Geochemistry

in Petroleum
Exploration
Neha Rawat
Sr. Chemist

KDMIPE

India’s only Energy Company in Fortune’s ‘World’s Most Admired’ List

 PRESENTATION OVERVIEW

Introduction

Concept of Petroleum system

Different geochemical methods

applied for hydrocarbon exploration
 PETROLEUM GEOCHEMISTRY

Petroleum geochemistry is the application of chemical principles to the

study of the origin, migration, accumulation and alteration of petroleum and
the use of this knowledge in exploring for and recovering petroleum (Hunt,
1996).

Petroleum geochemistry evaluates:

• Quality, quantity and thermal maturity of organic matter contained in source
rocks, which are precursors of hydrocarbons.
• Adequacy of quantum of charge of petroleum.
• Migration and entrapment processes to achieve a better focus on
occurrence of locales of petroleum and to arrive at better regional priorities
for exploration and development of petroleum resources.
 ORGANIC MATTER TO PETROLEUM

Global Organic Carbon flow

is a closed cycle.

106g Approx. 0.1% organic carbon

escapes the carbon cycle and
0.1% gets incorporated in
Biosphere sediments (SOM)
This SOM is the precursor of
103g Petroleum.
Sedimentary
2.0%
rocks

20 g
generated 0.5%
petroleum

0.1 g
Petroleum within
reservoir rocks
GENERATION OF OIL
 ORGANIC MATTER

• Organic matter consists of :

Kerogen Insoluble-high M. Wt.
Bitumen Soluble-low M. Wt.
• Bitumen is further classified into saturates, aromatics and NSO compounds.
 PETROLEUM SYSTEM

Petroleum system (Magoon and Dow, 1994) is a natural system that encompasses a
pod of active source rock and all related oil and gas and includes all the geologic
elements and processes that are essential if a hydrocarbon accumulation is to exist

ELEMENTS:
 A pod of active source rock
 Reservoir Rock
 Seal Rock
 Overburden Rock

PROCESSES:
 Trap formation
 Generation
 Expulsion
 Migration
 Accumulation
 Preservation
 GEOCHEMICAL METHODS IN PETROLEUM EXPLORATION

 Surface Geochemical Exploration (Chemical and Microbial)

 Source Rock Evaluation

 Organic Petrography

 Kinetic studies and 1D modeling

 Biomarker and isotopic studies

 Oil to oil, oil to source correlations

 Chemostratigraphy
OBJECTIVES OF SURFACE GEOCHEMICAL EXPLORATION

Surface Geochemical Prospecting

provides a tool to map the micro
seepages of hydrocarbons or
related alterations

Objectives:
• To locate hydrocarbon seeps
• To map the seeps to relate
them to subsurface
accumulations/ prospects.

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SAMPLE PROCESSING AND METHODOLOGY

 Samples are dried at ambient temperature, grinded and sieved using 230
mesh (ASTM) sieve to get 63μ particle size

 Desorption of gases from the soil sample

 The acid extracted HCs gases are analysed (C1 to C5) over GC using FID

 Analyze the data statistically to draw concentration contour maps using

Surfer-7 and Arc-GIS

 Concentration of adsorbed gases is to be reported in ppm

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GAS CONCENTRATION MAP OF THE STUDY AREA

Methane (C1 )
anomalies are
confined to the
northeastern and
western parts of
studied area as
depicted in the map

C2+ anomalies are confined

to thenortheastern and
western part of the studied
area as shown in the map
SUCCESS RATIO ANALYSIS:KRISHNA-GODAVARI BASIN

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 PETROLEUM SOURCE ROCK

A petroleum source rock is defined as fine-grained sediment that has

generated and released adequate hydrocarbons due to degradation of
organic matter to form an accumulation of oil and/or gas

EFFECTIVE SOURCE • Any Sedimentary rock that has already generated

and expelled hydrocarbons.
ROCK

POTENTIAL SOURCE • Any immature sedimentary rock known to be

capable of generating and expelling hydrocarbons
ROCK if its level of thermal maturity were higher.
SOURCE ROCK EVALUATION

Quantity of OM

Quality of OM

Thermal maturity
 ROCK EVAL PYROLYSIS
• Rock sample is heated in inert atmosphere (flow of Helium)
• Pyro products are evolved from the rock.
• This gives vital information about the hydrocarbons already present in
the rock and hydrocarbons that can be generated by further heating.
RESULTS & OUTPUT FROM ROCK-EVAL
DETERMINATION OF TOC

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 PARAMETERS DERIVED FROM RE DATA

PI = S1/(S1+S2)

HI= S2/(TOC x 100)

OI= S3 /(TOC x 100)

Production Index (PI) is a maturity indicator like Tmax. Value of 0.1 represents Onset of generation,
while values 0.4 are characteristic of Peak oil generation. High PI may also indicate occurrence of
Contamination by migrated fluids or drilling additives
Hydrogen Index (HI) is an indicator of the remaining hydrocarbon generative capacity of a Kerogen
Oxygen Index (OI) The amount of CO2 produced from Kerogen during Rock Eval Pyrolysis. It is related
to the oxygen content of the Kerogen.
 ROCK EVAL PARAMETERS AND THEIR SIGNIFICANCE

Analysis Parameter Interpretation Application

TOC TOC %wt 0.5-1.0 marginal Defines basis for
1.0-2.0 fair source rock quality
>2 good source
ROCK Eval Tmax (oC) <435 immature Defines source rock
Pyrolysis 435-470 mature maturity and quality
> 470 post mat
S1(mg HC/ Free/ migrated
g rock) hydrocarbons
S2 (mg HC/ 0-2 poor Defines remaining
g rock) 2-5 fair generation potential
>5 good

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 ROCK EVAL PARAMETERS AND THEIR SIGNIFICANCE
Analysis Parameter Interpretation Applications
Rock Eval HI <150 poor, gas prone Defines source type and
Pyrolysis (mg HC/g 150-300 gas/oil prone HC generation potential
TOC) >300 oil prone

OI Low in oil prone or Defines source type

(mg CO2/g mature SR, high in gas
TOC prone SR

PI 0.1-0.4 oil window Screening for indigenous

>0.4 contamination/ or
migrated bitumen Migratory HC

VRo and % VRo & <0.6 immature Defines organic matter

maceral % macerals 0.7-0.9 peak oil type, maturity
studies 0.9-1.2 postmature
> 1.2 gas window

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TYPES OF ORGANIC MATTER

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IDENTIFIED SOURCE SEQUENCES IN WELL-AMDAI-1

Eocene-Kopili (1228-1242m)
(Av. TOC%: 2.4 and S2:4 mg
HC/g rock)Immature

Eocene-Sylhet (1242-1335m)
(Av. TOC%: 1.9 and S2:2.4mg
HC/g rock)Immature

Paleocene-Jalangi (1335-
1694m)
(Av. TOC%: 5.84 and
S2:16.21mg HC/g
rock)Immature

Lower Gondwana (2434-

3250m)
(Av. TOC%: 21.84 and
S2:41.81mg HC/g
rock)Immature to early mature
SOURCE ROCK MAPS OF EARLY EOCENE (YOUNGER CAMBAY SHALE FM)

TOC Map HI Map VRo Map

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 ORGANIC PETROGRAPHY

Organic petrography deals with microscopically visible solid

organic matter occurring in sedimentary sequences, particularly
in coal(concentrated organic matter) and finely disseminated in
sedimentary rocks(dispersed organic matter).

Macerals are the microscopic constituents of Coal/shale that can be

recognised by its shape , morphology, reflectance and fluorescence.

• Macerals are Classified after the original plant material :

• Liptinite : Mostly from Algae or Spores

• Vitrinite : Higher Land Plant Tissues

• Inertinite : Higher Land Plant Tissues and Fungal material with

higher Oxidized OM
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 LIPTINITES
• Liptinites are derived from hydrogen-rich plant organs and their decomposition
products.
• They show predominantly low reflectance and characteristic fluorescence.
REFLECTED LIGHT FLUORESCENT LIGHT

Resinites are fossilised Resins derived from trees

The Sporinites from the Skins of Spores and Pollens in Lignite and Bituminous coal
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 VITRINITE

• Vitrinite is derived mostly from Lignin and Cellulose of Vascular

plants from their stems, leaves, branches and roots
• Vitrinite is a source of catagenic gas at high levels of maturation

Telovitrinite

Detrovitrinite

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 INERTINITE

• Inertinites are formed from plant material which undergoes a pyrolysis or partial
combustion stage prior to burial, normally as a result of fire.
• They are Carbon-rich, have Low-Hydrogen content and have High Reflectance.

Fusinite Funginite

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EFFECT OF MATURITY ON STRUCTURE OF VITRINITE

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 VRO DEPTH PROFILE

• Vitrinite Reflectance is the most

widely used maturity parameter

Maturity of organic matter VRo, %

Immature <0.55*
Early mature 0.55-0.75
Peak mature 0.75-1
Late mature 1-1.3
Over mature >1.3

*Typical of Type III organic matter.

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 KINETIC STUDIES

• Kinetic measurements on source Rock samples quantify the rate at which

kerogen decomposes into petroleum under increasing thermal stress. Kerogen
conversion can be related to measured thermal-maturity parameters, but varies
depending on kerogen composition and structure.

• A and E are properties of the reactant (i.e.

oil- or gas-generating kerogen); A’s and E’s

k = Ae ( -Ea RT ) characterizing the various chemical bonds

which are broken in response to thermal
stress.

• Rate of kerogen decomposition increases exponentially with increasing

temperature:
k = reaction rate constant
A = frequency factor (in s-1)
Ea. = activation energy (Kcal/ mol)
R = Universal gas costant, 1.987
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T = temperature (K)
ACTIVATION ENERGY DISTRIBUTION DERIVED PYROLYSIS SHOWING KINETIC
PARAMETERS OF SOURCE ROCK FACIES

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 OIL TO OIL AND OIL TO SOURCE CORRELATION

• Organic matter type of mother source rock

• Environment of deposition of the mother source rock

• Maturity level of the source rock

• Oil to oil and oil to source correlation method helps in

developing models of oil generation, migration and
accumulation in a basin

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 CORRELATION PARAMETERS

Gross level parameters

• API gravity of oil
• Sulphur content of oil
• Wax content of oil
• Saturates, aromatics, NSOs content

Molecular level parameters

• Light hydrocarbons by Gas Chromatography

• Normal alkanes and Isoprenoids by Gas Chromatography
• Biomarkers by Gas Chromatography-Mass Spectrometry
• Stable carbon isotopic of saturates and aromatics by Stable
Isotope Mass Spectrometry
 API GRAVITY

Type of molecules in crude oil:

• Paraffins
• Naphthenes
• Aromatics
• NSO compounds
Classification of oils °API
Heavy oils 10-22.3
Medium gravity oils 22.3-31.1
Light oils 31.1-55
Very light oils/ Condensates >55

API Gravity is affected by original organic matter input, biodegradation, water washing,
migration and evaporative fractionation.

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 BIOMARKERS

•Biomarkers are a group of compounds, primarily hydrocarbons, found in oils,

rock extracts, recent sediment extracts and soil extracts.

•Organic compounds whose carbon structure or skeleton is formed by living

organism and is sufficiently stable to be recognized in crude oil or the organic
matter of ancient sediments are called biomarkers i.e., their carbon
structures or skeletons can be traced back to living organisms.

•Biomarkers retain all or most of the original carbon skeleton of the original
natural product and this structural similarity is what leads to the term
"molecular fossils".

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IMPORTANT CLASSES OF BIOMARKERS AND THEIR PRECURSORS

Biomarker Precursor
n-alkanes(> C-22) Terrestrial plant waxes
n-alkanes (C-17, C-22) Algal lipids
isoprenoids (< C-20) Various chlorophylls
Isoprenoids (> C-20) Lipids or chlorophyll of hypersaline
algae

porphyrins chlorophylls
steranes steroids
triterpanes Bacterial triterpenoids
diterpanes Hydrocarbons in plant resins
Large naphtheno-aromatics Steroids, triterpenoids
 ORGANIC MATTER INPUT

Chromatograms indicating variations in source input

Terrestrial Input

Marine Input
 CROSS PLOTS FOR CORRELATION

Ternary Diagram Pr/nC17 vs Ph/nC18

Sofer Plot C29 Sterane maturity plot 38

(GCMSMS) STERANE DISTRIBUTION IN AN OIL SAMPLE

If High- Marine

If High -Lacustrine

If High -Terrestrial
Source rock
depositional
environment

Marine

C30 freshwater lacustrine

steranes

Fresh to brakish
water lacustrine

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m/z 191 MASS FRAGMENTOGRAMS IN OIL-TO-OIL CORRELATION

RDS-38 G-138

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m/z 191 MASS FRAGMENTOGRAMS IN OIL-TO-SOURCE CORRELATION

Oil Source
 GAS TO GAS CORRELATION

Bernard's diagram Cross plot C2+ v/s δ13C1 (Modified after Schoell, 1983)

Origin C2+, % δ13C1, ‰

Bacterial ~0.05 -80 to -55
Thermogenic (Catagenetic) >5 -55 to -30
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Thermogenic (Metagenetic) <5 -30 to -20
 CHEMOSTRATIGRAPHY

 A suite of dominant lithophile

elements such as Zn, Mn, Fe, Mg,
Ca, K, Na, Ni, Cu, Cr, Co, Li, Pb and
stable isotopes of other rare earth
elements are usually chosen for
determining their abundance to
characterize and correlate
subsurface strata
 Using geochemical (elemental)
signatures or ‘fingerprints’,
sedimentary units are defined and
correlated over wide areas
 This technique is of immense use
when paucity of diagnostic fossils

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