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ISOTOPIC, RADIOCARBON AND MIXTURE ANALYSES FOR METHANE SOURCE

DETERMINATION IN GAS EXPLOSIONS AND FIRES


Brian C. Dunagan, CSP, CFEI, CFII
IFO Group: Incident Free Operations, Inc.
INTRODUCTION
The investigation of explosions can be very challenging and determining the fuel involved can be one
of the more complex issues associated with the process. Even when a gas is known to be the fuel for
an explosion, determining the source or origin of that fuel gas can often become a challenging issue
for the investigation team. In a situation where multiple potential gas sources exist, determining the
correct source is of the gas that fueled the explosion is absolutely essential to prevent recurrence.
Methods to understand natural gas and methane sources are examined in this paper, however, the
methods presented are applicable to the positive identification of other fuel gases and even liquid fuels
[Murphy].
Stable isotopes of carbon and hydrogen ( 13C and D) in methane or other natural gas molecules can
provide information on the mechanism and origin of a gas. The unstable or radioactive carbon isotope
(14C) can be used in many cases to estimate the age of a gas. Additionally, the mixture profile of
natural gas (ethane/methane ratio or other present hydrocarbons) can provide important information
regarding a fuel gas source. These analytical approaches can be combined to assist investigators in
determining the origin of methane involved in an incident.
This paper explores several analytical methods for examining natural gases to help determine the
source or origin of the gas. First, standard methods of isotopic analysis and the use of those results for
the determination of methane fuel source are presented. Second, the use of radiocarbon dating for
more precise biogenic methane fuel determination will be discussed. In addition, mixture ratios of
ethane and methane in gas is examined as a potential tool for identifying source. The collection of gas
samples can present challenges to the field investigator, so the equipment and methods for sampling
will be presented. Finally, it will be demonstrated through the case studies that the use of this
methodology is applicable and valuable in the determination of methane origin as a fuel source in
fires and explosions.
NATURAL GAS AND METHODS OF ANALYSIS
The focus of this paper is natural gas and methane. Natural gas is a mixture of methane (CH4) and
some percentage of ethane (C2H6) and possibly longer chain gases C3-C4. When the gas contains
longer carbon chains C2+ the gas is considered wet [Devold]. The geological and chemical conditions
a natural gas is formed under, in addition to where and how it is trapped in a geologic formation, has
an impact on the chemical make up of that mixture [Wang].
Methane develops from non-biogenic (thermogenic) and biogenic (microbial) processes.
Thermogenic processes tend to take place deeper (than biogenic) processes in the Earth. The biogenic
sources are typically landfills, marshes, wetlands and other near surface decomposition sources.
Thermogenic methane is formed by heat and pressure deeper in the earth. The formation methods can
be complex and are beyond the scope of this paper. For forensic investigation purposes the important
point is that methane form different types of formation and different underground sources have
different characteristics that can be exploited to help identify them.
Isotopes and Atoms
The basic building block of all elements is the atom. An atom is the smallest particle any element can
be parsed into and keep its physical properties. Atoms are made up of a nucleus containing protons
and neutrons (hydrogen has a one proton in its nucleus and no neutrons); in addition, electrons orbit

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.

Figure 1. Simplified model for three isotopes of carbon.


The 13C and 14C are common isotopes of carbon; 13C is a stable and makes up about 1.1% of the
carbon on Earth. 14C is radioactive and because it decays in a predicable way, can be used in dating
materials. 14C makes up about 1 part per trillion of the carbon atoms on Earth [Murphy, 2007].
Isotopic Analysis
Isotopic analysis involves the identification of chemical mixtures by using the distribution of isotopes
to provide a chemical fingerprint of the origin and potentially the age of a substance. Isotopic
analysis has significant applications in environmental forensics and is widely used to detect and
resolve problems related to landfill contamination, determining the source of stray methane gas in
soils, and deciphering the origin of natural gas in surface and groundwater as a result of oil and gas
exploration activity.
Isotopic analysis involves examining ratios of isotopes in a mixture. This involves determining the
number of stable carbon-13 isotopes in a sample and comparing that to the number of carbon-12
isotopes. This is called the Stable Carbon-Isotope Ratio (R) and is defined is defined as:

where;

13

C = total carbon-13 isotopes


C = total carbon-12 isotopes

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].

Figure 2. Stable Isotope Distribution of

13

C vs. D Projected to Location [Coleman]

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.

Figure 3. Compositional Ratios for Methane and Natural Gases


Many of the differences in natural gas mixtures occur because of variations in processing methods.
Natural gas sources range from gas only reservoirs to oil reservoirs that contain gas. Depending on
the condition of the raw gas various amounts of processing may be required. This processing changes
the composition ratios or the gas. Any processed gas product (from a given pipeline or storage tank)
will likely have mixture characteristics that can be used to differentiate it from other sources.
Natural gas is also soluble in water to ~24 ppm (methane) [Matheson] and can saturate water under
the right circumstances. This is often an issue in water contamination claims, but understanding any
water contamination of gas for a facility may help show infiltration pathways and gas sources.

SAMPLING EQUIPMENT, COLLECTION METHODS, AND LABORATORY ANALYSIS


Sampling Equipment
The equipment used to collect air or water samples for isotopic analysis is fairly simple but it is
essential that appropriate sample containers are used for the types of samples collected. Investigators
are strongly encouraged to use sample containers provided by the lab that will perform the analysis to
ensure the integrity of the sample and compatibility with the analytical equipment. Gas present at
atmospheric pressure is collected by using a hand pump and tubing to fill small bags that are then
sealed in a steel-shipping container for transport as a hazardous material shown in Figure 4. Samples
collected from pressurized sources such as pipelines or manifolds can be collected in small gas
cylinders or reduced in pressure and collected in gas sample bags, Figure 5. Investigators should
exercise extreme caution when collecting gas samples for analysis and control all ignition sources in
the area prior to sampling.

Figure 4. Gas Sample Bags and Shipping Container

Figure 5. Gas Sample Cylinder


Water sources can also be sampled to determine dissolved methane concentration and again, it is
important that the proper container is used to collect the sample, usually a sterile jar or a soft bag with
a sealable valve on the end. Water sampling equipment as shown in Figure 6 should also be sent to
the laboratory on the same day of collection for analysis the following day.

Figure 6. Water Sample Kit


Collection Methods
Collection of samples for isotopic analysis can appear to be as simple as scooping up a water sample
from a basement sump but improper selection of sampling container, methodology, or location can

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.

Table 1. Analytical Precision of Instruments used for Isotopic Analysis

LEGAL ISSUES AND CONSIDERATIONS


Isotopic analysis has been in use for more than 25 years for the forensic identification of stray
methane gas. In the event of legal proceedings, it isnt necessary for investigators to have an expert
level of knowledge of the science of isotopic analysis, but its important that they be capable of
explaining how and why samples were collected and be able to clearly explain the basics of how the
process works and how the results are applicable to their findings.
Admissibility of Analytical Data
Investigators should be prepared to address questions regarding the admissibility of isotopic analysis
data and how to respond to the gatekeeping factors laid out by the Frye and Daubert standards for
admitting scientific expert testimony. In general, these factors include:
Can the technique be subjected to empirical testing: is the theory or technique is,
refutable, and/or testable? Answer: Yes, the underlying theory is testable and can be
validated by using chemistry and physics.

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.

CASE STUDY 2013 PEMEX HEADQUARTERS BUILDING B-2 EXPLOSION


On the afternoon of 31 January, 2013 a powerful explosion ripped through Building B-2 within
Pemexs Mexico City headquarters complex, resulting in the deaths of 37 people and seriously
injuring more than 125 people working in and around the building. This explosion was fueled by
methane gas that infiltrated into the sub-basement compartments of Building B-2 and was ignited by
contractors performing routine maintenance work on the buildings piling control system. In the days
following the explosion, the investigation team detected methane gas continuing to infiltrate into the
sub-basement of Building B-2. Due to the heavily urbanized nature of the area surrounding the scene,
it was deemed essential to quickly determine the origin and route of the methane infiltration. This was
achieved through the utilization of high precision isotopic and radiocarbon analyses.

Figure 7. First floor of building showing blast damage from below

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.

Figure 8. Building jack with sampling tube

Figure 9. Isolated jack to collect gas sample

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

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