Title: Petroleum Geochemistry Research Laboratory Programmed Pyrolysis Method

By: Mark Dreier and Augusta Warden

Date Published: 2021
Suggested Citation: Dreier, M. and Warden, A., 2021, Petroleum Geochemistry Research
Laboratory Programmed Pyrolysis Method: U.S. Geological Survey Web Page,
https://doi.org/10.5066/P9HQSBGH
Keywords: Petroleum Geochemistry Research Laboratory, Programmed Pyrolysis, source rock
potential, HAWK, Flame ionization detector, IR cells, Rock Eval
Method Summary
Programmed pyrolysis is a rapid analytical technique used as a screening tool to evaluate
source rock hydrocarbon-generating potential and thermal maturity. The Petroleum
Geochemistry Research Laboratory (PGRL) method is a modification of the original and most
widely used temperature program for this kind of analysis (Barker, 1974; Espitalie and others,
1977; Peters, 1986; Espitalie and Bordenave, 1993; Peters and Rodriguez, 2017). The entire
temperature program used by this method, which includes modifications, is detailed in the
sample analysis section below. Modern instruments are equipped with infrared detectors,
rather than a thermal conductivity detector, to detect carbon monoxide and carbon dioxide.
Refer to the publications listed in the reference section for further information on the history of
programmed pyrolysis. This PGRL method is intended for use on programmed pyrolysis
instrumentation capable of generating the most commonly reported parameters, including
total organic carbon (TOC), S1, S2, S3 and Tmax.

Scope and Application

This document describes the PGRL programmed pyrolysis method for fast and reliable
screening of large numbers of rock samples prior to analysis by more time-consuming or labor-
intensive procedures. Programmed pyrolysis measurements generate the following parameters
on ground rock samples:
S1: the free hydrocarbon (HC) content present in a sample generated at 300°C (units: mg HC/g
rock). This peak is generally referred to as ‘free oil’ and is measured by the flame ionization
detector (FID).
S2: the HC-generating potential of kerogen present in a rock sample determined by pyrolysis
between temperatures from 300 to 650°C at a heating rate of 25°C/min. (units: mg HC/g rock)
and is measured by the FID.
S3: the carbon dioxide generated during pyrolysis or cracking of kerogen in the rock between
300 and 390°C (units: mg CO2/g rock) and is measured by an infrared (IR) detector.

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Tmax: the temperature in degrees Celsius (°C) where the maximum amount of S2 hydrocarbons
is generated. Tmax is related to thermal maturity and the type of organic matter present in a
rock sample.
Several calculated indices are also determined from programmed pyrolysis data (Hydrogen
Index, Oxygen Index, Production Index, and normalized oil content). These indices are used for
interpretive purposes to help describe petroleum systems, particularly to assess source rock
quality and thermal maturity. Interpretation is not covered in this method, but guidance related
to the use of these parameters and indices is available in the publications listed in the reference
section.
Interferences
Nonindigenous contamination may be present in samples. Common contaminants include
organic liquids and drilling additives such as walnut hulls or gilsonite. In some cases,
contaminants may be filtered or manually removed.
Safety Precaution
This method does not attempt to address health and safety concerns. Adherence to
appropriate health, safety, and regulatory practices are the responsibility of the end user.
Sample Handling, Preservation, Storage, and Holding Times
No particular type of container is preferred; however, it is important to use containers that do
not contaminate the sample. Glass is the preferred container after the sample is ground.
Preservation, storage of samples, and holding times are not a concern for this method as rock is
a geologically stable material.
Apparatus
Example List
Hydrocarbon Analysis With Kinetics (HAWK) instrument with autosampler and associated
computer and software (or equivalent)
Balance capable of accuracy within 0.1 mg
Tweezers
Spatula, scoop, or other device to transfer rock sample
Crucibles from Wildcat Technologies (or equivalent)
Ultra high purity helium
Ultra high purity hydrogen
Zero grade air or higher

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Desiccant such as Drierite (or equivalent)
Sample Preparation
Samples must be ground to a flour-like consistency prior to analysis; this is roughly equivalent
to passing a 60-mesh sieve.
Reagents
There are no reagents used for this method.
Calibration
A single point calibration is used (Beti and Ring, 2019; David Weldon, personal communication,
2015; Weiss and others, 2000). FIDs are linear over a wide range as described by Shellie (2013),
who stated “[f]lame-ionization detector (FID) has a nearly universal response to organic
compounds…and a wide linear response range (107)”. The PGRL verifies the linearity of the FID
annually by analyzing a calibration standard at varying weights. The current calibration standard
used in the PGRL has a TOC value of approximately 3.6 weight percent and is linear from
approximately 30 mg to approximately 150 mg. Linearity is confirmed when the standard meets
acceptance criteria. Verification of the calibration is performed within each sample batch by
analysis of the PGRL daily operating standards that have accepted values and acceptance
criteria (see Quality Control section for further information).
Sample Analysis
Approximately 70 mg of ground rock sample is weighed into a sample crucible. The crucible is
then placed into the autosampler. Samples are automatically run through use of an
autosampler and the sample sequence is established using the instrument software.
The PGRL programmed pyrolysis method was verbally communicated to PGRL staff during the
installation of the HAWK programmed pyrolysis instrument and is pictorially represented in the
HAWK Workstation Manual (from Wildcat Technologies) version 1.1, 2015, page 20. An
example pyrogram is shown in Figure 1. Samples are usually analyzed under the following
conditions using helium as the carrier gas for the pyrolysis phase and air as the carrier gas for
the oxidation phase: a sample is heated in a helium atmosphere for 5 minutes at 100°C, the
oven then ballistically heats to 300°C and the temperature is held for 3 minutes. A ramp rate of
25°C/min heats the oven from 300°C to 650°C completing the pyrolysis phase where S1, S2, S3,
and Tmax are measured. The oven cools to 300°C and is then ramped from 300°C to 750°C at
25°C/min and held at 750°C for 5 minutes to complete the oxidation phase.

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Figure 1. Typical pyrogram plot showing flame ionization detector (FID) signal (black line),
temperature (red line), carbon monoxide (CO) (yellow line) and carbon dioxide (CO2) (green
line) infrared (IR) signals. Hydrocarbon is abbreviated ‘HC’ in the pyrogram.
Quality Control
Reference materials are not readily available for programmed pyrolysis. The only reference
material currently available for programmed pyrolysis is from Wildcat Technologies,
manufacturer of the HAWK, named WT1. The Norwegian Petroleum Directorate (Weiss and
others, 2000) has two rock standards for interlaboratory testing, JR-1 and SR-1. To adequately
cover the range of S1, S2, S3 and Tmax (each reference material has a single S1, S2, S3 and
Tmax) values present in samples analyzed, the PGRL uses daily operating standards that include
reference materials that are under development within the USGS that represent a broad range
of typical source rocks (Birdwell and Wilson, 2019) as well as standards developed within the
PGRL. Daily operating standards (standards that have an established value determined through
repeat analysis in the PGRL with acceptance criteria) are analyzed within each batch of samples
minimally at the beginning and the end of a batch. To determine acceptance criteria, the PGRL
performs multiple analyses on a daily operating standard and determines an average value and
the standard deviation. To determine acceptance criteria, three times the standard deviation is
added to the average value (for upper acceptance criteria) and subtracted from the average
value (for lower acceptance criteria). The acceptance criteria for one of the reference materials
under development, ShBOQ-1, are shown in Table 1. Should a daily operating standard fail to
meet acceptance criteria within a batch, samples associated with the failed standard are either
reanalyzed or a comment is associated with the data.

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 ShBOQ-1*
TOC** (wt. S1 (mg S2 (mg S3 (mg CO2/g
%) HC***/g rock) HC***/g rock) rock) Tmax**** (°C)
Average 4.95 0.96 30.76 0.61 425
Standard Deviation 0.10 0.10 0.96 0.08 1.4
3x Standard Deviation 0.29 0.30 2.88 0.23 4.2
Lower Acceptance Criteria 4.66 0.67 27.88 0.38 421****
Upper Acceptance Criteria 5.24 1.26 33.64 0.84 429****
Table 1. Example determination of upper and lower acceptance criteria for a daily operating standard (ShBOQ-1) from 220
analyses (see Table 2 for more information) on a single programmed pyrolysis instrument (HAWK). Samples were analyzed
from 8/19/2019 to 8/25/2021.
* Raw data are available in Data used to determine acceptance criteria for the Petroleum Geochemistry Research Laboratory
Programmed Pyrolysis Method (Dreier and Warden, 2021).
**Total organic carbon is abbreviated TOC.
***Hydrocarbon is abbreviated ‘HC’ in the table
****Tmax is rounded to the nearest whole degree

Data Reduction, Calculations, and Reporting

Data reduction automatically occurs after analysis of each sample by the instrument software
for TOC, S1, S2, S3, and Tmax. This involves integration of the FID and IR signals to obtain S1, S2,
and S3 values. The calculations below are determined and reported. Note that TOC may be
determined by a number of analytical techniques besides programmed pyrolysis. When
reporting data, it is important to state the TOC technique used (TOC values from the Petroleum
Geochemistry Research Laboratory Total Organic Carbon and Total Carbon Method (Oliver and
Warden, 2020) are commonly used in these calculations by the PGRL).
Hydrogen Index (HI) = S2×100/TOC (mg HC/g Corg*)
Oxygen Index (OI) = S3×100/TOC (mg CO2/g Corg*)
Production Index (PI) = S1/(S1+S2)
Kerogen type indicator = S2/S3
Normalized oil content = S1×100/TOC (mg HC/g Corg*)
*
Corg = organic carbon.
Reports include TOC (with appropriate technique listed), S1, S2, S3, Tmax, and PI for each
sample. HI, OI, and normalized oil content are reported when a TOC value has been determined
in the PGRL or made available to the PGRL. All associated quality control sample results are also
reported.
Method Performance
To demonstrate method performance, three USGS reference materials currently under
development were chosen: ShBOQ-1, ShWFD-1 and ShMCO-1. These reference materials were
analyzed by the PGRL on a HAWK programmed pyrolysis instrument. To show precision, the

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average and the variability (standard deviation) for TOC, S1, S2, S3, and Tmax are listed in Table
2. Table 3 demonstrates accuracy and precision by comparing the average value from the PGRL
analyses on ShBOQ-1, ShWDF-1 and ShMCO-1 reference materials to the interlaboratory study
results on these reference materials (Dreier and Warden, 2021; Birdwell and Wilson, 2019).
Daily Operating Standard

TOC Standard Deviation

Tmax**** (°C) Average

TOC **(wt. %) Average

S1 Standard Deviation

S2 Standard Deviation

S3 Standard Deviation
S1 (mg HC***/g rock)

S2 (mg HC***/g rock)

Tmax (°C) Standard

S3 (mg CO2/g rock)

Deviation
Average

Average

Average
Name

Count

ShBOQ-
220 4.95 0.10 0.96 0.10 30.76 0.96 0.61 0.08 425 1.4
1*
ShWDF-
49 7.79 0.14 0.90 0.07 41.49 1.60 0.69 0.08 429 0.8
1*
ShMCO-
42 2.77 0.06 0.23 0.01 4.76 0.28 1.12 0.10 423 0.5
1*
Table 2. Average and variability from the Petroleum Geochemistry Research Laboratory analyses on the daily operating
standards ShBOQ-1, ShWDF-1 and ShMCO-1. The standards were analyzed on a HAWK programmed pyrolysis instrument from
August 19, 2019 through August 25, 2021.
* Raw data are available in Data used to determine acceptance criteria for the Petroleum Geochemistry Research Laboratory
Method (Dreier and Warden, 2021).**Total organic carbon is abbreviated TOC.
***Hydrocarbon is abbreviated ‘HC’ in the table
****Tmax is rounded to the nearest whole degree
TOC** (wt. %)

TOC** (wt. %)
Tmax ****(°C)

Tmax**** (°C)
HC***/g rock)

HC***/g rock)

HC***/g rock)

HC***/g rock)
S3 (mg CO2/g

S3 (mg CO2/g
S1 (mg

S2 (mg

S1 (mg

S2 (mg
rock)

rock)
ShBOQ-1* ShWFD-1*
Birdwell and Wilson Birdwell and Wilson
152 112 108 90 92 146 120 128 119 127
(2019) Count (2019) Count
PGRL Count 220 220 220 220 220 PGRL Count 49 49 49 49 49
Birdwell and Wilson Birdwell and Wilson
5.09 1.27 31.59 0.7 424 7.99 1.08 41.65 0.64 428
(2019) Average (2019) Average
PGRL Average 4.95 0.96 30.76 0.61 425 PGRL Average 7.79 0.90 41.49 0.69 429
Birdwell and Wilson Birdwell and Wilson
(2019) Standard 0.18 0.11 2.57 0.08 1.1 (2019) Standard 0.25 0.09 2.24 0.21 2.1
Deviation Deviation
PGRL Standard Deviation 0.10 0.10 0.96 0.08 1.4 PGRL Standard Deviation 0.14 0.07 1.60 0.08 0.8
ShMCO-1*
Birdwell and Wilson
(2019) Count 109 117 113 135 137
PGRL Count 42 42 42 42 42
Birdwell and Wilson
(2019) Average 2.9 0.3 4.51 1.25 422
PGRL Average 2.77 0.23 4.76 1.12 423

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 Birdwell and Wilson
(2019) Standard
Deviation 0.11 0.02 0.2 0.42 2
PGRL Standard Deviation 0.06 0.01 0.28 0.10 0.5

Table 3. Comparison of Petroleum Geochemistry Research Laboratory (PGRL) analytical results to results contained in the
Birdwell and Wilson (2019) interlaboratory study for ShBOQ-1, ShWDF-1 and ShMCO-1 demonstrating accuracy and precision.
Note that outliers were removed from the Birdwell and Wilson dataset based on criteria described by the authors.
* Raw data for analyses performed in the Petroleum Geochemistry Research Laboratory (PGRL) are available in Data used to
determine acceptance criteria for the Petroleum Geochemistry Research Laboratory Method (Dreier and Warden, 2021). All
results were determined in the PGRL from August 19, 2019 through August 25, 2021.
**Total organic carbon is abbreviated ‘TOC’.
***Hydrocarbon is abbreviated ‘HC’.
****Tmax is rounded to the nearest whole degree.

Trademark Disclaimer
The use of trade, product, or firm names in this method is for descriptive purposes only and
does not imply endorsement by the U.S. Government.
References
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Beti, D.R., Ring, T.A., 2019, Programmed Temperature Pyroysis: Alterations to the Standard
Method: Encyclopedia of Petroleum Geoscience. DOI: 10.1007/978-3-319-02330-4_302-1
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Unconventional Resources Technology Conference, 19 p., DOI:10.15530/urtec-2019-457.
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