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BASIC PETROLEUM GEOCHEMISTRY

Prepared for: AAPG ITS SC Short Course


21st April 2018
Who knows how oil and gas produced?

Dinosaurs pool of hydrocarbon??


PETROLEUM SYSTEM
ACTUALLY, THERE ARE TWO HYPOTHESIS

1 2
Abiogenic: petroleum was formed Biogenic: pooled oil and gas in
from deep carbon deposits, porous reservoirs can only be
perhaps relating to the formation explained by its origin in
of the Earth, and that petroleum thermally mature, organic-
migrate upward from the mantle. rich, sedimentary source
(Thomas Gold, 1999). rocks. (Wallace Dow, 2002).
BRIEF HISTORY OF
ABIOGENIC THEORY
• The hypothesis was first proposed
by Georg Agricola in the 16th
century and various abiogenic
hypotheses were proposed in the
19th century, most notably by
Prussian geographer Alexander von
Humboldt, the Russian chemist
Dmitri Mendeleev and the French
chemist Marcellin Berthelot.
• The abiogenic hypothesis is usually
traced to the early part of the 19th
century. At the time, the chemical
nature of petroleum was not
known.
• Russian geologist Nikolai
Alexandrovitch Kudryavtsev
proposed the modern abiotic
hypothesis of petroleum in 1951
• Astronomer Thomas Gold was the
most prominent proponent of the
abiogenic hypothesis in the West
until his death in 2004. More
recently, Jack Kenney of Gas
Resources Corporation has come to
prominence.

www.viewzone.com
Abiogenic Origin of Petroleum: Mechanisms
• Primordial deposits: Thomas Gold's work was focused on hydrocarbon deposits of primordial
origin. Meteorites are believed to represent the major composition of material from which the
Earth was formed. Some meteorites, such as carbonaceous chondrites, contain carbonaceous
material. The thermodynamic conditions within the mantle would allow many hydrocarbon
molecules to be at equilibrium under high pressure and high temperature.
• Creation within the mantle: Russian researchers concluded that hydrocarbon mixes would be
created within the mantle. Experiments under high temperatures and pressures produced many
hydrocarbons—including n-alkanes through C10H22—from iron oxide, calcium carbonate, and
water.
• Hydrogen generation: Hydrogen gas can be created by water reacting with silicates, quartz, and
feldspar at temperatures in the range of 25 °C (77 °F) to 270 °C (518 °F). These minerals are
common in crustal rocks such as granite. Hydrogen may react with dissolved carbon compounds
in water to form methane and higher carbon compounds.
Abiogenic Origin of Petroleum: Mechanisms
• Serpentinite mechanism: In 1967, the Ukrainian scientist Emmanuil B. Chekaliuk proposed that
petroleum could be formed at high temperatures and pressures from inorganic carbon in the
form of carbon dioxide, hydrogen and/or methane. This mechanism is supported by several lines
of evidence which are accepted by modern scientific literature. This involves synthesis of oil
within the crust via catalysis by chemically reductive rocks. A proposed mechanism for the
formation of inorganic hydrocarbons is via natural analogs of the Fischer-Tropsch process known
as the serpentinite mechanism or the serpentinite process.
• Spinel polymerization mechanism: Magnetite, chromite and ilmenite are Fe-spinel group
minerals found in many rocks but rarely as a major component in non-ultramafic rocks. In these
rocks, high concentrations of magmatic magnetite, chromite and ilmenite provide a reduced
matrix which may allow abiotic cracking of methane to higher hydrocarbons during
hydrothermal events.
• Carbonate decomposition: Calcium carbonate may decompose at around 500°C (932 °F)
through the following reaction:
Hydrogen + Calcium carbonate → Methane + Calcium oxide + Water
Biogenic Origin of Petroleum: Mechanisms
How Hydrocarbon
Formed

Organic material
overburden

Sediment rock
anaerob reaction
(lipids to waxy
substance)

Kerogen
• Deeper burial
• Greater
overburden
• Greater
temperature

HC Chains
Thermal cracking
Oil window (80°-180° C)

Oil window (>180° C) Oil Gas


Oil cracking

Gas
www.oilandgasuk.co.uk
Biogenic Origin of Petroleum: Mechanisms
Certain chemicals found in naturally occurring petroleum contain chemical and structural similarities
to compounds found within many living organisms. The presence of these chemicals in crude oil is a
result of the inclusion of organic material in the oil formation.

Structure of a biomarker extracted from petroleum and simplified structure of chlorophyll.


“Biogenic theory” of oil and gas origin subsequently led to the “generative basin” concept and
eventually to the “petroleum system” paradigm that is widely used with great success by the
petroleum industry today.
Petroleum Geochemistry
Petroleum Geochemistry
• Geochemistry is the application of chemistry to the study of rocks and fluids.
(Selley, 1985 : Elements of petroleum geology)

• Petroleum is a material occurring naturally in the earth which is predominantly


composed of mixtures of chemical compounds of carbon and hydrogen (hydrocarbon)
and including various forms from solid bitumen, through the normal liquids to gases.
(Tver and Berry, 1980 : The petroleum dictionary)

• The application of chemical principles to the study of the origin, migration,


accumulation, and alteration of petroleum and the use of this knowledge in the
exploration and production of oil and gas.
(Hunt, 1996: Petroleum geochemistry and geology)
BP Research (1991)
The Essences of Petroleum Geochemistry
• To make it benefit, inputs from petroleum geochemistry should be integrated with petroleum
geology (broad basin analysis).

• Petroleum geochemistry is more exact (not much interpretive) than other petroleum geosciences,
but it heavily depends on laboratory analyses.

• Geology-Geophysics-Geochemistry (3G) is a trinity of petroleum geosciences. If one of them were


ignored, risk for exploration failure increases

TRILOGY OF EXPLORATION SUCCESS

Needs integration of geology, geophysics, and


geochemistry

“3G” - Approach
Geochemical Survey
• Surface geochemistry (surface geochemical prospecting)
• Well geochemistry (hydrocarbon mud logging, wireline logs,
geochemical logs)
Surface Geochemistry-Airborne
Surface Geochemistry-Offshore
Well Geochemistry
Wireline logs may be used to evaluate oil source rock potential if they have been suitably calibrated with
geochemical data and if the TOCs are > 1.5 %. Good oil source rocks within the oil window show high electrical
resistivities, high gamma ray response, low densities, high neutron porosity, and low transit time on the sonic log.

Meyer and Nederlof (1984)


Source Rock
• Organic matter, source, kerogen, and preservation in sediments
• Source rock depositional environments
• Source rock characterization
Problem with Source Rocks
• Organic richness of source rocks (TOC).
• Kerogen type of source rocks (I, II, III, IV)
• Maturation of source rocks (Ro, Tmax)
Lithology of
Potential Source
Rocks
(Coal, Carbonaceous
shale, mudstone,
organic-riched
limestone)

Mahmud et. al. (2006)


Kinds of Source Rocks
Active source rocks : a volume of rock that has generated or is generating and expelling
hydrocarbons in sufficient quantities to form commercial oil and gas accumulations. The
contained sedimentary organic matter must meet minimum requirement of organic
richness, kerogen-type and organic maturity.

Spent source rocks : a volume of rock that had generated, possibly a long time ago, its
hydrocarbons and now contains thermally altered organic matter.

Potential source rocks : a volume of rock that has the capacity to generate hydrocarbons in
sufficient quantities to form commercial oil and gas accumulations, but has not yet
reached the state of minimum hydrocarbon generation because of insufficient organic
maturation.
Kerogen (from kerosene generator) is defined
as the organic component of source rocks that
is insoluble in common organic solvents and
aqueous alkali (NaOH solution). The soluble
portion of the organic matter is termed
bitumen or total soluble extract (TSE)

Kerogen is of complex biological origin; it is


derived from dead organisms whose organic
remains survive the early stages of diagenesis
and lithification. This biological origin is
frequently apparent when kerogen is
analysed by microscopic or chemical
techniques. It is derived from the lipid, lignin,
protein, and carbohydrate portions of
organisms.

Brooks (1987)
Organofacies and Kerogen Types
Preservation of Organic Matter
• The principal control on organic richness is the efficiency of
preservation of organic matter in sedimentary environments.
• Three factors affect the preservation (or destruction) of organic
matter:
•the concentration and nature of oxidizing agents
•the type of organic matter deposited
•the sediment-accumulation rate
• Of these, oxidizing agents are probably the most crucial factor.

Factors Enhancing Preservation


• Stagnant basins: density stratification with O2-poor bottom waters
• Oxygen-minimum layer (OML): the rate of oxygen consumption
exceeds the rate of oxygen influx
• Restricted circulation: presence of shallow and deep silling, coal
swamps (poor water circulation, high influxes of organic matter,
diminished bacterial activity).
Silled Basin

Brooks et al. (1987)


Depositional Environment Favoring Source Rock Development
Evaluating Source Rocks from Wireline Log
• Source intervals are identified by:
– an increase in sonic travel time
– an increase in neutron porosity
– a decrease in bulk density
– either no change or increasing resistivity
• The source interval often, but not always, has enhanced levels of uranium
concentration and total radioactivity.
• Carbonate source rocks are characterized by the low K and Th, high U.
• Shale source rocks are characterized by the moderate K and Th, high U.
• Mature organic-rich shales are characterized by higher resistivities than immature
ones and the increase in resistivity is proportional to the amount of generated
petroleum.
BP Research (1991)
Wireline logs and oil source rock potential
EXERCISE
Determine what and where the
reservoir and possible source rock
are!
EXERCISE
Determine what and where the
reservoir and possible source rock
are!
Rock-Eval Pyrolysis
• S1 (P1) (ppm): free HCs released when furnace temperature is 250ºC
• S2 (P2) (ppm): HCs cracked from kerogen when furnace temperature is 550ºC
• S3 (P3) (ppm): carbon dioxide released during early stages of pyrolysis
• T max ºC: maximum temperature of S2
• HI (hydrogen index): S2/TOC (mg/g) or ratio of released HCs to organic carbon
content
• OI (oxygen index): S3/TOC (mg/g) or ratio of released carbon dioxide to organic
carbon content
• PI (production index): S1/S1+S2
• PY (pyrolysis yield): S2 (ppm) or total of HCs released during cracking of kerogen
compared to original weight of rock
• Source potential: S1+S2
• Tmax, HI, and OI are each functions of both maturity and kerogen type.
Peters and Cassa (1994)
Source Rock
Characterization
Source Rock
Characterization
Source Rock
Characterization
Source Rock
Characterization
Peters and Cassa (1994)
Hydrocarbon Generation
• Maturity: Optical and Molecular Parameters
• Petroleum Generation and Expulsion
• Volumetric Calculation
OPTICAL MATURITY
VITRINITE REFLECTANCE

(Uky.edu, 2018)
Well X
OPTICAL MATURITY
SPORE COLORATION INDEX
MOLECULAR MATURITY PARAMETER
• Loss of oxygen containing functional groups followed by isomerisation at chiral centres
• Increase of aromacity in cyclic compounds
Mechanism of Petroleum Generation and Destruction

(< 100°C)

(100-150°C)

(150-230°C)

(150-230°C)

(> 230°C)
Mechanics of Expulsion
• Expulsion is also known as primary
migration
• Cycles of petroleum generation,
pressure build up, micro-fracturing,
pressure release, petroleum migration
continue until the source rock is
exhausted
Hydrocarbon Migration
The Driving vs Resistive Force
The main driving forces for secondary migration :
• buoyancy: caused by the density difference between oil (or gas) and the
pore waters of carrier beds
• pore pressure gradients: which attempt to move all pore fluids (both
water and petroleum) to areas of lower pressure.

The main resistive forces for secondary migration:


• capillary pressure, which increases as pore size become smaller when
• capillary pressure exceeds the driving forces, entrapment occurs.
Migration Pathways
• Petroleum will tend to move perpendicular to structural contours.
• Petroleum flow may be split when encountering a low, and concentrated along
regional highs.
• The geometry of the kitchen also affects petroleum charge volumes; prospects
located close to the ends of strongly elongate source kitchens will receive
relatively little charge.
• Sealing faults may deflect petroleum flow laterally.
• Nonsealing faults allow petroleum to flow across the fault plane into juxtaposed
permeable units at a different stratigraphic level.
Principle of Migration Pathway
• Petroleum will tend to move perpendicular to structural
contours along the area of lower pressure in subsurface (i.e.
structural noses)
• Migration is focused along regional highs/noses
• Most migrations direct perpendicular to long axis of kitchen
(in foreland basin)
Allen and Allen (1990)
HC Generation – Migration –Loss – Accumulation – Preservation

England (1994)
EXERCISE

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