Geol 463.3 Supplementary Notes 463-RWR-3,4.

5
1
GEOL 463.3RWR-3
FORMATION OF PETROLEUM, 1
Recommended sections to read in the textbook:
Chapters 5 and 11 cover the relevant material, but provide more detail than is covered in class.
Both inorganic and organic theories have been suggested to explain the origin of oil and natural
gas. Although some gases (especially CH
4
) and individual components in petroleum may
originate by inorganic processes, the weight of evidence strongly supports an origin in organic
matter produced at and near the earths surface.
Inorganic hypotheses
Cosmic origins?Consolidation of H and C during consolidation of the Earth? Carbonaceous
chondrites and space dust contain hydrocarbonsevidence of primary organic source?
Petroleum should be more widespread in space and time if there was a cosmic source.
Reactions of metal carbides within the Earth?
FeC
2
+ 2H
2
O = C
2
H
2
[acetylene] + Fe(OH)
2
Al
4
C
3
+ 12H
2
O = 3CH
4
+ 4Al(OH)
3
Fischer-Tropsch reaction:
CO
2
+ H
2
= CO + H
2
O, then CO + 3H
2
= CH
4
+ H
2
O
There is no evidence that metal carbides exist in the mantle.
Hydrocarbons in igneous rocks as evidence?Hydrocarbons, including bitumens, can be found
in igneous rocks:
1. In vesicles and inclusions in alkaline igneous rocks (e.g. Arendal, Norway). Origin is
controversial.
2. In thermal aureoles around basic intrusions in sediments. Can be explained by
distillation of kerogen in surrounding sediments due to heat of the intrusionpetroleum
may be incorporated in the igneous rocks as they cool.
3. In weathered and fractured igneous rocks. Normally explained by hydrocarbon
migration into the rocks from a sedimentary (organic) source.
Mantle degassing?Polymerization of inorganic gases such as CH
4
that are produced in the
mantle. It is difficult to produce the range of complex hydrocarbons by polymerization; also
problems of permeability and porosity in lower crust.
Geol 463.3 Supplementary Notes 463-RWR-3,4.5
2
Main problems with inorganic theories of petroleum genesis:
Poor correlation between petroleum and volcanism
Paucity of Precambrian oil
Isotopic evidence favours organic origin
Petroleum is optically active linked to organic origin
Presence of homologous series
Geological association with sedimentary basins
GENERAL MODEL FOR ORIGIN AND MATURATION OF PETROLEUM
(MODIFIED FROM FIG. 4.1 IN HUNT, 1996)
LIFE
(Photosynthesis and
the food chain)
Lipids, proteins,
carbohydrates, etc.
Hydrocarbons
synthesized by
organisms
Bacterial and
chemical action
Kerogen
minor
change
Catagenesis
Diagenesis
Maturation
Light oil
Gases
Methane
Heavy oil
Pyrobitumens
Graphite Metagenesis
50C
200C
25C
PETROLEUM
Geol 463.3 Supplementary Notes 463-RWR-3,4.5
3
GEOL 463.3RWR- 4 and 5
SOURCES AND ENVIRONMENTS OF ORGANIC MATTER
(Which depositional settings produce good source rocks?)
Sources of organic matter
Organic matter may be allochthonous (derived, detrital, washed in) or autochthonous
(produced in the depositional environment).
Allochthonous organic matter
Terrestrial plant and animal debris
Spores and pollen (eolian or waterborne)
Recycled (old) kerogen from sedimentary rocks
Autochthonous organic matter
Phytoplankton (algae, diatoms, etc.) primary C producers by photosynthesis
Zooplankton (copepods, foraminifera, etc.)
Fish (nekton)
Benthos (corals, sponges, etc.)
Bacteria
ORGANIC MATTER (OM) ACCUMULATION IN DIFFERENT
DEPOSITIONAL ENVIRONMENTS
Deserts (< 0.05% OM)
Waxy organic matter
Almost all converted to CO
2
and H
2
O
Almost no source-rock potential (but sandstones in deserts may have high reservoir potential)
Abyssal Ocean Plains (< 0.1% OM)
Pelagic muds and oozes
Oozes may be calcareous (e.g., from coccoliths, foraminifera) or siliceous (e.g., from
diatoms, radiolaria)
In the deepest, central parts of the oceans, bottom waters are undersaturated with respect to
CaCO
3
and amorphous silica: oozes cannot form (shells dissolve); only detrital clays can
accumulate
Most OM produced is consumed in water column and recycled
OM that sinks through the water column to reach the ocean floor may then be consumed by
benthic organisms
Fecal pellets allow rapid delivery of OM to the seabed
Nutrients are not abundant in the central part of the oceans, so primary productivity is often
low
Geol 463.3 Supplementary Notes 463-RWR-3,4.5
4
High Energy Coasts (0.20.5% OM)
Adequate productivity nutrients often supplied from the land; abundant oxygen
Waves and currents may produce coarse sediments
High oxygenation of the permeable sediment can lead to early biodegradation (biological
breakdown of organic matter to CO
2
and water
Low Energy Coasts (0.55% OM)
High productivity
Muds or carbonate muds deposited
Can produce good source material if rate of biogenic decay of OM is not too high
Distal Floodplains and Deltas (0.5 > 10% OM)
Mainly clay sedimentation
Organic matter is mainly terrestrial (produces Type III kerogen)
Yields much coal and gas, but little oil
Silled Basins, Enclosed Seas (< 2 > 10% OM)
High productivity
Clays
Often anoxic
Can produce highly favourable source rocks
Epeiric (Epicontinental) Seas (< 1 - > 10%)
Muddy sediments
Can be very favourable if circulation is restricted
Lakes, Coastal Lagoons (< 1 - > 10%)
Favourable if:
Low clastic input
Clay sedimentation
Stratified waters
Most are not stratified
May be eutrophic (algal blooms)
Coastal Swamps (10 100%)
High vegetation; stagnant
Peat produced (coal + methane)
Geol 463.3 Supplementary Notes 463-RWR-3,4.5
5
PRODUCTION AND ACCUMULATION OF ORGANIC MATTER
Most oil is biological in origin and derived from organic matter in sediments. Marine organic
matter is formed in the photic zone by phytoplankton (primary producers) that fix carbon through
photosynthesis. The highest productivity occurs in the uppermost 50 m of the ocean, declining
with depth as sunlight penetration decreases.
Solar Energy
Sea surface
Photic
(less dense)
Aphotic
(dense)
Phytoplankton (algae) fix carbon photosynthetically
Bacteria, zooplankton and
animals consume organic matter
MOST (90%) OF THE ORGANIC
MATTER AND NUTRIENTS ARE
RECYCLED
Benthic organisms consume OM
About 10% OM
reaches seafloor
Microbial diagenesis
Fecal
material
Most organic matter [C] fixed by photosynthesis in upper 100150 m is recycled in the water
column by passing through the food chain. Phytoplankton (diatoms, algae: primary producers of
OM) are oxidised or eaten by zooplankton. Both types of plankton are then consumed by other
higher organisms. They defecate, producing pellets that contain the indigestible part of the
organic matter. The pellets sink relatively quickly to the bottom, whereas plankton are
commonly degraded in the water column. The organic matter that arrives on the ocean (or lake)
floor can then be consumed by benthic organisms. Only a few percent of the organic matter
produced is buried in sediments, especially in the deepest parts of the oceans.
High organic productivity in the oceans depends mainly on adequate sunlight (for
photosynthesis) and availability of nutrients. In surface waters, sunlight generally is not a
limiting factor except seasonally (winter) at high latitudes. Nutrients (mainly N and P) have a
very heterogeneous distribution in marine waters. The highest concentrations are commonly
found in coastal regions, where they are land-derived (e.g., soil erosion with leaching to rivers),
and in zones of upwelling. Upwellings are present mainly on the western margins of the
Geol 463.3 Supplementary Notes 463-RWR-3,4.5
6
continents (e.g., offshore Peru, Chile, Namibia, etc.), and in areas of oceanic divergence, as for
example in the equatorial Pacific. In polar regions, cold oxygen and nutrient-rich water sinks to
great depths and flow slowly toward low latitudes. In areas with strong prevailing land winds,
that cold water may well up to the surface. The nutrients stimulate phytoplankton growth that, in
turn, sustains an abundance of zooplankton, fish, etc. At such locations, above average
quantities of organic matter may reach the ocean floor.
Simplified setting of a coastal upwelling
On the ocean floor, organic matter will be degraded by microorganisms (mainly bacteria) and
consumed by burrowing organisms. The organisms reduce the organic content of the sediments
because most of the organic matter is digested. Bioturbation may stir up the sediments and allow
exposure to oxygen-bearing bottom water. If the water is stagnant, with little (dysaerobic or
suboxic) or no (anaerobic) oxygen, more organic matter can be preserved.
Coriolis Effect causes surface waters to veer
away from the continent -- allows deeper
nutrient-rich waters to well up
N, P
Organic-rich
muds
Geol 463.3 Supplementary Notes 463-RWR-3,4.5
7
OXIC vs. ANOXIC WATERS
In anaerobic muds, sulphate-reducing bacteria may use much of the organic matter, and
precipitate sulphides (e.g. FeS
2
). If the sediments have little free iron or other metals, more
sulphur will be incorporated in the OM and will eventually be enriched in the oil derived from
such source beds.
In oxygenated waters most OM is
consumed (broken down to CO
2
and H
2
O). Most OM that reaches
the substrate is then destroyed by
benthic organisms, including
microbes.
In oxic waters, OM preservation is
a function of SEDIMENTATION
RATE: with rapid burial, more OM
survives biodegradation.
The OM that survives is usually H-
poortherefore, more GAS
PRONE.
OXIC
ANOXIC
Where the water column is
stratified, the bottom waters may
become depleted in oxygen.
OM sinking into anoxic waters
can be degraded only by
anaerobic microbes: these are less
efficient than aerobic microbes.
More OM survives because of the
lack of biogenic activity. It tends
to be rich in H and lipids, and is
OIL PRONE. The OM
accumulates in laminated (no
bioturbation) black muds and
shales.
Geol 463.3 Supplementary Notes 463-RWR-3,4.5
8
STRATIFICATION in water masses may result from several processes. Surface waters are
generally warmer and less dense than colder bottom waters, only overturning (i.e. exchanging
with bottom waters) when they cool to the same temperature (commonly 4C: maximum density
of water). Tropical waters are often permanently stratified. The water can also develop a
chemical stratification (meromixis), where less saline waters rest upon denser, more saline
waters. This may happen when fresh inflow waters "float" on top of saline waters, but do not
mix with them unless they evaporate to produce the same salinity and density. If the salinity and
density difference is great, this condition may be stable for very long periods (> 10,000 y).
The development of anoxic bottom waters, however, usually results from biological processes in
the water column and sediments that deplete it of oxygen.
CH
2
O + O
2
= CO
2
+ H
2
O
Such reactions are rapid when mediated by microbes. This process can occur in the water
column and on the seabed. As organic matter sinks, oxygen is consumed. If water circulation is
low, resulting from density stratification of the water column, the oxygen will eventually become
exhausted.
A zone of biologically-induced oxygen depletion and anoxicity is common in ocean waters at
depths of a few hundred to 1000 m. Where this zone intersects the continents, the sediments on
the seafloor may underlie anoxic waters, giving high potential for preservation of organic matter.
During periods of high eustatic sea-level, the zone of oxygen depletion may be displaced onto
shallow seas covering the continents (i.e., epeiric and epicontinental seas). This can result in
deposition of favourable source rocks (e.g.. Devonian Bakken Formation shales in
Saskatchewan). Many, but not all, of the worlds best source rocks were formed during marine
transgressions.
Continental shelf
Oxygen minimum
zone
deep
O
2
Oxic
(TOC: <3%)
Oxic
Anoxic
(TOC: 3-10%)
Intense biological activity
Geol 463.3 Supplementary Notes 463-RWR-3,4.5
9
The other setting where stratification plays a major role is in silled marine basins (e.g. modern
Black Sea) and deep stratified lakes (e.g., Lake Tanganyika, in E. Africa).
Simplified setting of Black Sea. The halocline marks the boundary between normal,
oxygenated seawater and the anoxic bottom waters, which have a salinity of about 20 g/l TDS
(total dissolved solids). The sill (Bosphorus) is 27 m below sea level. The sediments on the
floor of the Black Sea contain up to 15% TOC (Total Organic Carbon), making them excellent
potential source rocks. Most of the organic matter derives from plankton.
TO CONCLUDE:
Most oil originates in the organic matter buried in fine-grained sediments clay (shale)
and carbonate mudstones.
For preservation of OM, the rate of generation should exceed the rate of destruction.
Favorable settings are:
Basins with rapid fine-grained sedimentation in regions of moderate to high productivity;
Restricted basins with slow fine-grained sedimentation, but with bottom water (and
sediment) anoxicity.
Restricted marine (and lacustrine) basins mainly have planktonic organic matter that is oil-prone
or sapropelic.
Sites of rapid clay sedimentation are found on continental shelves, especially near sites of deltaic
sediment influx. The organic matter, however, is often derived from terrestrial plants (humic),
and may produce more gas than oil.
Transgressive cycles are more important than regressive cycles in making good source
rocks.
Please READ PAGES 111-124 in Hunt (1996) for more details.
SILL
ANOXIC
OXIC
HALOCLINE
H
2
S CH
4