ASTM E1618-97
(Guide)Standard Test Method for Ignitable Liquid Residues in Extracts from Fire Debris Samples by Gas Chromatography-Mass Spectrometry
Standard Test Method for Ignitable Liquid Residues in Extracts from Fire Debris Samples by Gas Chromatography-Mass Spectrometry
SCOPE
1.1 This test method covers the identification of residues of ignitable liquids in extracts from fire debris samples. Extraction procedures are described in the referenced documents.
1.2 While this test method is suitable for all samples, it is especially appropriate for extracts that contain high background levels of substrate materials or pyrolysis products. This guide is also suitable for the identification of single compounds, simple mixtures, or non-petroleum based ignitable liquids.
1.3 The values stated in SI units are to be regarded as the standard. The values given in parentheses are for information only.
1.4 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.
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Designation: E 1618 – 97
AMERICAN SOCIETY FOR TESTING AND MATERIALS
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Reprinted from the Annual Book of ASTM Standards. Copyright ASTM
Standard Guide for
Identification of Ignitable Liquid Residues in Extracts from
Fire Debris Samples by Gas Chromatography-Mass
Spectrometry
This standard is issued under the fixed designation E 1618; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.
1. Scope Samples by Passive Headspace Concentration
E 1413 Practice for Separation and Concentration of Flam-
1.1 This guide covers the identification of residues of
mable or Combustible Liquid Residues from Fire Debris
ignitable liquids in extracts from fire debris samples. Extrac-
Samples by Dynamic Headspace Concentration
tion procedures are described in the referenced documents.
E 1492 Guide for Receiving, Documenting, Storing, and
1.2 While this guide is suitable for all samples, it is
Retrieving Evidence in a Forensic Laboratory
especially appropriate for extracts that contain high back-
ground levels of co-extracted materials from the substrate or
3. Summary of Guide
pyrolysis products. This guide is also suitable for the identifi-
3.1 The sample is analyzed with a gas chromatograph (GC)
cation of single compounds, simple mixtures, or non-petroleum
which is interfaced to a mass spectrometer (MS) and a data
based ignitable liquids.
system (DS) capable of storing and manipulating chromato-
1.3 This guide is intended as an alternative to the method
graphic and mass spectral data.
described in Test Method E 1387. It is not intended to be a
3.2 Post-run data analysis generates mass chromatograms
replacement of that document or to supersede any of the
(selected ion profiles) characteristic of the chemical compound
information contained therein.
types commonly found in petroleum-based ignitable liquids
1.4 This standard does not purport to address all of the
and specialty products. Additionally, specific chemical compo-
safety concerns, if any, associated with its use. It is the
nents (target compounds) may be identified by their mass
responsibility of the user of this standard to establish appro-
spectra and retention times. Semi-quantitative determination of
priate safety and health practices and determine the applica-
specific chemical components (target compounds) which are
bility of regulatory limitations prior to use.
identified by mass spectra and retention time may be used to
2. Referenced Documents develop target compound chromatograms (TCCs).
3.2.1 The total ion chromatogram (TIC), selected ion pro-
2.1 ASTM Standards:
files (SIP) for the alkane, alkene, alcohol, aromatic, cycloal-
E 752 Practice for Safety and Health Requirements Relating
kane, ester, ketone and polynuclear aromatic compound types,
to Occupational Exposure to Carbon Disulfide
or target compound chromatograms (TCC), or combination
E 1385 Practice for Separation and Concentration of Flam-
thereof, are evaluated by visual pattern matching against
mable or Combustible Liquid Residues from Fire Debris
known standards.
Samples by Steam Distillation
3.2.2 Petroleum-based products may be grouped into one of
E 1386 Practice for Separation and Concentration of Flam-
five major petroleum classifications or one miscellaneous class,
mable or Combustible Liquid Residues from Fire Debris
3 as described in this guide.
by Solvent Extraction
3.2.3 Non-petroleum distillate-based specialty products
E 1387 Test Method for Flammable or Combustible Liquid
may be identified by specific compound identification or
Residues in Extracts from Fire Debris Samples by Gas
categorized in the Miscellaneous (Class 0) category, or both.
Chromatography
E 1388 Practice for Sampling of Headspace Vapors from
4. Significance and Use
Fire Debris Samples
4.1 The identification of an ignitable liquid residue in
E 1412 Practice for Separation and Concentration of Flam-
samples from a fire scene can support the field investigator’s
mable or Combustible Liquid Residues from Fire Debris
opinion regarding the origin, fuel load, and incendiary nature
of the fire.
This guide is under the jurisdiction of ASTM Committee E-30 on Forensic
4.2 Materials normally found in a building, upon exposure
Sciences and is the direct responsibility of Subcommittee E30.01 on Criminalistics.
Current edition approved April 10, 1997. Published February 1998. Originally to the heat of a fire, will form pyrolysis products. Selected ion
published as E 1618 – 94. Last previous edition E 1618 – 94.
profiling and target compound identification techniques de-
Annual Book of ASTM Standards, Vol 11.03.
scribed herein may facilitate the identification of an ignitable
Annual Book of ASTM Standards, Vol 14.02.
E 1618
liquid in the extract by reducing interference by components affinic solvents, and specialty products (lacquer thinner, carbu-
generated as products of pyrolysis and identification of pyroly- retor cleaner, spot removers, and the like), as described in Table
sis products. 1.
6.3 Solvent/Diluent—Carbon disulfide, pentane, or other
5. Apparatus
solvent that will not interfere with the analysis. It is generally
5.1 Gas Chromatograph—A chromatograph capable of us-
desirable to use a solvent whose volatility greatly exceeds that
ing capillary columns and being interfaced to a mass spectrom- of the solute to facilitate sample concentration by evaporation,
eter.
if necessary.
5.1.1 Sample Inlet System—A sample inlet system that can
6.4 Carrier Gas—Helium or hydrogen of purity 99.995 %
be operated in either split or splitless mode with capillary
or higher.
columns; the inlet system may use on-column technology.
7. Tuning of Mass Spectrometer
5.1.2 Column—A capillary, bonded phase, methylsilicone
or phenyl methylsilicone column or equivalent. Any column
7.1 Tune the mass spectrometer using perfluorotributy-
length or temperature program conditions may be used pro- lamine (PFTBA), or another appropriate calibration standard,
vided that each component of the test mixture is adequately
according to the instrument manufacturer’s specifications,
separated. prior to use. This should be done at least on a daily basis.
5.1.3 Oven—A column oven capable of reproducible tem-
7.2 Maintain tuning documentation as a portion of the
perature program operation in the range from 50 to 300°C. quality control documentation.
5.2 Mass Spectrometer—Capable of scanning between 20 to
8. Sample Handling
600 m/e with unit resolution or better, with continuous data
output. 8.1 Only samples of appropriate dilution should be analyzed
on a GCMS system. Generally, standards of flammable/
5.2.1 Sensitivity—The system must be capable of detecting
each component of the test mixture and providing sufficient ion combustible liquids are diluted 1:1000. Depending on column
capacity and injection technique, petroleum distillates can be
intensity data to identify each component, either by computer
library search or by comparison with standard spectra. made somewhat more concentrated to ensure detection of
minor target compounds.
5.3 Data Station—A computerized data station, capable of
storing chromatographic and mass spectral data from sample 8.1.1 If carbon disulfide is used, read and follow the safety
runs. precautions described in Practice E 752.
5.3.1 Data Handling—The data system must be capable of 8.2 Methods for isolating ignitable liquid residues from fire
performing, either through its operating system or by user debris for analysis by this guide are described in Practices
programming, various data handling functions, including input E 1385, E 1386, E 1412, and E 1413.
and storage of sample data files, generation of selected ion 8.3 System blanks will be periodically analyzed and the
profiles, searching data files for selected compounds, and documentation maintained. System blanks are obtained by
qualitative and semi-quantitative compound analysis. using the same methods employed to extract and concentrate
5.3.2 Mass Spectral Libraries—The system must be ca- the sample.
pable of retrieving a specified mass spectral scan from a data 8.4 Cleaning of Equipment:
8.4.1 Change septa and clean injector liner on a periodic
file and comparing it against a library of mass spectra available
to the data system. This capability is considered an aid to the basis to avoid sample contamination by “carry-over.”
8.4.2 Clean syringes thoroughly between injections. For
analyst, who will use it in conjunction with chromatographic
data and known standards to identify unknown components. autosamplers, perform and document periodic syringe carry-
over studies.
5.4 Syringes—A microsyringe capable of introducing a
sample size in the range from 0.1 to 10.0 μL. 8.4.3 System blanks should be run to ensure no carry-over
between samples.
6. Chemicals, Reagents, and Standards
8.5 Run and maintain reference files of known standards
6.1 The test mixture shall consist of equal parts by volume which have been analyzed in the same manner as the ques-
of the even-numbered normal alkanes (ranging from n-hexane
tioned samples.
through n-eicosane), methylbenzene (toluene), 1,4-
9. Procedure—Data Handling
dimethylbenzene (p-xylene), 1-methyl-2-ethyl benzene (o-
ethyltoluene), 1-methyl-3-ethyl benzene (m-ethyltoluene), and 9.1 The hydrocarbon compounds of ignitable liquids de-
1,2,4-trimethylbenzene. Additional compounds may be in- rived from crude oil consist of five major hydrocarbon types:
cluded at the discretion of the analyst. The final test solution is alkane (both normal and branched), alkene, cycloparaffin,
prepared by diluting the above mixture to a concentration of aromatic, and polynuclear aromatic. Other types exist, but are
0.05 % volume/volume (0.5 microlitre per millilitre) in the considered insignificant for the purposes of this guide
chosen solvent (see 6.3). 9.1.1 Hydrocarbon compounds of each type produce char-
6.2 Standards (commercially available products) must be acteristic major ion fragments. These ions are listed in Table 2.
available for gasoline, kerosene, diesel fuel, mid-range petro- 9.1.2 Additional data analysis may be carried out using
leum distillates (mineral spirits, paint thinners, charcoal start- either mass chromatography or target compound analysis, or
ers, and the like), light petroleum distillates (camp fuels, both.
VM&P naphthas, cigarette lighter fluid, and the like), isopar- 9.2 Mass Chromatography Analysis:
E 1618
TABLE 1 Ignitable Liquid Classificaiton System
Class Number (Class Name) “Peak Spread” Based on N. Alkane Carbon Examples
Numbers (Unevaporatted Liquid)
1. Light Petroleum Distillates (LPD) C –C Petroleum ethers, pocket lighter fuels, some
4 11
rubber cement solvents, Skelly solvents, V M
and P naphtha, some camping fuels
2. Gasoline C –C All brands and grades of automotive gasoline,
4 12
including gasohol.
3. Medium Petroleum Distillates (MPD) C –C Mineral spirits, some paint thinners,some
8 12
charcoal starters,“ dry-cleaning” solvents,
some torch fuels, some solvents for
insecticides and polishes, some lamp oils
4. Kerosene C –C No. 1 Fuel Oil, Jet-A (aviation) fuel, insect
8 17
sprays, some charcoal starters, some torch
fuels, some paint thinners, some solvents for
insecticides and polishes, some lamp oils
5. Heavy Petroleum Distillate (HPD) C –C No. 2 Fuel Oil, diesel fuel
9 23
0. Miscellaneous variable Single compounds, turpentines, specialty
mixtures which cannot be further classified
into one of the categories below.
0.1 Oxygenated solvents variable Alcohols, esters, ketones
0.2 Isoparaffins variable Isoparaffin products, some charcoal starters,
some copier fluids, some aviation gasolines,
some lamp oils, some solvents for
insecticides and polishes, some camping
fuels
0.3 Normal alkanes variable Specialty products formulated from normal
alkanes, insecticides and polishes
0.4 Aromatic solvents variable Light, medium and heavy “aromatic naphtha”
used as solvents for paints and plastics
0.5 Naphthenic/paraffinic solvents variable Specialty solvent/fuel products made from
Class 3 or Class 4 distillates treated to
remove normal alkanes and aromatics, with
higher cycloalkane content than isoparaffin
products
TABLE 2 Major Ions Present in Mass Spectra of Common
9.3 Target Compound Analysis:
A
Flammable and Combustible Liquids
9.3.1 Target compound analysis uses key specific com-
Compound Type m/e
pounds to characterize an ignitable liquid. These target com-
Alkane 43, 57, 71, 85 pounds are listed in Table 3, Table 4, and Table 5.
Cycloalkane and alkene 55, 69
9.3.2 Semi-quantitative ratios for the target compounds
n-Alkylcyclohexanes 82, 83
must be derived and compared against standards to ensure not
Aromatic—alkylbenzenes 91, 105, 119; 92, 106, 120
indanes 117, 118; 131, 132
only their presence but also that their chromatographic patterns
Alkylnaphthalenes 128, 142, 156, 170
match. Computerized pattern matching techniques are accept-
Alkylstyrenes 104, 117, 118, 132, 146
able, providing results are verified by the analyst.
Alkylanthracenes 178, 192, 206
Alkylbiphenyls/acenaphthenes 154, 168, 182, 196
9.3.2.1 Target compound pattern recognition may be im-
Monoterpenes 93, 136
proved by the production of target compound chromatograms,
Ketones 43, 58, 72, 86
which are graphical representations of semi-quantitative peak
Alcohols 31, 45
A areas for the target compounds. Target compound data may be
R. Martin Smith, Analytical Chemistry, Vol 54, No. 13, November 1982, pp
1399A–1409A. plotted as a bar graph, with the x-axis representing retention
time and the y-axis representing peak area. Each target com-
9.2.1 The data station is used to extract and draw mass
pound is depicted by a single bar on the graph.
chromatograms (selected ion profiles) for major ions charac-
9.3.2.2 Target compound chromatograms for unknown
teristic of each compound type. Individual mass chromato-
grams for two or more characteristic ions may be summed to TABLE 3 Gasoline Target Compounds
enhance signal-to-noise and decrease interference by extrane-
1. 1,3,5-Trimethylbenzene
2. 1,2,4-Trimethylbenzene
ous compounds that contain only one of the ions.
3. 1,2,3-Trimethylbenzene
9.2.2 Mass chromatograms for an unknown sample are
4. Indane
compared against the corresponding mass chromatograms from
5. 1,2,4,5-Tetramethylbenzene
6. 1,2,3,5-Tetramethylbenzene
standard samples. This is generally done by visual pattern
7. 5-Methylindane
recognition; computerized pattern recognition techniques are
8. 4-Methylindane
also acceptable, provided tha
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