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the nucleus. Isotopes are atoms that have a different number of neutrons from protons in the nucleus.
This difference in the number of protons and neutrons results in a different atomic mass; however,
isotopes have all (for the most part) the physical properties of other atoms for a given element.
Carbon is used as an example here, but the structure and statistical methods presented apply to all
isotopes. The number of isotopes any particular element varies; carbon has seven isotopes with
carbon-12 being most common (~99% of the carbon on Earth). Carbon-12 is the standard for the
atomic weight of carbon. Figure 1 illustrates some structures for carbon.
where;
13
12
The ratio, Rsample, for a given sample is then compared to an Rstandard for a standard. The deviation for
the sample from the standard is noted as 13C and defined as:
1 1000
The same type of analysis can be done for the hydrogen isotopes contained in a methane sample.
Once the ratios for both the carbon isotope deviation and hydrogen isotope deviation are established,
these values can be plotted to determine the potential source of the gas. Figure 2 shows a how these
ratios relate to source location [Coleman].
13
Radiocarbon Dating
The isotopes of carbon, 14C and 12C, are present in roughly constant proportions and absorbed by
plants in the form of carbon dioxide. When the organism dies and begins to decay and form other
compounds, such as methane, the isotope (12C) remains stable and the unstable isotope (14C) begins to
decrease at a known constant rate. This radiocarbon, or 14C, is detectable from compounds formed
from living plants or animals within the last 40,000 to 50,000 years, allowing the identification of
biogenic methane resulting from natural processes.
Natural Gas Mixtures
Natural gas is predominantly methane (CH4) and include significant amounts of ethane (C2H6),
propane (C3H8) and other higher and non-normal hydrocarbons, nitrogen, CO2 and sulphur
compounds. There is no generalized standard for natural gas, usually when a supplier delivers it, it
has an average composition analysis provided. Figure 3 shows several mixtures for natural gases
from various sources.
result in samples that do not represent the circumstances at a given site. As an example, merely
collecting an atmospheric sample from a basement space may or may not result in a sample
concentrated enough for analysis. It may be necessary to construct a gas collection apparatus in the
area where stray methane intrusion into the structure is suspected and monitor with a gas detector
capable of reading concentrations in parts per million (ppm). Once the concentration of methane has
reached 5,000-10,000 ppm in the area or within the collection apparatus, then a sample can readily be
collected for analysis.
It would be very difficult to provide examples for every potential methane gas collection scenario,
especially for situations in which the rate of gas intrusion into a structure is slow. The investigator
should be prepared to improvise and use a bit of trial and error to construct an apparatus that suits the
site conditions and situation.
Water suspected of containing dissolved methane is a bit easier to sample. Samples from water wells
can be easily collected by connecting a sample hose to the appropriate container and then filling and
sealing the container. Water containing high levels of dissolved methane may have a number of
bubbles and even appear to fizz if the water is agitated.
All types of samples submitted to the lab should include a control sample if possible. For water
samples, this can be as simple as filling a sample bottle with store purchased bottled drinking water.
For samples of stray methane gas, the appropriate control(s) can be collected from any nearby natural
gas or propane distribution systems or sources. Not only does this provide the investigator with
assurance that the lab has correctly identified a known source, it can also eliminate (or identify) that
source as the origin of the stray gas.
Investigators should clearly mark all collection containers and use proper evidence chain of custody
forms and logs with all samples collected. If the lab selected isnt familiar with chain of custody
procedures, it may be necessary to explain the process and procedures to the lab staff that will be
handling and processing the samples.
Laboratory Analysis
There are only a handful of laboratories throughout the world that are capable of conducting isotopic
analyses and staffed by personnel familiar with the process. Investigators should use care when
selecting a laboratory and ensure that the laboratory is not only equipped to perform isotopic analyses,
but has staff properly trained and certified with supporting written standard operating and quality
control procedures. In addition, it is a great idea to request that the lab provide you with all of their
supporting quality control data in addition to the corresponding analytical report for each of your
samples. It is also appropriate to request that the lab provide the curriculum vitae (CV) for each
laboratory technician that handled or processed the sample and produced the analysis report.
The laboratory fees for analyses can vary widely based on type of analysis and processing speed. A
water sample tested for dissolved methane concentration and accompanying analysis of components
will cost approximately $250 per sample for standard speed processing of 8 days. An analysis of
biogenic methane requiring radio carbon dating will cost approximately $1300 for standard speed
processing of 35 days. Most laboratories can perform rush processing of samples with results
available in 1-2 days, especially if they are informed that the samples are related to a fire or explosion
incident.3
PRECISION AND ACCURACY OF ISOTOPIC ANALYSIS
The instruments used for isotopic analysis range from gas chromatographs to mass spectrometers and
all are capable of providing quality data that is precise and reproducible. The analytical precision is
presented in Table 1 [Isotech, 2014]. The analytical laboratory will be responsible for properly
calibrating the instruments and equipment used to process isotopic samples, but its appropriate to
inquire about their use of working standards and calibration standards. The lab should be using
certified standards and be able to produce the instrument calibration records and logs upon request.
If the lab is unable to provide quality assurance data for their instruments upon request, then another
lab should be considered.
Has the technique or process been subjected to peer review and publication?
Answer: Yes, since 1985 numerous papers have been written and research studies
completed addressing the use of isotopic analysis in forensic identification of stray methane
gas. Additionally, the technology has been accepted by U.S. state and federal courts as a
valid scientific process.
Is the potential error rate known and is it reasonable?
Answer: Yes, analyses are within reasonable accuracy levels. The sources of error are
known and controllable.
Are there standards for the application of the technique or process?
Answer: Yes, the National Institute for Science and Testing (NIST) has adopted minimum
standards for the testing of isotopic samples.
Has the relevant (scientific) community accepted the theory or technique?
Answer: Yes, since 1985 numerous papers have been written and research studies
completed addressing the use of isotopic analysis in forensic identification of stray methane
gas. Additionally, the technology has been accepted by U.S. state and federal courts as a
valid scientific process.
The investigators constructed gas collection apparatuses and installed them over the tops of the piling
control jacks that had been identified as a probable intrusion point for the stray methane into the
building. (See Figures 8 and 9.) The contents of the atmosphere were sampled over the following
days and once the concentrations within the sampling apparatus exceeded 5,000 ppm, samples were
collected by use of a collection hose, hand pump and gas collection bags. The samples were
packaged and shipped to a laboratory in the United States and preliminary results were received a few
days later that indicated the methane was biogenic in origin but of undetermined age. In order to
further narrow down the origin of the gas, the carbon was extracted from the samples and submitted
for radiocarbon dating which indicated that the methane sampled had a very high probability (more
than 95%) of originating as a result of bacterial consumption of sewage that had leaked from lines in
the area of the explosion.
The collection and analysis of methane gas samples from the site of the explosion allowed the
investigators to positively rule out leaks from the citys natural gas distribution as well as naturally
occurring methane from the ancient sea bed far below the surface as potential sources of the methane
that fuelled the explosion. In addition, it has prompted the installation of mechanical ventilation
systems in commercial buildings throughout Mexico City, including in the area of the explosion
scene.
CONCLUSIONS
Isotopic analysis is the identification of chemical compounds by using the distribution of specific
components in known ratios and the presence of isotopes to fingerprint the origin potentially the age
of those compounds. Isotopic analysis, along with gas mixture analysis, can be important components
of a forensics explosion investigation. Methane and/or natural gas are frequently suspected as fuels
for fires and explosions, the ability to positively identify the origin of a fuel gas with isotopic analysis
is a major benefit to investigators.
This paper has shown the basic concepts behind isotopic analysis and provided a case study that
illustrated the practical issues of sample collection and analysis. This is a sound methodology used in
other forensic analysis and has application in fire and explosion investigations.
ABOUT THE AUTHOR
Brian C. Dunagan, CSP, CFEI, CFII is a Principal Consultant with the IFO Group and is a
Certified Safety Professional and a Certified Fire and Explosion Investigator and Instructor. He is
also a Professional Member of the American Society of Safety Engineers with inclusion in the Fire
Protection and Oil and Gas Practice Specialties. Mr. Dunagan has a record of successfully leading
and managing high profile / high value loss incident investigations involving process related
explosions and fires, process equipment failures, human factors / errors, and acts of terrorism /
sabotage. In addition, Mr. Dunagan is a frequent industry event speaker and has been recognized as
an expert witness for cases filed in state, federal and international courts.
REFERENCES
Coleman, D. D., C. L. Liu, K. C. Hackley, and L. J. Benson. (1993), Identification of Landfill
Methane Using Carbon and Hydrogen Isotope Analysis, Proceedings of 16th International Waste
Conference, Madison: Univ. of Wisconsin.
Devold, H., Oil and Gas Production Handbook, ABB Publications. 2006
Isotech Laboratories, Inc., (2014), Gas Analysis Pricing and Turnaround Times, Champaign: Isotech
Corporation. 2014.
Isotech Laboratories, Inc., (2014), High Precision Isotopic Analysis, Champaign: Isotech
Corporation. 2014.
Murphy, B.L., Morrison, R.D., Introduction to Environmental Forensics, 2 ed. Academic Press,
Elsevier, 2007.
Wang, X., Economides, M., Natural Gas Engineering, Gulf Publishing Company, Houston,
Texas. 2009