Source Rock Analysis
Source Rock Analysis
Source Rock Analysis
Manual Information
Author(s): K. Fujine
Reviewer(s): L. Brandt
Manager Approval (Name, Title, Date): D.J. Houpt
Audience: Scientists, Laboratory Technicians
Origination date: 5/12/08
Current version: V1.0 | 8/20/13
Revised: V1.1 | 1/6/2014 (IODP-II)
Domain: Chemistry
System: Rock Maturity
Keywords: Rock-Eval, Tmax, Source Rock, Hydrocarbon Maturity
Introduction 1
Instrument Calibration 8
Sample Preparation 8
Sample Analysis 9
LIMS Integration 15
Introduction
This user guide contains standard operational procedures for the Source Rock Analyzer (SRA). The chemistry labor-
atory technician performs maintenance and configuration of the SRA. Information for the laboratory technician is
presented in the SRA Analyzer Advanced User Guide.
Method Overview
Pyrolysis analysis is conducted on dried and ground sediments or borehole source rock for the purpose of safety
monitoring. The analysis yields information about thermal maturation and source of hydrocarbons at the drilled
site, as well as petroleum potential.
Method Theory
The pyrolysis method consists of a programmed temperature heating in a pyrolysis oven in an inert atmosphere
(helium) of a small sample (~50100 mg) to quantitatively and selectively determine free hydrocarbons contained
in the sample and the hydrocarbon- and oxygen-containing compounds that are volatilized during the cracking of
unextractable organic matter in the sample (kerogen).
Free hydrocarbons volatilized below 330C and measured by the flame ionization detector (FID) comprise
the S1 peak.
Very heavy hydrocarbons (>C40) volatilize and nonvolatile organic compounds crack at temperatures up to
550C. These are measured by FID and comprise the S2 peak.
CO2 released during kerogen cracking in the 300390C range is measured on an infrared detector (S3
peak).
Maturation of organic matter can be estimated by the Tmax range:
Tmax = 400430C: immature organic matter
Tmax = 435450C: mature or oil zone
Tmax > 450C: overmature zone
Pyrolysis data may be compromised in samples containing >10 wt% carbonate and for young (<1 Ma) or very im-
mature organic matter (Tmax < 400C) (Peters, 1986). Samples with <0.5 wt% TOC may not give reliable results be-
cause of the small size of the S1, S2, and S3 signals.
Data Values
The data obtained from the Rock-Eval/TOC analyses are defined by the following parameters (Espitali et al.,
1977):
S1, S2, S3, S4
Tmax
Total Organic Carbon (TOC)
Hydrocarbon Index (HI)
Oxygen Index (OI)
Production Index (PI)
S1/TOC
Pyrolysis Carbon (PC)
Residual Carbon (RC)
S2/S3
S1 Parameter
S1 (milligrams of hydrocarbon per gram of rock) is an indication of free hydrocarbons (gas and oil) in the sample.
S1 > 1 mg HC/g rock may be indicative of an oil show. S1 normally increases with depth.
Free thermally extractable hydrocarbons in the whole rock sample that vaporize at temperatures up to ~330C are
included in S1. Heavier free hydrocarbons and nonhydrocarbons (resins, asphaltenes) that vaporize or crack at
higher temperatures are included in the S2 peak (Clementz, 1979). Determination of the total thermal extractable
content (S1) in some cases may require analysis of extracted rock samples that add the reduction in S2 (S2 whole
rock S2 extracted rock) to the whole rock S1 to account for the heavy free hydrocarbons that carry over into the
S2 peak.
S1 can be elevated by contamination from organic drilling fluid additives such as diesel, walnut shells, Qwik-Seal,
Lubra beads, gilsonite, etc. Nonindigenous hydrocarbons expelled from source rocks elevate the S1 value in a res-
ervoir rock. Also, fungi growth on wet samples increase S1 (Peters, 1986). Ratios (PI, S1/TOC) are increased as a
result of any of these factors.
To convert S1 from mg HC/g rock to ppm, multiply the S1 value by 1000. To convert the original S1 value to an ap-
proximate barrels of oil per acre foot, multiply by 20.082.
(mg HC/g) (20.082 bblg/acreft mg HC) = bbl/acre ft
S2 Parameter
S2 (milligrams of hydrocarbon per gram of rock) hydrocarbons result from the cracking of kerogen and high molec-
ular weight free hydrocarbons that do not vaporize in the S1 peak. S2 is an indication of the quantity of hydrocar-
bons that the rock has the potential of producing should burial and maturation continue. This parameter normally
decreases with burial depths >1 km. The shape of the S2 peak is characteristic of the organic matter type.
S2 values may be reduced by weathering effects, as atomic H/C ratios are reduced by oxidation (van Krevelen,
1984). Also, S2 values may be affected by salt ionization due to saltwater/mineral decomposition at very high tem-
peratures (>550C) or a high FID/splitter block temperature on the pyrolysis instrument (Espitali et al., 1985).
To convert to ppm, multiply the S2 value by 1000. To convert the original S2 value to an approximate barrels of oil
per acre foot, multiply by 20.082.
TOC Parameter
TOC = weight percent of carbon (unit weight of carbon per unit weight of whole rock). TOC is composed of con-
vertible fraction, which represents the hydrocarbon already generated (S1) and the potential to generate hydro-
carbons (S2). The residual fraction (S4) has no potential to generate hydrocarbons. In Rock-Eval terms the TOC is
defined as:
TOC = PC + RC
TOC = [k (S1 + S2)]/10 + S4/10
Where PC = pyrolyzed carbon and RC = residual carbon. k = 83 (an average carbon content of hydrocarbons by
atomic weight); for inertinitic-rich samples, the k value may be as high as 89.
Hydrocarbon Index (HI) Parameter
HI = normalized hydrocarbon content of a rock sample. Kerogen type information is derived from this value as fol-
lows:
Type I kerogens are hydrogen rich
Type III kerogens are hydrogen poor
Type II kerogens are intermediate between Type I and Type III
HI decreases as the sample matures. HI may be lowered by weathering or mineral matrix interactions, which cause
reduction in the S2 value. Marine organisms and algae, in general, are composed of lipid- and protein-rich organic
matter, where the ratio of H to C is higher than in the carbohydrate-rich constituents of land plants. HI typically
ranges from ~100 to 600 in geological samples. High HI values (>400) indicate large proportions of well-preserved
algal and microbial organic matter.
HI = (S2 100)/TOC
S1/TOC Parameter
The ratio of free hydrocarbons (S1) to TOC may be used to identify source or reservoir rocks (Jarvie and Baker,
1984). The S1 determination yields lighter hydrocarbons, which are usually lost during solvent evaporation. Solvent
extraction is much more complete in the nonhydrocarbon (NSO and asphaltene) fraction. This parameter can be
evaluated as follows:
Source rocks have above average S1/TOC ratios
Bibliography
Claypool, G.E., and Reed, P.R., 1976. Thermal-analysis technique for source-rock evaluation: quantitative estimate
of organic richness and effects of lithologic variation: AAPG Bull, 60:608612.
Clementz, D.M., 1979. Effect of oil and bitumen saturation on source-rock pyrolysis. AAPG Bull, 63:22272232.
Espitali, J., Laporte, J.L., Madec, M., Marquis, F., Leplat, P., Paulet., and Boutefeu, A., 1977. Mthode rapide de
caractrisation des roches mres, de leur potential ptrolier et de leur degr d'volution. Revue de l'Institut Fran-
ais du Ptrole, 32:2342.
Espitalie, J., 1982. Institute Francis du Petrole, Syntheses Geologiques et Geochimie. 7020 dated April 8.
Espitali, J., Deroo, G., and Marquis, F., 1985. La pyrolyse Rock-Eval et ses applications. Part I, Revue de l'Institut
Franais du Ptrole 40 (1985), pp. 563-578.
Jarvie, D. M., and Baker, D.R., 1984. Application of the Rock-Eval III Oil Show Analyzer to the study of gaseous hy-
drocarbons in an Oklahoma gas well, 187th ACS National Meeting, St. Louis Missouri, April 8-13.
Peters, K.E., 1986. Guideline for evaluating petroleum source rocks using programmed pyrolysis. AAPG Bull,
70:318329.
Pimmel, A., and Claypool, G., 2001. Introduction to shipboard organic geochemistry on the JOIDES Resolution. ODP
Tech. Note, 30. doi:10.2973/odp.tn.30.2001
Shipboard Scientific Party, 2004. Explanatory notes. In Erbacher, J., Mosher, D.C., Malone, M.J., et al., Proc. ODP,
Init. Repts., 207: College Station, TX (Ocean Drilling Program), 194. doi:10.2973/odp.proc.ir.207.102.2004
van Krevelen, D.W., 1984. Organic geochemistry old and new. Organic Geochemistry, 6:110.
Main control unit: oven and detector temperature control unit and gas flow controllers for the FID com-
bustion gas, carrier gas, and oxidation gas
Infrared (IR) section
Combustion with gas separation and FID (pedestal, oven, and conversion FID)
Laboratory Equipment
Analytical balance (see Figure 2; Analytical Balance User Guide)
SR Analyzer, Humble Instruments and Services
Reagents
Methanol
Compressed gases
o Hydrogen, 6080 psi (45.5 bar)
o Helium carrier gas, 6080 psi (44.5 bar)
o Air, GC analysis grade, 6080 psi (44.5 bar)
o Air, laboratory grade, 60100 psi (46.8 bar)
Standards
Colorado Oil Shale Silica (COSS) house standard
Standard material (99986)
Instrument Calibration
The first sequence for an expedition must include a Blank and a Standard to calibrate the SRA each time the in-
strument is turned on after power off (e.g., loss of power). After this initial calibration, a Blank and a Standard
should be measured once per day to verify calibration of the SRA.
If one calibration applies to several batches, each batch should include a QA/QC Standard to verify calibration.
See the SR Analyzer Advanced User Guide for information about calibrating the detectors.
Sample Preparation
Sediments and sedimentary rock samples logged into the LIMS system as SRANL are analyzed by SRA. During sam-
ple preparation, keep in mind that sample container numbers must correlate with autosampler place numbers.
Sample preparation includes the following steps:
Freeze-dry sample
Grind and homogenize sample
Weigh sample
Place sample in a crucible in the autosampler tray
Text ID (parent) Text ID (child) Mass Container number LIMS code SRA code
Blank 99 (Calibration blank; always 99) BLK
STD99986 OTHR137987 65.0 100 (Calibration STD; always 100) QAQCSTD STD
: : : : : :
: : : : : :
Weighing Samples
See Quality Assurance/Quality Control for sample amounts and explanation of sample codes.
1. If a weight recording chart is not available on the SRA PC desktop, prepare a weight recording chart with the
following headers (see table above):
Text ID: copy new text ID from Cahn software window after uploading the mass
Mass: sample amount weighed into crucible (mg)
Container number: same as autosampler tray number the sample will be placed in
LIMS code: Objective - Mass (part of sample): QA/QC - QAQC
SRA code:
o BLK: calibration blank
o STD: calibration standard
o TPH: unknown sample, QA/QC_blank, QAQC_CV
2. Wipe sample filler, spatula, and forceps with methanol.
3. Log into the balance system for Cahn electrobalance using LIMS user ID.
4. Click Test Options, enter a value from 150 to 200, then click Save/Exit.
5. Place weighing paper on both balance pans, close the door, and click Tare and Start on the balance software
main screen.
6. Once the measurement is completed and the value is acceptable, click Get Mass at the bottom of the Dual
Balance Plot area.
7. Place sample on the weighing paper in the left pan and click Weigh and Start on the screen.
8. Once the measurement is completed and value is acceptable (S1 not equal to 0), click Get Mass.
9. Place weighed sample material in a crucible using sample filter.
10. Select Mass (part of sample) from the Objective drop-down list, enter a part of the text ID in the box below
Objective, and click Search.
11. Highlight the appropriate sample from the search list and click Assign.
12. Click Save at the bottom left of the screen to save mass with a measurement code to LIMS.
13. Write text ID for child sample, mass, container number, and codes in weight chart.
Sample Analysis
Sample analysis workflow is as follows:
Prepare the instrument (see Preparing the SRA Instrument).
Set up software for sequence acquisition (see Setting up the Software).
Acquire samples (see Running Samples).
Running Samples
To analyze samples, fill in the Acquisition Setup screen and confirm sample information on the Analysis screen.
1. Select Main Menu > Acquisition to open the Acquisition Setup screen (Figure 10). Fill in the fields:
Operator: operators last name. This name is the key to access LIMS.
Sample Selection: select the samples to be run from the list shown on the screen.
2. Specify the data folder:
Select parent folder EXPxxx from the explorer window on the screen.
Enter subfolder name EXPxxx_sequence number (e.g., EXP777_1, EXP777_2) in Data Folder field.
3. Click Next to open the Analysis screen (Figure 11).
4. Click Info at the bottom right to open detail information and confirm the information for the first sample.
5. Click Start Sequence above the sample window to start the run. The software will ask for confirmation of SRA
function after starting the first measurement (e.g., autosampler arm position, turn on the FID, etc.).
Calibration Blank
Calibration Standard
Calibration standard is ~80 mg of CS material
One CS is included in each sequence of 50 samples; more samples require additional calibration
For smaller batches, the instrument is calibrated once per day
QA/QC Standard
Calibration verification (CV) is conducted for each batch of 10 samples, one of the following:
CS (60 mg)
COSS (80 mg)
Standard 999986 (60 mg); results:
o S1 = 0.16 mg HC/g
o S2 = 8.41 mg HC/g
o S3 = 0.39 mg CO2/g
o S4 = 23.99 mg C/g
o Tmax = 418C
o TOC = 3.11 wt%
QA/QC Blank
A QA/QC blank can be measured in either of the following ways:
Measure an empty used crucible to check background (mass = 1).
Measure an empty crucible as an unknown (TPH).
Unknown Sample
5070 mg powdered sample material
Maximum sample = 200 mg
Precision
Precision of analysis is determined by measuring unknown samples in duplicate or triplicate and determining the
standard deviation of the replicate samples.
Accuracy
Accuracy is determined by running a calibration verification (CV) with every batch or every 10 samples.
LIMS Integration
Results are stored in the LIMS database associated with an analysis code and an analysis component. Analysis
codes and their components, definitions, and units are listed below.
Compressed Gases
Always wear safety glasses when handling and using compressed gases. Read the MSDS information for
the gases used in this procedure.
Hydrogen gas (CAS 1333-74-0) is highly flammable, explosive limits in air = 4%74%. Be careful with igni-
tion sources and oxidizers.
Helium gas (CAS 7440-59-7) is inert but may cause suffocation by displacing oxygen in the air during a re-
lease.
Check for leaks in compressed gas lines.
Use only wrenches approved for use on compressed gas tanks and lines.
Ground all equipment and lines associated with hydrogen usage.
High Temperatures
High oven and detector temperatures (325600C) are reached during operation. Use proper heat pro-
tective equipment when operating the instrument.
Make sure the FID cover is always installed during operation to protect from burns.
Pollution Prevention
Trace amounts of pyrolysis products are consumed by the flame ionization detector.
Helium gas has no adverse ecological effects. It does not contain Class I or Class II ozone-depleting chemi-
cals. Helium is not listed as a marine pollutant by DOT (49 CFR 171).
Waste Management
This procedure consumes the sample during pyrolysis, so no waste is generated.
Sample crucibles are reused.
Unused quantities of compressed gases are stored in labeled cylinders with protection cap in place until
return to manufacturer.