SME Annual Meeting
Feb. 28-Mar. 03, 2010, Phoenix, AZ
INSTRUMENTS FOR GAS ANALYSIS AT MINE FIRES/EXPLOSIONS
M. P. Valoski, MSHA, Pittsburgh, PA
ABSTRACT
In the United States, the occurrence of underground mine
fires/explosions continue to decrease; however, they pose great
danger to the miners and any subsequent mine rescue teams and/or
fire brigades. Tragically, 19 coal miners lost their lives in 2006 at fires
or explosions. Fires/explosions can devastate a mine and cause its
permanent closure. It is vitally important to obtain accurate information
on the gas content (concentration and composition) of the mine
atmosphere after the event so that appropriate action can be instituted
to rescue any trapped miners while not exposing the mine rescue
teams to unnecessary hazards. Additionally, the fire fighting
techniques (spraying water, sealing, etc.) will be dictated by the gas
content. Finally, the gas content will determine when it is safe to
recover the mine. The gas content of the air can be determined using
detector tubes, handheld instruments, portable instruments, or gas
chromatographs. No single instrument is suitable for all analyses.
Each type of instrument has its advantages and disadvantages. This
paper discusses these attributes.
INTRODUCTION
Underground mine fires/explosions have become uncommon
events in United States mines. Despite the low rate of occurrence of
mine fires/explosions, they occur almost every year and are very
dangerous to miners and mine rescue teams. While most mine
fires/explosions occur in coal mines, metal/nonmetal mines have also
had these events. The last event at a US metal/nonmetal mine
occurred in 2001.
During 2006, 19 coal miners tragically lost their lives at Sago,
Alma #1, and Kentucky Darby Mines because of fires or explosions.
Other miners were injured. Besides injuring or killing miners, mine
fires/explosions can devastate the underground working environment.
The devastation can permanently close a mine and cause a mine
operator to declare bankruptcy. This unfortunate event costs miners
their jobs.
The Mine Safety and Health Administration (MSHA) responds to
mine fires/explosions with fire experts to assess the situation and
chemists to operate sophisticated gas analysis instruments in a Mobile
Gas Laboratory. MSHA is responsible for the safety and health of
every U.S. miner. In order for the experts to deduce what is occurring
underground, accurate measurements of the gas constituents
(identification of the gases and determination of their concentration)
are vital. Because it takes time for the MSHA personnel to arrive, any
samples/measurements collected by the mine operator would give the
first responders valuable information about the current situation.
The mine operator presents a plan of action to control the
emergency situation to the MSHA District Manager who must
determine the appropriateness of the course of action proposed by the
mine operator. MSHA experts use mine fire indices and trend analysis
to interpret the gas analysis results. Using this information the experts
assist the District Manager in determining the appropriate course of
action for the mine operator to institute. This may be permitting mine
rescue teams to be sent in or withdrawing them. Gas analysis results
may dictate whether mine rescue teams can be safely utilized.
Furthermore, the mine operator may be able to fight the fire directly, to
fight the fire remotely, or to seal the mine totally.
1 Copyright © 2010 by SME
Preprint 10-039
Few mine operators have gas chromatographs or trained and
experienced personnel on staff to operate them. Therefore, most mine
operators will need to rely on detector tubes and handheld instruments
until MSHA’s Mobile Gas Laboratory arrives on the scene. Because
MSHA has gas chromatographs located in Pittsburgh, Pennsylvania;
Mt. Hope, West Virginia; and Denver, Colorado, it may take many
hours before a gas chromatograph is on-site and operating.
DETECTOR TUBES
Detector tubes (also known as colorimetric stain tubes) are easy
to use and are intrinsically safe because they are manually operated,
not battery powered. This is important as the measurement may be
made in a potentially explosive atmosphere. Moreover, detector tubes
are inexpensive and small. Many detector tubes can easily fit into a
shirt pocket. Figure 1 shows an example of a detector tube and pump.
1
Figure 1. Detector tube and sampling pump .
The specific targeted gas changes the color of the material inside
the tube. The gas concentration is determined by the length of the
stain compared to the marking on the tube’s side. Calibration gases
are not needed to use detector tubes. Detector tubes are made for
measuring various gases. Essentially each model of tube measures a
single gas. Therefore a miner would need to carry multiple models to
measure multiple gases. Table 1 presents detector tubes that use only
one stroke and are useful at mine fires/explosions. Even when using
only a single pump stroke, it may take 30 seconds to collect a sample.
Collecting more than one gas could take several minutes. Some
detector tubes require multiple strokes to determine a gas
concentration. These multistroke tubes are not considered very useful
at mine fires/explosions because of the time required to obtain a
measurement.
Unfortunately detector tubes have many drawbacks. Some gases
other than those targeted for measurement react with the chemicals in
the tube to give false positive readings. This is known as cross
sensitivity. The interfering gas can cause the detector tube to read
either high or low. The magnitude of the effect depends upon the
interfering gas. Table 1 lists the cross sensitivity of selected detector
tubes. By using a pretube to capture an interfering gas, cross
1
Reference to brand names or manufacturers is made to facilitate
understanding and does not constitute an endorsement by the Mine
Safety and Health Administration.
 SME Annual Meeting
Feb. 28-Mar. 03, 2010, Phoenix, AZ

sensitivity can be minimized. A pretube is another detector tube may exceed the upper range of the instrument. This concentration can
connected via shrink tubing to the measurement detector tube. destroy the sensor, thus rendering subsequent measurements
meaningless. For the catalytic methane sensor to work properly the
Table 1. Selected Detector Tubes. oxygen concentration needs to exceed 12%. Electrochemical sensors
1
Gas Range Cross Sensitivity also require oxygen for proper operation. Infrared detectors will work
Acetylene, petroleum in oxygen depleted environments. Finally only a few mine fire indices
Carbon monoxide 2 ppm to 7% hydrocarbons, chlorinated can be calculated using data from handheld instruments. To measure
hydrocarbons all the gases listed in Table 2 at least two instruments are required.
Carbon dioxide 0.5 to 2% Sulfur dioxide
Carbon dioxide, hydrogen
2
Oxygen 1.5 to 23% sulfide, nitrogen dioxide, sulfur
dioxide
Acetylene, alcohol, ammonia,
Hydrogen 0.2 to 2.0%
carbon monoxide
Carbon monoxide, nitrogen
Ethylene 0.5 to 100 ppm dioxide, acetylene, hydrogen
sulfide, hydrogen
1
Only considered the range determined with a single pump. To obtain
the entire range several different detector tubes may be needed.
2 0
Tubes can reach 100 C – therefore do not use in potentially
explosive atmospheres. Please note that one manufacturer makes a
non-heating tube but it has a limited measurement range.

Detector tubes have expiration dates (typically two years) and are
good for only a single measurement. Consequently they must be
replaced, even if not used. Another major deficiency is the poor
accuracy of detector tubes. For some gases the accuracy is only
±25%. A few other gases can be measured with an accuracy of ±10%.
Finally the person taking the measurement generally needs to be in the
gas stream to use a detector tube. This can place a miner in an
extremely hazardous location. After an explosion or during a fire, Figure 2. Multigas handheld detector.
some gases such as carbon monoxide can exceed concentrations that
Table 2. Gases Measured with Handheld Instruments
are their immediately dangerous to health or life. 1
Gas Sensor Type Range Cross Sensitivity
HANDHELD INSTRUMENTS Methane Catalytic 0 to 5% Flammable gases
Carbon Hydrogen,
Handheld instruments are made by many manufacturers. Figure Electrochemical 0 to 9999 ppm
monoxide hydrogen sulfide
2 shows one model of handheld detector. Some instruments can Carbon dioxide Infrared 0 to 6% Moisture
measure only one gas while others can measure up to five gases Methane Infrared 0 to 100% Moisture
(channels) simultaneously. Instruments with multiple gas capability are
Oxygen Electrochemical 0 to 30% Carbon monoxide
preferred to those that measure a single gas. Three types of sensors
Carbon
are used to measure the gas – catalytic, electrochemical, and infrared.
Hydrogen Electrochemical 0 to 1000 ppm monoxide,
Of course, the handheld instrument must be intrinsically safe to be
2 hydrogen sulfide
used. Handheld instruments can measure the concentration of gases 1
such as methane, oxygen, carbon monoxide, and carbon dioxide. Gases typically found in mining.
Table 2 presents the gas measured along with the sensor type and PORTABLE INSTRUMENTS
cross sensitivities. A few handheld instruments are equipped with an
internal pump that can pull a sample from up to 100 feet away. Portable instruments use the same technology as the handheld
Handheld instruments are more accurate and can respond faster to instruments – electrochemical or infrared sensors. These instruments
gases of interest than detector tubes. These instruments require are larger than handheld units and can generally measure a wider
minimal warm-up time (a few minutes) before they are usable. range of gas concentrations. Figure 3 shows portable instruments.
Because the instruments are small, they can be used nearly Notice that these instruments are considerably larger than handheld
everywhere. Mine rescue teams carry these instruments to prevent units. MSHA usually brings these instruments in a mobile laboratory to
entering hazardous environments without taking proper precautions. the mine. These instruments can also be set up in an office at the
Typically the instrument is kept continually operating. Handheld mine. Each instrument typically measures one gas although newer
instruments sound an alarm when encountering a hazardous models can measure up to four gases. These instruments require line
environment. MSHA district personnel have handheld instruments to power; therefore, they are not suitable for underground use (not
use when they arrive on site at a mine fire or explosion. intrinsically safe). The gas from the mine is plumbed into the
instrument via tubing from the sampling location. The sampling
Handheld instruments require calibration to assure accuracy. The location can be thousands of feet from the instrument thus requiring
calibration gas has an expiration date and this gas must be used within the use of a sampling pump. Because an explosive mixture may be
the expiration date for reliable results. Generally, only one gas encountered, the sampling pump must be intrinsically safe and have a
concentration is used to calibrate each channel of the instrument. flame arrester installed. The long distance away can be an advantage
Moreover, the sensors for the instrument need to be replaced and in that the person taking the measurement is not in harm’s way. Long
some sensors have a short storage life, whether or not they are used. sampling lines require connectors that may leak and dilute the sample.
Cross sensitivity is also a problem. Some interfering gases cause the Portable instruments have minimal warm-up and calibration time (up to
instrument to read high or low. The maximum concentration of gases 1 hour).

2
For the United States mining industry, MSHA approves instruments
for intrinsic safety in methane-air atmospheres. Approved
instruments carry a sticker attesting to their use in potentially
explosive atmospheres.
2 Copyright © 2010 by SME
 SME Annual Meeting
Feb. 28-Mar. 03, 2010, Phoenix, AZ

Figure 4. Benchtop gas chromatograph with a reduction gas analyzer

Figure 3. Portable instruments in a mobile laboratory. (blue box) in the Mobile Gas Laboratory.

Table 3. Gases Measured with Portable Instruments. Table 4. Gases Determined by Gas Chromatography.
Gas Sensor Type Range Cross Sensitivity
1 Gas Range
Methane Catalytic 0 to 5% Flammable gases Oxygen 0.01 to 21%
Carbon Hydrogen, Nitrogen 0.01 to 100%
Electrochemical 0 to 10% Hydrogen 5 ppm to 5%
monoxide hydrogen sulfide
Carbon dioxide Infrared 0 to 30% Moisture Carbon monoxide 10 ppm to 10%
Methane Infrared 0 to 100% Moisture Carbon dioxide 0.03 to 20%
Oxygen Electrochemical 0 to 40% Methane 0.01 to 100%
1
Gases typically found in mining. Ethane 10 ppm to 20%
Ethylene 5 ppm to 0.5%
Portable instruments also require calibration to assure accuracy. Acetylene 5 ppm to 0.5%
The calibration gas has expiration dates, and this gas must be used Argon 0 to 0.93%
prior to the expiration date for reliable results. Generally only one gas
concentration is used to calibrate the instrument. Only a few mine fire The exact range depends upon the detector(s), analytical
indices can be calculated using data from portable instruments column(s), calibration gas(es), and carrier gas. Multiple concentrations
because only a few gases are measured. of each gas of interest are used to calibrate the gas chromatograph.
The portable instruments have the advantage that they are used Ideally the calibration concentrations will blanket the range of gases
at the surface and can continually monitor the mine’s atmosphere. being measured. There are multiple acceptable combinations of
Detector tubes and gas chromatographs are used to determine gas detectors, analytical columns, and carrier gas to analyze mine air.
concentrations for discrete times. While handheld instruments can Unfortunately, no consensus organization has standardized the
measure continuously, people typically use these instruments to make analytical equipment or method for analyzing mine fire gases. Table 5
discrete measurements at appropriate intervals. The continuous presents the combination used in MSHA’s benchtop gas
measurement permits a quick determination of any changes chromatographs with ultrapure helium as the carrier gas. MSHA uses
underground. If a change would occur, the mine operator can collect a precolumns to scrub contaminants from the gas samples to protect the
sample for analysis by gas chromatography. Typically each location is analytical columns. During the run the precolumns are backflushed to
connected to a bank of portable instruments. The bank has an remove the contaminants. The reduction gas analyzer is used to
instrument for each gas of interest. measure low concentrations of hydrogen and carbon monoxide.
Because of the variety of gases measured, mine fire experts can
GAS CHROMATOGRAPHS calculate every important mine fire index. Depending upon the
temperature programming, a gas chromatograph may require
Gas chromatographs give the most complete analysis of the substantial warm-up and calibration time (several hours) before a
gases in the mine atmosphere. These instruments have been used usable analysis can be conducted.
since the 1970’s to analyze gas samples. Figure 4 shows an example
of a gas chromatograph. Modern gas chromatographs are more user There are two types of gas chromatographs – benchtop and
friendly than the early models. The new models have enhanced portable (micro). Benchtop gas chromatographs, which are heavy and
ruggedness, stability, and their software processes data faster and bulky, are designed to be used in a laboratory while portables are
more accurately. designed to be able to be transported to remote locations. A portable
gas chromatograph is similar in size to a portable instrument described
From a single sample an analyst can determine the concentration in the previous section. No gas chromatograph is intrinsically safe;
of the gases listed in Table 4. In order to obtain the lower therefore, all need to be operated on the surface.
concentrations of carbon monoxide and hydrogen, a reduction gas
analyzer is used in conjunction with the gas chromatograph. Some MSHA Technical Support transports benchtop gas
organizations measure the concentration of additional gases such as chromatographs in a Mobile Gas Laboratory to mine fires/explosions.
propane and propylene. Unfortunately few mines have a gas Inspectors collect gas samples at selected sites and bring the samples
chromatograph on-site. A properly equipped gas chromatograph has to the mobile laboratory for analysis. Gas samples collected for
specificity for a gas (correctly identifies the gas) and can accurately immediate analysis are collected in plastic syringes with rubber septa.
measure a wide range of concentrations.

3 Copyright © 2010 by SME

 SME Annual Meeting
Feb. 28-Mar. 03, 2010, Phoenix, AZ

Samples can be collected in evacuated glass bottles or sampling bags

and stored for later analysis.
Table 5. Gases Measured by Detector.
Poropak Q in line with a
Poropak T with Thermal Molecular Sieve 5A with Reduction Gas
Conductivity Detector Thermal Conductivity Analyzer after the
and Flame Ionization Detector Molecular Sieve
1
Detector
Methane Hydrogen Hydrogen
Carbon dioxide Oxygen Carbon monoxide
Ethylene Nitrogen
Ethane Methane
Acetylene Carbon monoxide
1
The flame ionization detector must be installed after the thermal
conductivity detector. A flame ionization detector destroys the sample
while the thermal conductivity detector does not. Flame ionization
detectors can measure lower concentration of hydrocarbons than
thermal conductivity detectors.

A major drawback of gas chromatographs is the length of time

necessary to separate the gases. Typically an analysis run takes
approximately 15 minutes for a benchtop with portables having a faster
analytical run time. Essentially this limits the analyst to analyzing only
four samples per hour. While this time is short compared to the time
required to collect and transport the sample to the laboratory, it is
substantial for the fire experts waiting for the analysis results.
Isothermal analysis keeps the analytical run times short. The benchtop
has the advantage of having a better Limit of Detection.
Another major drawback is that trained experienced personnel are
necessary to operate gas chromatographs and interpret the
chromatograms correctly. Also, gas chromatographs, which are very
expensive to purchase, need to be used on a routine basis so that they
will perform adequately during an emergency. Therefore, maintenance
costs are high.
CONCLUSION
The type of instrument available at a mine emergency determines
the type and quality of information that can be collected. Each
instrument type has its role at a mine fire/explosion. The most useful
instrument is a gas chromatograph and the least useful is a detector
tube. By using several different kinds of instruments, the results can
be compared. If the results do not agree then remedial steps must be
taken. Portable instruments, because they continually analyze the gas
stream, give a quick indication if something changes underground.
Gas chromatographs need to be used at all mine fires/explosions
because they can measure the concentration of the important fire
gases thereby allowing mine fire experts to calculate mine fire indices.
Unfortunately considerable time may elapse before a gas
chromatograph can reach the mine site; therefore, handheld
instruments make a good first response instrument and can
complement gas chromatographs.

4 Copyright © 2010 by SME