Origin of Hydrocarbons

Hydrocarbons from the mantle

Abundance of ~1,0004,000 ppm
Carbon content of Earths core may be
quite high (~5 wt %) can there be
diffusion from core to mantle?

Projected transport
distances (kilometers) as a
function of temperature and
corresponding pressure.
Number in parentheses show
the activation volume used (in
cm3/mol) to estimate the effect
of pressure on grain-boundary
diffusivity. Transport distances
may be as high as 10 km

Carbon is recycled into the mantle via subduction mainly as

carbonates and is released to the atmosphere via volcanism mostly
as CO2. The stability of carbonates versus decarbonation and melting
is therefore of great interest for understanding the global carbon cycle

Mg-Fe carbon-bearing compound at depths greater than 1,800 km

Boulard et al. (2011)

An abiogenic source for hydrocarbons was suggested by examples

where oil occurs close to serpentinized plug

Example from Lytton Springs oil pool, Caldwell County, Texas

Lake Siljan. A meteorite impact crater in Sweden drooled in 1986 to

test for mantle derived petroleum. It proved existence of deep porosity
and permeability and recovered oil and gas. The oil proved to have
been produced by the alteration of diesel in the mud system

Drilling reached 6957 m and produced 85 barrels of oil

Urengoy gas field is the worlds

second largest natural gas field
located in the grabenof the
West Siberian basin

Region has long lived history

of mantle activity including
Siberian traps and active rifting
since the Neoproterozoic

Ternary plot of common source

rock biomarkers in oil and gas
from Jurassic age reservoirs
and sources in West Siberia

biomarkers in gas condensate and

oil are almost identical to the
Jurassic source rocks confirming
them as the source

Urengoy gas composition

compared with carbon isotopes
in methane

most of the gas samples plot on

a mixing trend between
thermogenic gas and an
isotopically light dry gas of
unknown provenance

Mantle source for Urengoy gas?

CO2 analyzed from mid ocean ridge hydrothermal systems
indicates that this is not the source. d13C enrichment is the
opposite of that expected.
Alternative mechanism is abiogenic formation via reduction
of HCO-3 catalyzed by Fe-Ni alloy which are common
reaction product of serpentinization.
Generates isotopically very light gas similar to the
compositions found at Urengoy - Subduction recycling?

What is Kerogen?
Kerogen is a mixture of organic chemical compounds that make up a portion of the
organic matter in sedimentary rocks. It is insoluble in normal organic solvents
because of the huge molecular weight of its component compounds.
The soluble portion is known as bitumen.
When heated to the right temperatures in the Earth's crust, (oil window ca. 60
160C, gas window ca. 150200C, both depending on how quickly the source rock is
heated) some types of kerogen release crude oil or natural gas.

Types of organic matter

In soil science, humus refers to any organic matter that has reached
a point of stability, where it will break down no further.
Lignin is a complex chemical compound most commonly derived
from wood, and an integral part of the secondary cell walls of plants
and some algae. A prime function is the support through
strengthening of wood in trees.
Lipids constitute a broad group of molecules that include fats, waxes,
sterols, fat-soluble vitamins, monoglycerides, diglycerides,
triglycerides, phospholipids, and others. The main biological
functions of lipids include energy storage, as structural components
of cell membranes.
A carbohydrate is an organic compound that consists only of carbon,
hydrogen, and oxygen.
Liptinite refers to the finely-ground and macerated remains found in
coal deposits. Liptinites were originally formed by spores, pollen,
dinoflagellate cysts, leaf cuticles, and plant resins and waxes.

Types of organic matter

A maceral is a component, organic in origin, of coal or oil shale. The
term 'maceral' in reference to coal is analogous to the use of the
term 'mineral' in reference to igneous or metamorphic rocks.
Examples of macerals are inertinite, vitrinite and liptinite.
Inertinite is considered to be the equivalent of charcoal and
degraded plant material.
Vitrinite is shiny, glass-like material that is considered to be
composed of cellular plant material such as roots, bark, plant stems
and tree trunks.
Liptinite macerals are considered to be produced from decayed leaf
matter, spores, pollen and algal matter.

Sources of kerogen

Composition of organic matter in organisms and shallow recent sediments

in different oceans worldwide

Chemical composition of animals and plants

Chemistry of Kerogen

Three basic types of carriage and are recognized and distinguished on the basis of its
chemistry. Each generates a different style of hydrocarbon

Molecular structure of Kerogen

Molecular structure of type I or algal kerogen, type II or liptinic

kerogen and type III or humic kerogen

Formation of kerogen

Diagenesis. This phase occurs in the shallow subsurface at near-normal

temperatures and pressures and includes biogenic decay aided by bacteria and
abiogenic reactions. Net result is reduction of oxygen content.

Catagenesis. This phase occurs in the deeper subsurface as burial continues.

Petroleum is released from kerogen during Catagenesis first oil then gas. The
hydrogen/carbon ratio declines with no significant change in the oxygen/carbon
ratio.
Metagenesis. The third phase occurs at high temperatures and pressures. The
last hydrocarbons, generally and the methane are expelled. The
hydrogen/carbon ratio declines until only carbon is left in the form of graphite.

Organic matter burial

Sulfate reduction followed by bacterial fermentation effect. Organic matter. Thermal

decarboxylation does not occur until burial of greater than 2 km

Van Krevelen diagram

Graph showing the maturation paths of the three different types of kerogen

Van Krevelen diagram

A Van Krevelen diagram showing the primary composition of the different types of
kerogen and in the changes as a function of heating during burial
Liptinite has replaced the term Exinite as one of the four categories of kerogen

Changes in temperature during burial means for effective

temperature must be integrated over the range of temperatures that
the kerogen is exposed to. This may be represented by the

time temperature index (TTI)

F is a factor dependent on the captivation energy of the reactions.

Rates approximately double each 10 C

Thermal maturation

Maturity of source rock is a function of the time-temperature index that can be calculated
from the burial and the geothermal gradient. The gradient is most critical during the deep
burial because maturation is an exponential function of the temperature.

Composition of petroleum

Hydrocarbons with a high C/H ratios tend to have low densities

API gravity is expressed as an inverse relationship API gravity = 141.5/-131.5

Hexane

Hexane is a hydrocarbon with the chemical formula C6H14; that is, an alkane
with six carbon atoms.
Alkanes (also known as paraffins or saturated hydrocarbons) are chemical
compounds that consist only of hydrogen and carbon atoms and are bonded
exclusively by single bonds without any cycles or loops

Cyclohexane

Cyclohexane is a cycloalkane with the molecular formula C6H12

Cycloalkanes (also called naphthenes) are types of alkanes that have one
or more rings of carbon atoms in the chemical structure of their molecules

Benzene

Benzene is an organic chemical compound with the molecular formula C6H6.

Its molecule is composed of 6 carbon atoms joined in a ring, with 1
hydrogen atom attached to each carbon atom.
An aromatic hydrocarbon is a hydrocarbon with alternating double and
single bonds between carbon atoms forming rings

Organic matter and sedimentation

Relationship between total organic carbon and sedimentation rate for Jurassic to recent
sediment. Different types of sediment have optimum sedimentation rates for maximum
preservation of organic matter. Too slow a rate and oxygenation occurs, too high and
organic carbon is diluted

Source rocks through geological time

Notice the concentration of rocks in the late Jurassic to early Cretaceous, the midCretaceous and the Miocene, times of known organic rich sediment deposition

Tools for determining the origin

of hydrocarbons and thermal
history

Gas chromatograph data

X-axis is the retention time in minutes. The peak height is a

function of abundance. Compounds with more carbon atoms
appear further to the right. The numerical codes on the peaks
equal the number of carbon atoms in each different molecule

Gas chromatograph

Gas chromatography data

Evolution of n-alkanes with increasing temperature and burial depth. Immature

source rocks show a broad whaleback with a bimodal distribution of unsolved
components. As the temperature increases the whaleback submerges and the
unsolved components form a single peak.
Degraded oils are characterized by a low, broad whaleback devoid of spikes.

Commonly used organic indices

Hydrogen index - The hydrogen index (HI) is the density of
hydrogen relative to that of water. when the kerogen type is
known it can be used to estimate the thermal maturity of the
rock. It is a key factor in the response of a neutron porosity
log.
Oxygen index - The ratio of S3 (mg CO2/g dry rock) to TOC
(in grams). This parameter measures the oxygen richness of
a source rock and can be used in conjunction with the
hydrogen index to estimate the quality and thermal maturity of
source rocks. This index is unreliable in rocks with high
carbonate content. High OI values (>50 mg/g) are
characteristic of immature hydrocarbons.

Rock-Eval pyrolysis data

Pyrolysis is a thermochemical decomposition of organic material at elevated
temperatures without the participation of oxygen.

Hydrogen index (HI) = (S2/TOC)x100 is a measure of the potential of the source

rock to generate petroleum and maturity. Total amount of CO2 generated is
measured as the S3 peak The oxygen index (OI) = S3/TOC

Rock-Eval data

Possible source rock is heated gradually to 550 C while the amount of hydrocarbon
generated is measured. At 300 C oil and gas is expelled and measured as the S-1 peak.
The peak at 400 to 460C represents the amount of hydrocarbons generated from the
sample. The temperature of peak HC generation is called the T max.

Geochemical well log

Well log illustrating the
lithology, total organic
carbon content and rockeval parameters S2 and HI

Geochemical well log

Logs of kerogen type give an
indication of the oil or gas
prone nature of the sources
and two paleo-thermometers
spore coloration and vitrinite
reflectance

Organic maturation

Correlation between hydrocarbon generation, temperature and some

paleo thermometers

What controls the thermal

evolution of a sedimentary basin?

Thermal evolution of basin partially reflects the lithospheric tectonics

Effect of internal heat production on geothermal gradients

Heat production varies very strongly based on the materials in the lithosphere

Heat production due to radioactive decay decreases

exponentially with depth

H = Hsexp(-y/hr)
Hs = surface heat production

What is the relationship between heatflux and thermal

gradient?

If the temperature is constant with depth (T/z = 0), there is no heat

flow
If T/z is constant (and nonzero) with depth, the heat flow will be
constant with depth; this is a steady state
The temperature at any point changes at a rate proportional to the
local gradient in the heat flow

Heat flux at surface

qs = qm + hrHs
qs = surface heat flux (W m2)
Hs = Heat production
= Density of crustal material
hr = depth length scale (6-10 km)

How to calculate temperatures at depth from heatflow

and conductivity data

Ts = surface temperature
qm = heat flux from the mantle (30 mW m -2)
qs = heat flux at the surface
y = depth
hr = depth length scale (~10 km)
k = thermal conductivity of the mantle (3.3 W m -1 K-1)

Simplified relationship of thermal conductivity to thermal

gradient and heatflow

T = temperature gradient
Q = Quantity of heat
t = time
L = depth
A = area
k = thermal conductivity

How to calculate temperatures in sediment deposited

at time t

T0 = Initial temperature at surface

qs = heat flux of sediments
km = thermal conductivity of mantle (3.3 W m -1 K-1)
ks = thermal conductivity of sediments (2.0 W m -1 K-1)
m = thermal diffusivity of mantle (1 mm2 s-1)

Heatflow: linked to
tectonic settings and age
of tectonic activity

Parson & Sclater (1977), Stein & Stein (1992)

Calculating Heatflow after Rifting

Extension initially increases heat flux by ; heat flow then decreases as
a function of:
Exp(-t/)
Where t is time and is thermal diffusivity.
= 63 Ma

Heatflow q at time t = qinf * (1+2*((/)*Sin(/ ))*(Exp(-t/)))

Basal heatflow qinf = 33.52 mW/m2

So rifting results in temporarily increased

heatflow due to steeper thermal gradient, as
mantle lithosphere thins, but extension can
reduced long-term heatflow because the
amount of heat-producing upper crust is less

Maturation of
organic matter with
burial and heating
Oil window 100150C
Gas >150C
How many km?

Vitrinite reflectance
versus depth:
global correlation
A measurement of the maturity of
organic matter with respect to
whether it has generated
hydrocarbons or could be an
effective source rock. The
reflectivity of at least 30 individual
grains of vitrinite from a rock
sample is measured under a
microscope. The measurement is
given in units of reflectance, %
Ro, with typical values ranging
from 0% Ro to 3% Ro

Vitrinite reflectance versus depth for different aged kerogens

Vitrinite Reflectance as a basin modeling tool

Vitrinite Reflectance versus Burial Depth