs ?

2770 m

1000

S2
2000 Oil zone Wet gas zone 430 440 450 460 T(C) 0 300 C 600 C 900 C

3000 0 300 C 600 C

S3

S1

S2

S3

Lectures Heubeck Geology FU Berlin

08/12/2004

Hydrogen Index

Indexes

S2 : (S1+S2) Hydrogen Index HI

S2:S3 Indicator of oil vs. gasproneness

How much Hydrogen remains (unoxidized) in the system ?

How oil-prone is the source rock ?

300 C

600 C

900 C

300 C

600 C

900 C

S1

S2

S3

S1

S2

S3

Oxygen Index S1/(S1+S2) maturation.

Other Indicators

LOM - Level of Organic Metamorphism. S3 : (S1+S2) Oxygen Index OI TAI - Thermal Alteration Index. Tmax- degrees C from S2 pyrogram. TTI - Time-Temperature Index.

How dry is the source rock ?

Ro% - Vitrinite Reflectance.

Compute generated volumes, estimate expelled volumes, compare to reservoir volumes

0 300 C 600 C 900 C

S1

S2

S3

Lectures Heubeck Geology FU Berlin

08/12/2004

Basin Analysis

Basin Modeling - A Tool for Exploration Oil and Gas Charge Pressure Prediction temperature formation pressure maturity overpressures generation drilling mudweight prediction expulsion migration direction migration production parameters accumulation fluid properties
http://www.geochemsol.com/

Todays Lecture:
Seal Integrity effective stress hydrofractures seal capacity rock properties

The (organic) origin of hydrocarbons Geology of Source Rocks Geochemistry of source rocks; accumulation
and maturation

Chemical composition of hydrocarbons Links and Literature

Chemical Composition of Hydrocarbons n-Paraffins (Alkanes)

H H C H Gases and Liquids Methane CH4 Ethane C2H6 Propane C3H8 Butane C4H10 Pentane C6H12 H H H H H C C H H H H Toluene H C H H 1-Methylnaphthalene Mostly Liquids Benzol Phenol Toluene H C H Indan
70 60 50 40 30 20 10 0

Chemical Composition; Classification of Crude Oil Waxes

Gasoline H C H C H H
80 100

Aromatics
H C H H

Kerose ne 150 200

Diesel 250 300

Light fuel oil 400

Heavy fuel oil

Tar oil 500 C

100

Normal Paraffins
90

Isoparaffins
Light California Borneo,Trinidad US Gulf Coast Heavy California Mexico, Venezuela, Heavy Middle East

Naphthenes (Cycloparaffins)
West Texas, North Sea, Alberta, Middle East

C C H H

iso-Paraffins
H H H C C H H C H H H C C H H H H

Cyclo-Paraffins

Aromatics

NaphthenoAromatics

Resins

Pennsylvania 0 Michigan, Wyoming

25

50

75

100

Weight % in Crude Oil

Lectures Heubeck Geology FU Berlin

08/12/2004

Chemical Composition of Hydrocarbons

Chemical Composition of Hydrocarbons

Composition of Reservoir Fluids

Typical crude oil fractions

100%

Crude Fraction

Boiling Approximate Point (F) chemical (melting point) composition C1-C2 C3-C6 C5-C10 C11-C12 C13-C17 C18-C25 C26-C38 C38+

8,21 22,57

Uses Fuel gas Bottled fuel gas, solvent Motor fuel, solvent Jet fuel, cracking stock Diesel fuel, furnace fuel Lubricating oil, bunker fuel Lubricating oil, paraffin wax, petroleum jelly Tars, roofing compoundsa, paving asphalts, coke, wood preservatives

80% 56,4

C7+ C6 nC5 iC5 nC4 86,12 92,46 73,19 57,6 iC4 C3 C2 C1 N2 CO2 34,62

Hydrocarbon gas Gasoline Kerosene Light gas oil Heavy gas oil Lubricants and waxes Residuum to 100 100-350 350-450 450-580 580-750 750-950 (approx. 100) 950+ (200+)

60%

40%

20%

0%

G as

G as

O il

sa te

W et

nd en

G as

co

vo la

Chemical Compositions; Viscosity

Composition (in mol% ) of several reservoir fluids
Component or Property CO2 N2 C1 C2 C3 iC4 nC4 iC5 nC5 C6 C7+ GOR (SCF/STB) API Gravity Dry Gas 0,10 2,07 86,12 5,91 3,58 1,72 0,00 0,50 0,00 0,00 0,00 Wet Gas 1,04 0,25 92,46 3,18 1,01 0,28 0,24 0,13 0,08 0,14 0,82 69000 65 Gas Volatile Condensate Oil 2,37 0,31 73,19 7,80 3,55 0,71 1,45 0,64 0,68 1,09 8,21 5965 48,5 1,82 0,24 57,60 7,35 4,21 0,74 2,07 0,53 0,95 1,92 22,57 1465 36,7 Black Oil 0,02 0,34 34,62 4,11 1,01 0,76 0,49 0,43 0,21 1,16 56,40 320 23,6

Literature and Links Links

Viscosity
Lard Peanut Butter Ketchup Chocolate Syrup Molasses Honey M otor Oil (SAE 60) M otor Oil (SAE 40) Maple Syrup Liuhua Oil Corn Oil M otor Oil (SAE 10) Liuhua Oil Ethylene Glycol Blood Water @ 70 degrees F
1 10 100 1000 10000 100000 100000 0

Effective Petroleum Source Rocks of the World: Stratigraphic Distribution and

Controlling Depositional Factors http://energy.er.usgs.gov/products/papers/World_oil/AAPG/Bulletin/

Time-Lapse sequence of worldwide source rock paleogeography, in low quality:

http://www.searchanddiscovery.com/documents/Animator/klemme2.htm

The analytical division of Humble Instruments has under its Application Notes
header a large selection of geochemical texts for the explorationist: http://www.humble-inc.com/indexhgs

http://www.baselinedgsi.com/ is another provider of geochemical analyses to the

industry. Its web page includes a virtual classroom with glossary, charts, samples etc. Highly recommended.
Bateman, 1989

http://www.geochemsol.com is another US-based company with excellent

information under its basin modeling header.

Lectures Heubeck Geology FU Berlin

Bl ac k

ry

til e

oi l

08/12/2004

bungen - Basin Modelling Exercise

There are several software packages available that will help the petroleum geologist to understand nature and timing of migration from the source rock. Among them are:

BasinMod (see http://www.platte.com/ps_suite/bmod/) PetroMod (see http://www.ies.de). A quite functionable basic version of PetroMod can be
downloaded for free.

TEMISPACK (see http://www.beicip.com/html/softwareproducts/temispack/temispack.html) is another competitor by a French company.

Lectures Heubeck Geology FU Berlin