Presentation on

BIOLOGICAL AND GEOCHEMICAL

FACTORS INFLUENCING THE
ACCUMULATION OF PETROLEUM
BASIC COMPONENTS OF ORGANIC
MATTER IN SEDIMENTS
• PROTEINS
• CARBOHYDRATES
• LIPIDS (Fats)
• LIGNIN

All of these + Time + Temperature +

Pressure = KEROGEN
 Organic Matter
• When an organism (plant or animal) dies, it is normally
oxidized

• Under exceptional conditions:

conditions: organic matter is buried and
preserved in sediments

• The composition of the organic matter strongly influences

whether the organic matter can produce coal, oil or gas.
gas.

• The bacteria play some part in the formation of petroleum, but

their role probably does not extend beyond modifying the OM.
OM.
phytoplanktons
 Where the organic matter can become mature, not all of it becomes
petroleum.
In a typical case a normal marine shale with only 1% original organic matter
will have less than a third of it converted to the hydrocarbon molecules that
make up oil and natural gas
The rest remains behind as an insoluble organic residue
Formation and Preservation of Organic
Matter
suggested that the original source material of petroleum is
organic matter formed at the earth's surface.
The process begins with photosynthesis, in which plants, in
the presence of sunlight, convert water and CO2 into
glucose, water &O2:
(6CO2 + 12H2O = C6H6O6 + 6H2O + 6O2).

Glucose is the starting material for the synthesis of more
complex polysaccharides and other organic compounds,
either in plants or the animals that eat them.

This can occur through plant and animal
respiration, or through oxidation and bacterial decay
when organisms die.
 In the open ocean, zones of high productivity occur at high
latitudes of about
60°north and south and along the equator.
These are regions in which cold, vertically moving
ocean currents bring nutrients and dissolved oxygen
from the deep ocean back up to the surface.
Productivity is very high in the shallow waters over the
continental shelves, particularly where large rivers enter the
ocean and supply abundant nutrients.
Also productivity is high in quiet water or low energy
environments.
These low energy environments are usually found in oceans
& lakes
Consequently, organic matter is found mostly in fine-grained
rocks (shale & lime mud).
Preservation and Organic Productivity

The main producers are phytoplankton

(diatoms, dinoflagellates & blue-green
algae) & Bottom-dwelling algae.

Phytoplankton are at the bottom of the

food chain. Their distribution controls
the animal forms such as the
microscopic zooplankton and higher
animal life, all of these contribute to the
biomass.
 amount of organic matter, about 1 part in 1000,
escapes recycling and is buried. Over geologic
time, this small influx has produced vast quantities
of fossil organic material

However, most of this material is widely

dispersed within the sedimentary column.
Only about one CO2 molecule out of every million
initially taken up by photosynthesis is eventually
converted into economically exploitable oil, natural
gas or coal.
 major groups of organic compounds or biopolymers that are
biologically synthesized by plants & animals ------

Carbohydrates occur in both animals & plants & include simple

sugars such as glucose & their complex polymers like cellulose &
starch.

Proteins are found largely in animals & to a lesser extent plants.

Lignin is built up of high molecular weight aromatic carbon rings &
occurs only in the higher land plants.

Lipids occur in both plants & animals. They are insoluble

compounds that include the fats, oils & waxes & are the major
source materials for the formation of liquid hydrocarbons.
Figure shows how during early diagenesis, the complex biopolymers
are broken down into smaller, simpler molecules, called
geomonomers.

The end product of the diagenesis
of organic matter is kerogen.

Kerogen is defined as the organic

material in sedimentary rocks that is
insoluble in organic solvents.
 Keroge Origin Organic
n Type Constituents

I Algal Algae of marine, lacustrine, Mostly algal components: of exinite

II Mixed Decomposition in reducing Amorphous particles derived mostly from

Marine environments, mostly phytoplankton & zooplankton
marine

III Coaly Debris of continental Mostly vitrinite & some exinite ( not algal )
vegetation ( wood, spores,
leaf cuticle, wax, resin, plant
tissue )
IV
Inert oxidized material Mostly inertinite

Table: Kerogen types, their origin,& organic particle constituents

How geochemical factors are
associated with oil
accumulation ?
 Relationship ?
1. The geochemical characteristics of
petroleum.
2. The geochemical characteristics of water.
3. The Associated substances in petroleum
deposits.
4. Through geochemical reactions.
5. Through geochemical environment.
6. Through geochemical mobility.
The geochemical characteristics of petroleum
 Tables !!
Phase Source C H S N N+O O
Crude oils Humboldt, Kans. 85.6 12.4 0.37 - - -
Healdton, Okla
SOURCE OF OIL 85.0TRACE
12.9 0.76
ELEMENTS -
IDENTIFIED - -
Canada Beaumont, Tex 85.7Fe, Al,11.0 0.7and Ag-
Ca, Mg, Au 2.61 -
Wax,Ohio
Natural Athabaska Tar 84.4Fe, Al,11.2
Ca, Mg, Au, Ag, Cu0.04
2.73` - -
Asphalt
Mexico Si, Fe, Al, Ti, Mg, Na, V, N, Sn, Pb, Co, Au
Japan Asphalt from Utah 89.9Si, Fe,9Ca 0 - - -
Egypt Limestone Fe, Ca, Ni, V
Asphalt
Iraq Gilsonite 85-86 8.5-10
Fe, Ni, Y 0.3 2 - -
Texas Glance Pitch 80-85
Si, Fe,7-12
Al, Ti, Ca,2-8
Mg, V, Ni,- Ba, Sr, Mn,
0-2 Pb, -
Asphalt 83.4-Cu, Cr, Ag
8.9-13- 1.2 0.4 - 2.0
Pyrobitumens Albertite 87.2 2
ELEMENTAL COMPOSITION OF SOME CRUDE OILS, MINERAL WAX AND ASPHALTIC
SUBSTANCES
The geochemical characteristics of water

• Brine – interstitial water and salinity.

• Bottom water or edge water.
• Irreducible minimum saturation and fully
water saturation.
• Salinity gradient and diffusion or
displacement.
• Common ions of Na, Mg, Cl, Ca, Al, Fe, Mn, Zn,
Ba, Cu, Ag, Rb, F, B, Ni and SiO2.
• Brine water also contains organic substances like naphthenates,
salts of aliphatic acids, phenols, phenols and benzene etc.
• It is proposed that a lateral increase in the benzene content of the
brine in a given statum may point towards an oil accumulation in
that stratum. (after W.M.Zerella, R.J. Mousseau, N.D. Coggeshall et
al 1967)
• In sea water, Mg is more abundant than Ca, whereas in oilfield it is
reverse. The formation of chlorite rather than dolomite, or to its
slow incorporation in fine grained mixed layer micas in the
sediments suggest relative decrease in Mg.
• High salinity in water found in coarse-pored rocks such as reservoir
rocks underlying clays or shales, the cap rocks of oilfields.
• Filtration mechanism – Ca++ is less mobile than Na+, and Cl- is less
than water molecule, Mg++ is slightly less mobile than Cl-, which is
more mobile than Ca++ and SO4--
Geochemical characteristics of
OTHER ASSOCIATES
 CO2
• Many N/gas contains small amount of carbon dioxide
• As much as 92% CO2 has been found in a gas from Upper
Cretaceous sandstones in the Walden Field in Colorado
• Sufficient CO2 was at one time produced from the Santa Maria
oilfield in California to Justify the operation of a local ‘dry ice’
plant on a commercial scale
• Canada – 15% in Alberta, New Zealand – 49% from Pliocene strata
• Much CO2 is clearly of magmatic origin, and is related to areas of
recent volcanism
• May also be a product of metamorphism
• Produce from breakdown or oxidation of many organic
substances
• Microorganisms can fix the CO2 in following ways:

– Reverse Krebs cycle (also known as the reverse

tricarboxylic acid cycle, the reverse TCA cycle, or the
reverse citric acid cycle). The reaction is basically the Citric
acid cycle run in reverse and is used by photolitho-
autotrophic eubacteria of the Chlorobiales and some
chemolitho-autotrophic sulfate-reducing bacteria.
– Reductive acetyl CoA Pathway is found in methanogenic
archaebacteria and in acetogenic and some sulfate-
reducing eubacteria as a way of fixing carbon.
– 3-Hydroxypropionate Pathway is found in photolitho-
autotrophically grown eubacteria of the genus Chloroflexus
and in modified form in some chemolitho-autotrophically
grown archaebacteria as a way of fixing carbon.
 Hydrogen sulphide H2S
• Mainly magmatic action – 3,00,000 tons per year produce from
one fumarole area in Alaska alone !!
• Non-volcanic origin – swamps, peat bogs, stagnant water etc.
• It is formed at the present time as a result of bacterial reduction
of sea water sulphates due to lack of circulation of oxygenated
water.
• Usually associated with N/Gas due to bacterial breakdown. e.g.
Spindletop field of US.
• Association with Anhydrites, gypsum, suggest there is a reducing
action of liquid bitumens on gypsum.
• When it contains appreciable amount of H2S, it is called as ‘sour’
and free of this is called ‘sweet’.
• It is actively corrosive, and so is generally removed by a chemical
desulphurisation process (along with dehydration).
Role played by different

GEOCHEMICAL REACTIONS
 The role of diagenesis in hydrocarbon generation

• Organic matter (lipids, proteins, carbohydrates and

lignin-humic compounds) > sedimentation > organic
molecules break down due to the increase in
temperature and pressure > creation of two primary
products: kerogens and bitumens.
• Thermal alteration > kerogens > break down to form
hydrocarbons through a chemical process known as
cracking, or catagenesis.
• Kinetic model > dissolution-precipitation mechanism.
COMPOSITION OF OIL- AND GAS-
BEARING ROCKS
 Solutional behaviour
• ion strength
• PH and Eh
• Dissolved CO2 and CH4 content
• Presence of organic acids
• water
• Presence of dissolved phases like halite, sylvite and
anhydrite.
 pH control
• Carbon dioxide can be used as a mean of
controlling the pH of swimming pools, by
continuously adding gas to the water, thus
keeping the pH level from rising. Among the
advantages of this is the avoidance of
handling (more hazardous) acids.
• where ∆Z = the free energy of reactions; n= the number of
electrons taking part in the reaction; F = the Faraday constant
(96,520C/g-eq.); and y = the constant for a given reaction.

As alkalinity of the environment declines, a less reducing

environment is needed for the reduction of the same
components.

It appears that a strongly alkaline environment is not

necessary and may even be detrimental for the
transformation of organic matter into hydrocarbons.
Minerals participating in the processes have significantly different pH and Eh stability
limits. A stage of syngenesis and early diagenesis (p<10MPa, T<60–700C), the pH
stability limits for various minerals are (after Minskiy, 1975, pp. 147–150):

A significant role in the postdepositional alterations of carbonate rocks

belongs to re- crystallization and dissolution. These processes usually result in
increased porosity. In some cases, however, the emerging pores are easily
filled-up with secondary (authigenic) minerals, mostly calcite and dolomite. In
1954, Chilingar and Terry have shown that dolomitization of limestones
creates additional porosity (up to the theoretical value of 12.1%) (also see
Chilingarian et al., 1992, 1996).
Role of different

GEOCHEMICAL ENVIRONMENT
 Factors which affects the post
depositional settings
• Temperature and Pressure
• Permeability
• appearance and redistribution of the cement,
• changes in the structural (textural) orientation
of rock-forming minerals, and
• dissolution of minerals unstable in a given
environment.
South Louisiana, USA.
Compaction of
unconsolidated Tertiary sands
with admixture of clay
(after P. A. Allen and J. E.
Allen, 1990). < Depth distribution of areas of
(1) reservoir rocks (OR) and (2) oil
accumulations (OA)(after
Maksimov and Minskiy, 1972)
POROSITY AND PERMEABILITY
DEFORMATION OF ROCKS IN
DEPTH
According to Eremenko et al. (1986), the
following vertical zones may be identified for
the platforms:
• Zone I. Karst zone
• Zone II. Calcite cementation zone
• Zone III. Decompaction zone
• Zone IV. Gravitational compaction and
silica/silicate generation/regeneration zone.
 Zone III
• montmorillonite-to-illite transformation is accompanied by
the release of water and shale loosening, after which shales
compact further.
• Released water (that had been previously chemically bonded)
is chemically aggressive and dissolves various salts as well as
hydrocarbons in the surrounding rocks.
Zone VI
• Reservoir pressure exceeds the pore pressure in shales.
• Silicified reservoir rocks become fluid barriers, whereas
compacted argillaceous rocks experience fracturing and
become reservoir rocks.
Factors: elevated subsurface pressures and temperatures; tectonic stresses, seismic
activity, changes in the energy and magnetic fields, and exothermal reactions of
mechanochemical nature.
The mobility of

PETROLEUM
 mobility
primary
• May be in situ accumulation
• Movement and segregation
SR
RSVR rock
• P/T and Solulilization -
colloidal electrolytes
• Aromatics >> nephthenes
>> paraffins
• Compaction effects
• Pore pressure and direction
of water flow
secondary
• capillary pressure,
displacement pressure or
diffusion
• Hydrodynamic gradient
• Buoyancy
• Differential entrapment
• Movement in structural and
stratigraphic traps.
Mobility of associated phases and
buoyancy
Scopes ?
The chemical composition of formation waters can
be used as an indicator for the presence of
petroleum (V.
(V. A. Sulin, in:
in: Vassoyevich, 1954)
1954):
The specific hydrochemical indicators for the presence of oil
include:
 Presented by:
Manash Pratim Gogoi
M.Sc. 4th semester
Department of Applied Geology
Dibrugarh University

gogoi.manash00@gmail.com
munmunhapun@live.com