GEOCHEMICAL ANALYSIS BASICS

Geochemical analysis is used to determine the type and quantity of organic carbon and other
properties of unconventional reservoirs and source rocks. Organic carbon in the form of
kerogen is the remnant of ancient life preserved in sedimentary rocks, after degradation by
bacterial and chemical processes, and further modified by temperature, pressure, and time.
The latter step, called thermal maturation, is a function of burial history (depth) and proximity
to heat sources. Maturation provides the chemical reactions needed to give us gas, oil,
bitumen, pyrobitumen, and graphite (pure carbon) that we find while drilling wells for
petroleum.

Organic carbon is usually associated with shales or silty shales, but may be present in
relatively clean siltstone, sandstone, and carbonate rocks.

A source rock is a fine grained sediment rich in organic matter that could generate crude oil or
natural gas after thermal alteration of kerogen in the Earth's crust. The oil or gas could then
migrate from the source rock to more porous and permeable sediments, where ultimately the
oil or gas could accumulate to make a commercial oil or gas reservoir.

If a source rock has not been exposed to temperatures of about 100 °C, it is termed a potential
source rock. If generation and expulsion of oil or gas have occurred, it is termed an actual
source rock. The terms immature and mature are commonly used to describe source rocks and
also the current state of the kerogen contained in the rock.

Total organic carbon (TOC) as measured by laboratory techniques historically has been used
to assess the quality of source rocks, but now is widely used to help evaluate some
unconventional reservoirs (reservoirs that are both source and productive).

Pathways that convert living

organisms to organic carbon, from
"Bitumens, Asphalts, and Tar Sands"
by George V. Chilingar, Teh Fu Yen,
1978.

In the lab, it is relatively easy to

distinguish kerogen from
hydrocarbons: kerogen is insoluble in
organic solvents, oil and bitumen are soluble. Pyrobitumen is not soluble but its hardness is
used to identify it from kerogen. Graphite is evident on resistivity logs because of the very low
resistivity; all other forms of organic carbon are resistive.

Organic carbon has a density near that of water, so it looks like porosity to conventional
porosity logs. High resistivity with some apparent porosity on a log analysis is a good
indicator of organic carbon content OR ordinary hydrocarbons OR both.

TYPES OF KEROGEN
Organic material can be classified according to the source of the material, as shown below.
 Origin, type, source, and hydrocarbon potential of different kerogens. Organic content in gas
shales is usually Type II, as opposed to coals, which contain mostly Type III

The most commonly utilized scheme for classifying

organic matter in sediments is based on the relative
abundance of elemental carbon, oxygen, and hydrogen
plotted graphically as the H/C and O/C ratio on a so
called Van Krevelen diagram.

The classic Van Krevelen diagram

Rather than plot the elemental ratios it is common to

plot indices determined by a pyrolysis technique
referred to as Rock Eval. In the pyrolysis techniques
two indices are determined: the Hydrogen Index (HI)
which is milligrams of pyrolyzable hydrocarbons
divided by TOC and the Oxygen Index (OI) which is
milligrams of pyrolyzable organic carbon dioxide
divided by TOC.

Cross-plots of both elemental H/C and O/C ratios or of

HI and OI are utilized to discriminate four ‘fields’ which
are referred to as Types I, II, III, and IV kerogen.

Type I kerogen is hydrogen rich (atomic H/C of 1.4 to 1.6: HI of > 700) and is derived
predominantly from zooplankton, phytoplankton, micro-organisms (mainly bacteria) and lipid
rich components of higher plants (H/C ratio 1.7 to 1.9).

Type II kerogen is intermediate in composition (H/C ≈ 1.2: HI ≈ 600) and derived from mixtures
of highly degraded and partly oxidized remnants of higher plants or marine phytoplankton.
Type III kerogen is hydrogen poor (H/C ratio 1.3 to 1.5) and oxygen rich and is mainly derived
from cellulose and lignin derived from higher plants.

Type IV kerogen is hydrogen poor and oxygen rich and essentially inert. This organic matter is
mainly derived from charcoal and fungal bodies. Type IV kerogen is not always distinguished
but is grouped with Type III.

The different types of organic matter are of fundamental importance since the relative
abundance of hydrogen, carbon, and oxygen determines what products can be generated from
the organic matter upon diagenesis. Since coal is comprised predominantly of Type III
kerogen, there is little liquid hydrogen generating capacity. If the coal includes abundant
hydrogen rich components (such as spores, pollen, resin, waxes - Type I or II), it will generate
some liquid hydrocarbons. Although not common, some oil deposits are thought to be sourced
by coals.

Note: Portions of the above Section, and the next Section, were taken verbatim (with moderate
editing) from CBM Solutions reports.

ANALYZING TOC IN THE LABORATORY

The total organic carbon content of rocks is obtained by heating the rock in a furnace and
combusting the organic matter to carbon dioxide. The amount of carbon dioxide liberated is
proportional to the amount of carbon liberated in the furnace, which in turn is related to the
carbon content of the rock. The carbon dioxide liberated can be measured several different
ways. The most common methods use a thermal conductivity detector or infrared
spectroscopy.

Many source rocks also include inorganic sources of carbon such as carbonates and most
notably calcite, dolomite, and siderite. These minerals break down at high temperature,
generating carbon dioxide and thus their presence must be corrected in order to determine the
organic carbon content. Generally, the amount of carbonate is determined by acid digestion
(normally 50% HCl) and the carbon dioxide generated is measured and then subtracted from
the total carbon dioxide to obtain the organic fraction.

Total organic carbon is often taken to mean the same thing as kerogen, but this is not the case.
Kerogen is made up of oxygen, nitrogen, sulphur, and hydrogen, in addition to carbon. The
standard pyrolysis lab procedure measures only the carbon, so total organic carbon excludes
the other elements.

About 80% of a typical kerogen (by weight) is carbon, so the weight fraction of TOC is 80% of
the kerogen weight. The factor is lower for less mature and higher for more mature kerogen:
1: Wtoc = Wker * KTOC
OR 2: Wker = Wtoc / KTOC

Where:
Wtoc = weight fraction of organic carbon
Wker = weight fraction of kerogen
KTOC = kerogen correction factor - range = 0.68 to 0.90, default 0.80
Another lab procedure, called RockEval, burns both hydrogen and carbon, so the data needs
to be calibrated to the standard method by performing a chemical analysis on the kerogen.
Typically the organic carbon needs to be reduced by about 10% (the weight of the hydrogen
burned) to match the standard method.

Rock Eval is the trade name for a set of equipment used in the lab to measure organic content
of rocks, as well as other properties of the organics that help to identify the kerogen type.
Rock-Eval combusts a crushed sample of rock at 600ºC. Refractory organic matter such as
inertinite does not combust readily at 600ºC so most coal samples yield Rock-Eval measured
TOC values much lower than actual values because of incomplete combustion. Rock-Eval is
not recommended for use with coals or source rocks with significant amounts of Type III and
IV kerogen.

A rock sample is crushed finely enough so that 85% falls through a 75 mesh screen.
Approximately 100 mg of sample is loaded into a stainless steel crucible capped with a micro
mesh filter. To ensure accuracy, standard samples are loaded at the beginning and end of the
run. Any drift in data can be detected and the samples rerun if necessary.

The analyzer consists of a flame ionization detector and two IR detector cells. The free
hydrocarbons (S1) are determined from an isothermal heating of the sample at 340 degrees
Celsius. These hydrocarbons are measured by the flame ionization detector. The temperature
is then increased from 340 to 640 degrees Celsius. Hydrocarbons are then released from the
kerogen and measured by the flame ionization detector creating the S2 peak. The temperature
at which S2 reaches its maximum rate of hydrocarbon generation is referred to as Tmax. The
CO2 generated from the oxidation step in the 340 to 580 degrees Celsius is measured by the IR
cells and is referred to the S3 peak.

Measured results from a typical Rock Eval

study will contain:
TOC% - Weight percentage of organic
carbon
S1 = amount of free hydrocarbons in
sample (mg/g)
S2 = amount of hydrocarbons generated
through thermal
cracking (mg/g) – provides the
quantity of
hydrocarbons that the rock has the
potential to
produce through diagenesis.
S3 = amount of CO2 (mg of CO2/g of rock) - reflects the amount of oxygen in the oxidation
step.
Ro = vitrinite reflectance (%)
Tmax = the temperature at which maximum rate of
generation of hydrocarbons occurs.

Calculated results include:

Hydrogen index
1: HI = 100 * S2 / TOC%
Oxygen index
2: OI = 100 * S3 / TOC%
Production index
3: PI = S1 / (S1 + S2)

Depth (m) TOC SRA Tmax Meas. HI OI S2/S3 S1/TOC*100 PI

 Top S1 S2 S3 (°C) % Ro
X025 1.35 0.05 1.72 0.63 444 128 47 3 4 0.03
X040 1.18 0.05 1.65 0.57 443 140 49 3 4 0.03
X050 0.83 0.03 1.31 0.55 443 158 66 2 4 0.02
X065 0.80 0.04 1.00 0.58 440 126 73 2 5 0.04
X075 0.75 0.05 1.04 0.72 438 138 96 1 7 0.05
X090 1.04 0.09 2.52 0.29 452 241 28 9 9 0.03
X110 1.02 0.05 1.16 0.56 441 114 55 2 5 0.04
X135 1.05 0.05 1.32 0.57 443 125 54 2 5 0.04
Laboratory measured TOC values (weight %) with measured and computed indices

HI versus OI plot example, indicating Type III kerogen

An alternate method for measuring TOC by solution rather than pyrolysis is described below,
from a 1980's TOC report from Australia.

"The samples are analyzed for total organic carbon (TOC) according to AS 1038 Part 6.
Moisture determinations are made to permit conversion to a dry basis. Carbon occurring as
carbonate ion is determined to correct the gross carbon data to give the organic carbon
content. This is done by driving off carbonate minerals with HCl acid.

The crushed and sieved (100 mesh) samples are weighed and exhaustively extracted in a
Soxhlet apparatus using a benzene-methanol mixture. After removal of methanol by azeotropic
distillation with benzene, the residue in benzene is diluted with hexane and the hydrocarbon
solution separated by filtration from the brown precipitate. The latter is then dissolved in
methanol. The yield of methanol soluble material is determined gravimetrically.

The hexane soluble portion of the extractable organic matter (E.O.M.) is weighed and
chromatographed on silica. Elution with hexane gives predominantly alkanes and subsequent
elution with hexane/benzene yields mainly monocyclic and polycycllc aromatic hydrocarbons.
The eluted hydrocarbons are weighed, and then analyzed by gas chromatography / mass
spectrometry."

GEOCHEMICAL LOGS
Measured and calculated indices can be plotted versus depth; the resulting log is called a
Geochemical Log.
A geochemical log from offshore East Coast Canada
 KEROGEN MATURITY
The hydrocarbon potential of organic
carbon depends on the thermal history of
the rocks containing the kerogen. Both
temperature and the time at that
temperature determine the outcome.
Medium temperatures (< 175 C) produce
mostly oil and a little gas. Warmer
temperatures produce mostly gas.

Hydrocarbon type versus temperature

defines "oil window" and "gas window",
with some obvious overlap

Vitrinite reflectance (Ro) is used as an

indicator of the level of organic maturity
(LOM). Ro values between 0.60 and 0.78
usually represent oil prone intervals. Ro >
0.78 usually indicates gas prone. High
values can suggest "sweet spots" for
completing gas shale wells.

Measurement of vitrinite reflectance was

described as follows from the 1980's TOC
report.

"Sample chips or sidewall core samples

are cleaned to remove drilling mud or mud
cake and then crushed using a mortar and
pestle to a grain-size of less than 3 mm.
Samples are mounted in cold-setting resin
and polished ''as received", so that whole-rock samples rather than concentrates of organic
matter are examined. This method is preferred to the use of demineralized concentrates
because of the greater ease of identifying first generation vitrinite and, for cuttings samples, of
recognizing cavings. The core samples are mounted and sectioned perpendicular to the
bedd1ng.

Vitrinite reflectance measurements are made using immersion oil of refractive index 1.518 at
546 nm and 23°C and spinel and garnet standards of 0.42%, 0.917% and 1.726% reflectance for
calibration. Fluorescence-mode observations are made on all samples and provide
supplementary evidence concerning organic matter type, and exinite abundance and maturity.
For fluorescence-mode a 3 mm BG-3 excitation filter is used with a TK400 dichroic mirror and a
K490 barrier filter."

Tmax is also a useful indicator of maturity, higher values being more mature.

Graphs of HI vs Ro and HI vs Tmax are used to help refine kerogen type and to assess maturity
with respect to the oil and gas "windows". Depth plots of Ro and Tmax are helpful in spotting
the top of the oil or gas window in specific wells, and in locating sweet spots for possible
production using horizontal wells.
 Crossplots of HI vs Tmax and HI vs Ro determine organic maturity, kerogen type,
and whether the rock is in the oil or gas window. Immature and post mature rocks are not
overly interesting as possible source or reservoir rocks.
Depth plot of Ro to determine trend line and location of oil and gas windows (Ro > 0.55).
Ro is plotted on a logarithmic scale, which makes the trend line relatively straight.
Thermal maturity as indicated by vitrinite reflectance (Ro) versus depth for a Barnett shale,
showing "sweet spot" and oil versus gas “windows”.

THIS PAGE
Geochemical Analysis Basics
Types Of Kerogen
Analyzing TOC In The Lab
Geochemical Logs

THIS CHAPTER
Total Organic Carbon TOC
Shale Gas Analysis
Immature Oil Shale Analysis
Tight Gas Analyzis
Tight Oil / Shale Oil Analysis

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