GEOCHEMISTRY

GEOCHEMISTRY IN PETROLEUM EXPLORATION

1 INTRODUCTION ............................................................................................................................. 2
1.1 PHILOSOPHY ......................................................................................................................................... 2
1.2 FORMATION OF OIL & GAS ................................................................................................................... 2
1.2.1 Diagenesis .................................................................................................................................... 2
1.2.2 Catagenesis................................................................................................................................... 2
1.2.3 Metagenesis .................................................................................................................................. 2
1.2.4 Migration ...................................................................................................................................... 3
1.3 APPLICATION ....................................................................................................................................... 3
2 ORGANIC FACIES .......................................................................................................................... 3
2.1 THE CARBON CYCLE ............................................................................................................................. 3
2.2 FACTORS INFLUENCING ORGANIC RICHNESS ....................................................................................... 3
2.2.1 Productivity .................................................................................................................................. 3
2.2.2 Preservation.................................................................................................................................. 3
2.2.3 Dilution......................................................................................................................................... 4
3 ORGANIC CHEMISTRY AND ISOTOPES .................................................................................. 4
3.1 NAMES & STRUCTURES ........................................................................................................................ 4
3.1.1 Hydrocarbons ............................................................................................................................... 4
3.1.2 Heterocompounds (NSO).............................................................................................................. 5
3.2 STEREOCHEMISTRY & STRUCTURES .................................................................................................... 5
3.3 REACTIONS........................................................................................................................................... 5
3.4 ISOTOPES .............................................................................................................................................. 5
4 KEROGEN ......................................................................................................................................... 5
4.1 INTRODUCTION ..................................................................................................................................... 5
4.2 FORMATION.......................................................................................................................................... 5
4.3 COMPOSITION....................................................................................................................................... 6
4.4 MATURATION ....................................................................................................................................... 6

5 RESERVOIR TRANSFORMATIONS............................................................................................ 7
5.1 WATER WASHING AND BIODEGRADATION............................................................................................ 7
5.1.1 Water washing .............................................................................................................................. 7
5.1.2 Biodegradation ............................................................................................................................. 7
5.2 OIL SEGREGATION BY GRAVITY ........................................................................................................... 7
5.3 LEAKAGE OF CAP ROCK, DYSMIGRATION THROUGH FAULT ................................................................ 7
5.4 INFILLING RESERVOIR WITH GASES, NATURAL DEASPHALTING .......................................................... 7
5.5 THERMAL CRACKING, MATURATION ................................................................................................... 7

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1 INTRODUCTION
1.1 PHILOSOPHY

We must understand how oil & gas are formed and use this knowledge to locate new HC reservoirs
1.2 FORMATION OF OIL & GAS

50°C

120°C

150°C

250°C

o Example of natural gas characteristics according to their maturity:

Evolution C1/C2+ IC4/nC4

Early diagenesis >0.97 >6
Catagenesis <0.98 <1
Metagenesis >0.97

o Plants and algae’s are buried in fine grained sediments and absence of O2.
o The organic matter is transformed in kerogen by low temperature chemical & biological
reactions.
o The large molecules of kerogen are the precursors of oil & gas.
1.2.1 DIAGENESIS

o Methanogen microorganisms transform debris in biogenic CH4

1.2.2 CATAGENESIS

o Temperature rises and the bacterial action stops (temp >80°C)

o Thermal reactions break the kerogen in smaller molecules called bitumen in an early
stage, then, with increasing maturity, to oil, condensate and finally gas.
1.2.3 METAGENESIS

o The thermal process continues and creates smaller molecules: thermal CH4

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1.2.4 MIGRATION

o The HC are expelled from the source rock and migrate to a trap where it will
accumulate.
1.3 APPLICATION

3 types of geochemical models : organic facies, thermal maturity and volumetric.

2 ORGANIC FACIES
2.1 THE CARBON CYCLE

Oxydation

o Most of organic matter is returned to the atmosphere through the carbon cycle (photosynthesis),
only 1% of the photosynthetic production is preserved in sediments.
o The oxidation in the sediments (down to 300m) will bring the Total Organic Carbon (TOC)
value down to 0.1%.
2.2 FACTORS INFLUENCING ORGANIC RICHNESS

The 3 factors influencing the amount of organic matter in a sediment are: productivity, preservation
and dilution.
2.2.1 PRODUCTIVITY

o Shallow water is the most productive environment (Plants + light: 20 000t/km2)

o In high water zones, water upwelling can increase productivity
2.2.2 PRESERVATION

o Preservation is the most important factor for organic richness. It is linked to:
Anoxia : linked to stagnancy, the sediments are very dark.
Oxygen Minimum Layer (OML): the O2 request is higher than the production, due to decay of
organic matter falling from the upper photic zone.

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Photic zone

High O2
request, no
vertical water
movement

Less O2
demand,

Rapid burial

2.2.3 DILUTION

If the burial becomes extremely rapid, the dilution may become higher than the preservation (Specially in
shales)

3 ORGANIC CHEMISTRY AND ISOTOPES

3.1 NAMES & STRUCTURES

3.1.1 HYDROCARBONS

o Only C & H
Alkanes or paraffins or saturated:
• straight line = n-alkanes (CnH2n+2) (normal…)
• Non linear = iso, meta, etc or use the methyl (CH3) radical

2 different heptanes

• Cyclic (CnH2n) every C is linked to 2 C and 2 H

• Isopropenoids: straight chain of C with a methyl on every 4 C

Unsaturated:

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• Able to combine with additional H

• Alkenes or olefins: double bond between C’s : react easily and do not persist in geological
environment
• Aromatics are cyclic alkenes but they are stable (BTX): they alternate single and double
bonds (delocalised electron) between the C’s
3.1.2 HETEROCOMPOUNDS (NSO)

o Contains also N, O or S
o Very often converted to HC during dia & catagenesis
o Porphyrins (from chlorophyll) are often present in oil
o Asphaltenes: big , highly aromatic molecules
3.2 STEREOCHEMISTRY & STRUCTURES

o Stereochemistry: 3D representation of the molecules

o Isomer: Same chemical formula but different atomic arrangement.(ie; nC4, iC4)
3.3 REACTIONS

o Oxidation: loss of e- which goes to the oxidation agent, or loss of H

o Reduction: gain of e- which comes from the reduction agent or gain of H
o Isomerisation: an isomer is converted to another
3.4 ISOTOPES

o Variation of the number of neutrons

4 KEROGEN
4.1 INTRODUCTION

o Kerogen = large organic matter molecules, insoluble in organic solvents.

o Bitumen = soluble portion.
4.2 FORMATION

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4.3 COMPOSITION

Rare, produces liquid HC

Produces liquid HC

Produces mainly gas

No HC

Maceral equivalent of a mineral for organic matter

4.4 MATURATION

o Maturation is due to high temperatures during a long time

Van Krevelen diagram

o A mature kerogen becomes more aromatic , as these molecules can stack neatly, the
reflectance increases. The vitrinite reflectance assesses the kerogen maturity.

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5 RESERVOIR TRANSFORMATIONS

Two types of transformations:

o Non thermal process
Water washing
Biodegradation
Leakage, transmigration
o Thermal process :
Cracking
Deasphalting

5.1 WATER WASHING AND BIODEGRADATION

o Unable to differentiate the 2 phenomenon as they occur frequently together and

biodegradation hides the water washing effect.
5.1.1 WATER WASHING

o affects high soluble components: benzene, toluene, light alkanes.

5.1.2 BIODEGRADATION

o affects n alkanes.
o GOR, light HC content increase and API gravity decrease.
o Viscosity, sulfur content increase.
o Temperature above 80°C will kill bacteria and stop biodegradation. (around 2000m deep)

5.2 OIL SEGREGATION BY GRAVITY

o Can be reversed ! (top with a lot of gas but less pressure than the bottom or different pore
sizes)

5.3 LEAKAGE OF CAP ROCK, DYSMIGRATION THROUGH FAULT

May result in 2 reservoirs, the upper one with high API gravity (light oil or gas), the lower one with
residual heavy HC and low API gravity.

5.4 INFILLING RESERVOIR WITH GASES, NATURAL DEASPHALTING

o Deasphalting may be due to gas injection (i.e. heptanes) or thermal cracking, the result is
lighter oil and solid residues.
o When the oil becomes lighter, the asphaltenes become less soluble and precipitate.
o Deasphalting brings an API gravity increase and a sulfur content decrease.

5.5 THERMAL CRACKING, MATURATION

o Function of time and temperature (linked to depth).

o Variation of depth, due to tectonic movements can stop or restart cracking process.
o With maturity, API gravity increases , Pour point and viscosity decrease.
o Break the molecules in lighter ones, the high maturity produces dry gas.
o The iC4/nC4 ratio will be high (i.e. > 8) in an immature HC (diagenesis) and will decrease
(ie <1) in the maturity zone (Catagenesis), as maturation creates predominantly n alkanes.

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