GAS DETECTION AND MONITORING

OBJECTIVES
The primary purpose of monitoring the concentrations of airbone pollutants in a mine is to
ensure that the atmosphere provides a safe environment free of toxicants that would create
a hazard to heath.
Three matters to be considered –
1. Threshold limit values of the gases or TLVs
[Link] of instrumentation for detection
[Link] and how often measurements are required.
We have discussed 1 and 2. in earlier work ( see tables)

PRINCIPLES OF GAS DETECTION

1) Filament and catalytic oxidation (pellistor) detectors)
2) Flame safety lamps
3) Thermal conductivity and acoustic detectors
4) Optical methods
5) Electrochemical methods
6) Mass spectrometers
7) Paramagnetic analysers
8) Gas chromatography
9) Semiconductor detectors
10) Stain tubes

1) FILAMENT AND CATALYTIC OXIDATION (PELLISTOR) DETECTORS

Methanometers
The methanometer is an instrument to measure the percentage of methane (or firedamp) in
the air in underground coalmines, and has been designed to alert miners of the presence of
potentially dangerous concentrations of this gas.
Mine officials carry methanometers to evaluate gas levels in work areas as well as to
inspect other areas of the mine. If methane is measured at 1.25% then work will cease and
equipment will be shut down, and if the methane level is measured at 2.50% then all
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personnel will be withdrawn to ensure their safety from risk of fire or explosion. Methane
levels are regularly measured using handheld methanometers in close proximity to the roof,
face, and rib of the working place. Readings are also taken across intake airways to keep
the methane level below 0.25 percent.
Continuously recording methanometers are used at or near upcast shafts as well as outbye
ventilation splits, unsealed goafs and waste workings. Fixed methanometers are also
installed at strategic locations near the face and on equipment to permanently monitor work
areas and initiate alarms or equipment shutdown.
Diesel vehicles being used in return airways in New South Wales and Queensland
underground coal mines carry methanometers with alarms set at 1.00% and vehicles will be
withdrawn to a safe area if this alarm level is reached.

Origin of the methanometer

The first electrical methanometer for use in coalmines was developed by MSA in 1949. It
was known as the W8 methanometer and was powered by an Edison cap lamp battery.
Several types of hand held electronic methanometers were developed around the world
during the 1950's but the first independently powered instrument, the GP (general purpose)
methanometer, was not introduced until 1961. The C4 methanometer was introduced by
MSA in 1966 and was later replaced by the D6, which is still the main hand held electronic
methane detector used in British coal mines.
The first recording methanometer was developed by Maihak in Germany but, as it analysed
each sample over a three minute cycle, continuous recording of methane was not possible
until new instruments were developed at SMRE (Safety in Mines Research Establishment)
in England and the Bureau of Mines in Pittsburgh, USA. As a result of the work done at
SMRE to develop a butane lamp methanometer, in 1961, the Sigma Recording Flame
Methanometer Type 208 was introduced into underground coalmines in England to
continuously chart methane levels.

Methanometer Operating Principles

The Butane Lamp Methanometer developed by SMRE in 1961 used a thermocouple to

measure the heat developed by the combustion of methane in a controlled pure butane
flame housed in a modified flame safety lamp. As the volume of methane in the mine
atmosphere varied so did the heat measured by the thermocouple, which was itself
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connected to an ammeter or clockwork operated chart recorder calibrated to continuously
record the actual methane level.

It was, however, more common for early methanometers to use sensors comprising two
filaments arranged in a Wheatstone Bridge circuit and the MSA GP methanometer used
such a sensor. One arm of the Wheatstone Bridge consisted of an electrical filament that
was heated to a high enough temperature to burn any methane in the air sample that passed
over the filament (housed within a porous flame proof barrier). The process of burning
raised the temperature of the filament further, which in turn increased the electrical
resistance of this active filament. This change of resistance could then be calibrated as a
current change proportional to the volume of methane present. The other arm of the
Wheatstone Bridge contained a similar filament that was exposed to the same air sample
but this filament was inactive as it was not heated. By having an active and inactive
filament in the same sample, a balancing control was established to allow for atmospheric
variations such as relative humidity, temperature, and pressure.

Research to overcome the inherent weaknesses of the filament detector (filament coils were
delicate and could cause inconsistencies in current output) led to an improved version of
the above Wheatstone Bridge principle known as a "pellistor". The pellistor is now the
most commonly used sensor in modern methanometers.

Despite its disadvantages of being susceptible to catalyst poisons (including sulphurous

gases, silicones and halogenated hydrocarbons), the pellistor's comparative low cost,
simplicity, and ability to run continuously for over eight hours on one battery charge have
resulted in its widespread use in coal mines as the sensor of choice in hand-held
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methanometers.

The concept of the pellistor is also based on the fact that the most foolproof way to
determine whether a flammable gas is present in air is to test a sample by trying to burn it.
A pellistor consists of a very fine coil of wire suspended between two posts. The coil is
embedded in a pellet of a ceramic material, and on the surface of the pellet (or 'bead') there
is a special catalyst layer.

In operation, a current is passed through the coil, which heats up the bead to a high
temperature. When a flammable gas molecule comes into contact with the catalyst layer,
the gas "burns" in a controlled environment behind a flameproof barrier known as a sinter.
Just as in a normal burning reaction, heat is released which increases the temperature of the
bead. This rise in temperature causes the electrical resistance of the coil to rise. There is
another bead in the circuit identical to the detector bead but not containing any catalyst.
This bead will react to changes in humidity, ambient temperature etc, but will not react to
flammable gas. All that is required is to compare the resistance of one bead against another
in a Wheatstone Bridge type circuit in order to obtain a meaningful signal.

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Displayed reading on a methanometer
Older methanometers manufactured from the 1950's to 1980's usually have an analogue
display with a needle indicating a reading within the range 0-2% or 0-5% methane.

Methanometers manufactured since the 1980's usually have a digital display reading 0.0-
4.9% methane or 0.00 - 4.99% methane.

An early methanometer
The GP methanometer was powered by two Mallory cells held in nylon mouldings, used
SMRE type filaments, had a probe attachment, and was housed in a stainless steel case
with the complete instrument weighing about three pounds.

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 MSA GP methanometer 1961

Mine officials were able to carry this methanometer around the pit and use it to take
accurate methane "spot readings" at specific times throughout each shift.

A modern methanometer
These days there are many manufacturers of methanometers who produce their gas
detectors in various configurations. Modern hand held methanometers are usually small,
comparatively light weight, sophisticated, electronic monitors capable of operating for over
twelve hours on one battery charge and able to store large numbers of gas readings.
Methanometers can also be sourced with continuous output to link into mine management
systems.

Apart from being able to provide continuous instantaneous methane readouts with visual
and audible alarms, electronic methanometers now have the ability to collect useful
information for later analysis. Tens of thousands of methane readings can be stored in
onboard datalogging chips and can be retrieved later on the surface for display on PC's and
in printed format.

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 OdaLog CH4 monitor 2002

Data collected, for example, over a 12 hour period could be very useful for ventilation
officers to establish methane profiles at selected locations throughout a mine.

MiniGas graph

With the ability to display the stored data in pictorial format on a PC (see graph above)
mine officials are now able to easily obtain an overview of methane levels collected by
portable methanometers.
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FOOTNOTES
Modern pellistor methanometers have a degree of reliability and operate continuously on
mining machines within conditions of high humidity, dust and vibration.
The bridge output signals may be used to indicate on dials, activate audio-visual alarms,
isolate electrical power to machines etc.
Disadvantages:-
1) Depend on availability of oxygen, pellistors will indicate increasing
concentrations of methane up to 10%. Beyond that the decreasing concentration of oxygen
will diminish the rate and temperature of catalytic oxidation giving a reduced and false
reading.
2) They are subject to poisoning by other gases and vapours, eg vaporized
components, electricals, greases or phosphate esters.
3) They will react with any combination of combustible gas (hydrogen, co, and
ethane) that pass through the absorbent filter. At 1% concentration of each gas the meter
will read
Methane 1%
CO 0.39%
H2 1.24 %
Ethane 1.61%
Propane 1.96%
So a mixture of air and ethane with a reading of 3.4% will have an actual concentration of
ethane = 3.4 ie 2.1%
1.61
Note that any given reading indicates approximately the fraction of the lower flammable
limit of the gas being monitored.

2) FLAME SAFETY LAMPS

These lamps were introduced early in the nineteenth century for the purposes of providing
illumination from an oil flame without igniting methane – air mixture (section 1.2). Their
use for illumination disappeared with the development of electric battery lamps. However,
the devices have been retained for the purposes of testing for methane and oxygen
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deficiency.

A blue halo of burning gas over the lowered flame of the lamp becomes visible at about 1%
methane. The size of the halo increases with methane concentration. At 4%, it forms a very
clear equilateral triangle. At 5% the flame spirals upwards into the bonnet of the lamp and
either continues burning or self-extinguishes in a contained explosion. In both cases, the
flame is prevented from propagating into the surrounding atmosphere by the tightly woven
wire gauzes (section 1.2). The use of the flame safety lamp for methane testing has now
largely been replaced by pellistor methanometers, as these are more accurate, reliable and
safer.

Some coal mining industries have retained the safety lamp for its ability to indicate oxygen
deficiency. The height of the flame reduces progressively with oxygen content and is
extinguished at 16% oxygen. However, in a methane-rich atmosphere, the flame may
remain lit down to an oxygen concentration of 13%.

Various attempts have been made to convert modified flame lamps into alarm and
recording devices (for example, Pritchard and Phelps, 1961). However, some ignitions of
methane have been attributed to flame safety lamps that have been damaged or
inadequately maintained (Strang and MacKenzie -Wood, 1985). The flame safety lamp has
a honourable place in the history of mine ventilation but its role is over.

3) THERMAL CONDUCTIVITY AND ACOUSTIC GAS DETECTORS

At 20 0C and at normal atmospheric pressures, the thermal conductivity of methane is

0.0328 W/(m 0C) compared with 0.0257 W/(m 0C) for air. This difference is utilized in
some high range methanometers. Two heated sensors are employed, exposed to the gas
sample and the other retained as a reference within a sealed air—filled chamber. A sample
of the ambient air is drawn through the instrument at a constant rate. The sample sensor
cools at a greater rate owing to the higher thermal conductivity of the methane. The change
in resistance of the sample sensor is detected within an electrical bridge to give a deflection
on the meter. Typical ranges for a thermal conductivity methanometer are 2% or 5% to
100%. The principle is sometimes used in conjunction with pellistors to provide a dual
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range instrument or to override the falsely low readings that may be given by catalytic
combustion detectors at high concentration (discussed earlier in this section). To reduce
interference from other gases, suitable filters should be employed. In particular, carbon
dioxide gives about half the response of methane but in a negative direction. For use in
mining, a soda lime filter is, therefore, advisable.

Acoustic gas detectors rely on changes in the velocity of sound as the composition of a
sample varies. They are used, primarily, for high concentrations and have been employed
in methane drainage systems.

4) OPTICAL METHODS
Subdivided into three groups.

Interferometers
Utilize the refraction of light that occurs when a parallel beam is split, one half passing
through the sample and the other through a sealed chamber containing pure air. The two
beams are recombined and deflected through a mirror or glass prism arrangement for
viewing through a telescope. The optical interference between the two beams causes a
striped fringe pattern to appear in the field of view. This typically takes the form of two
black lines in the centre with red and green lines on both sides. The fringe moves along a
scale in proportion to the amount of gas present. Rotational adjustments of one of the
deflecting prisms can be read on a vernier and added to the optical scale in order to widen
the range of the instrument. Interferometers are sensitive to the presence of other gases and
appropriate filters should be used when necessary. Hydrogen gives a negative response
with respect to methane. At equal concentrations of the two gases, the reading is near zero.
Carbon dioxide and methane give similar responses. For air containing both carbon dioxide
and methane two readings are taken, one with a soda lime filter to remove the carbon
dioxide and gives the methane concentration only, and the second without that filter. The
difference between the two readings is an indication of the carbon dioxide concentration.
The effects of other gases render the interferometer unsuitable for situations where the
composition of the sample is dramatically different from that of normal air, for example,
afterdamp, downstream: from fires or samples taken from behind seals.

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The non-dispersive infrared gas analyser
Is one form of absorption spectro-meter that is frequently used for mine gas analysis.
Identical beams of slowly pulsating infrared radiation pass sequentially through two
parallel chambers, one containing a gas that does not absorb infrared (typically nitrogen)
and the other fed by a stream of the sample. The pulsations of 3 to 4 Hz may be achieved
electronically or by a rotating chopper arrangement. Beyond the sample and reference
chambers are two-compartment sealed container (detector unit) filled with a pure specimen
of that particular gas which is to be detected. Detector units can be interchanged to
determine the concentrations of different gases. The two compartments of the detector unit
are at the same nominal pressure and are separated by a flexible diaphragm. The pulses of
infrared radiation are directed sequentially into the two sides of the detector unit, heat the
contained gas and, hence, raise its pressure. However, the beam that has passed through the
sample chamber has already been partially absorbed at the relevant wavelength by
molecules of the sought gas. Hence, the pulses of pressure induced in that corresponding
side of the detector unit are weakened. The amplitude of the vibrating diaphragm is sensed
by an electrical capacitor and translated electronically to an output signal. Infrared gas
analysers are employed primarily at fixed monitoring stations. However, portable versions
are available.

Laser spectroscopy
Is another means of air analysis that has considerable potential for subsurface application.
There are two systems that can be employed. One is the differential absorption unit (DIAL
system) in which two similar lasers are used, one tuned to the absorption wavelength of the
gas to be detected, and the other to a slightly different wavelength. The two laser beams
pass through the sample gas stream and are reflected back to a single receiver unit. The
difference in the two signals is processed to indicate the concentration of the gas being
monitored. The employment of a reference beam eliminates the effects of dust, humidity or
other gases.
The second laser technique for gas analysis is the light detection and ranging (LIDAR)
method, which depends on the Raman effect. When ~ gas is excited by monochromatic
radiation from a laser, a secondary scattered radiation is produced. The spectrum of this
scattered radiation can be analysed to indicate the concentrations of the gases that caused it.

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The attraction of laser techniques for mine air sampling is that the laser beams may be
directed across or along subsurface openings to give continuous mean analyses for large
volumes of air. Furthermore, the lasers can also be used to monitor air velocity. At the
present time, the high cost of the units precludes their use in other than isolated cases.

Another technique that is most promising involves passing pulses of light along fibre
optics. This method may also be used to indicate variations in temperature along the length
of the fibre.

5) ELECTROCHEMICAL METHODS

Very small concentrations of many gases can be detected by their influence on the output
from an electrochemical cell. There are two primary types, both based on oxidation or
reduction of the gas within a galvanic cell. The cell has at least two electrodes and an
intervening electrolyte. In the polarographic or voltametric analyser, a voltage from an
external battery is applied across the electrodes in order to induce further polarization (or
retardation) of the electrodes. The gas sample is supplied to the interface between the
electrolyte and one of the electrodes (the ‘sensing electrode’). This may be accomplished
by diffusion of the sample gas through a hollowed and permeable sensing electrode. The
electrochemical reaction at the electrode—electrolyte interface changes the rate at which
free electrons are released to flow through the electrolyte and to be collected by the
‘receiving electrode’. For example, in a sulphur dioxide electrochemical analyser, the
oxidation is as follows:

SO2 + 2H2O SO4-2 + 4H+ +2e-

The resulting change in electrical current is proportional to the concentration of sulphur

dioxide in the sample.

In amperometric cells, the gas reacts directly with the electrolyte and, hence, enhances or
reduces the current produced. Both types of cell are subject to interference by other gases.
This is minimized by appropriate selection of the materials employed for the electrodes and
electrolyte, the polarizing voltage applied to the polarographic cells and a suitable choice of
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filters.

Electrochemical cells may indicate the partial pressure rather than the concentration of a
gas. These require the zero to be reset when taken through a significant change in
barometric pressure—as will occur when travelling to different levels in a mine. Another
disadvantage of electrochemical analysers is that they can become temporarily saturated
when exposed to high concentrations of gas. The recovery period may be several minutes.

6) MASS SPECTROMETERS

In these instruments, the gas sample passes through a field of free electrons emitted from a
filament or other source. Collision of the electrons with the gas molecules produces ions,
each with a mass/charge ratio specific to that gas. The ions are accelerated by
electromagnets and then pass through a magnetic deflection field, which separates them
into discrete beams according to their mass/charge ratios. The complete mass spectrum can
be scanned and displayed on an oscilloscope or the signals transmitted to recorders.

7) PARAMAGNETIC ANALYSERS
Oxygen is one of the very few gases that is paramagnetic, i.e. it aligns itself as a magnetic
dipole in the presence of an applied magnetic field and, hence, creates a local anomaly
within that field. This property is utilized in a paramagnetic oxygen analyser. A weak
permanent dumb-bell magnet is suspended against a light applied torque within a non-
uniform magnetic field. One end of the dumb-bell is encapsulated within a bulb of nitrogen
while the other end is exposed to the gas sample. A rotation of the magnet is induced as the
oxygen content of the sample varies. The movement is amplified optically or electrically
for display or recording.

8) GAS CHROMATOGRAPHY
Gas chromatographs are used widely for the laboratory analysis of sampled mixtures of
gases. Portable units are also manufactured. An inert carrier gas is pumped continuously
through one or more columns (or coils), which contain gas adsorbents. The latter may be
granulated solids or liquids. A small pulse of the sample gas mixture is injected into the
line upstream from the columns. The constituent gases are initially adsorbed by the column
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materials. However, the continued flow of the carrier gas causes subsequent desorption of
each gas at a time and rate dependent on its particular adsorption characteristics. The result
is that the gases leave the adsorbent columns as discrete and separated pulses. Their
identification and measurement of concentration is carried out further downstream by one
or more of the detection techniques described in this section.

9) SEMICONDUCTOR DETECTORS
One of the most recent techniques introduced for gas detection involves passing the sample
over the surface of a semiconducting material that is maintained at a constant temperature.
Adsorption of gas molecules on to the surface of the semiconductor modifies its electrical
conductance. Selectivity of the gas to be detected may be achieved by the choice of
semiconductor and the operating temperature. However, filters may be necessary to avoid
interference or poisoning from other airborne pollutants. Coupled with the development of
thin film technology, the semiconductor technique holds promise for increased future
utilization.

10) STAIN TUBES

Stain tubes are used widely for a large variety of gases. They are simply glass phials
containing a chemical compound that changes colour in the presence of a specified gas.
The phials are sealed at both ends. To carry out a test, the ends are snipped open and a
metered volume of sample air pulled through at a constant rate, usually by means of a
simple hand pump. The concentration of gas is estimated either from the length of the stain
or by comparing the colour of the stain with a chart. Despite the lack of precision, stain
tubes are used extensively in practice because of their simplicity, portability and low cost.

METHODS OF SAMPLING

The methods of sampling for subsurface gases vary from judicious positioning of the
human nose to sophisticated telemetering systems. The techniques most commonly applied
can be divided into two classes:
(a) manual and
(b) automatic or remote.

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Manual methods

The locations and times at which hand-held equipment should be employed to measure
methane concentrations in gassy mines are normally mandated by the governing
legislation. These include pre-shift inspections by qualified persons prior to entry of the
work force, and at intervals of some 20 mm throughout the shift on a working face.

The instruments that are most widely used for manual detection and measurement are
catalytic oxidation methanometers, stain tubes and, in some countries, flame safety lamps.
Light gases, including methane, are most likely to collect at roof level while carbon dioxide
will tend to pool in low lying areas. Hence, measurements should be taken in those
locations in addition to within the general body of air. Extension probes provide a means of
drawing a sample from a location that is unsafe or out of reach.

Grab samples are volumes of air or gas mixtures that are collected in sample containers
underground for subsequent laboratory analysis. Typically, the sample is drawn into a
metal or plastic container by means of a hand-operated pump or by water displacement.
This is usually the method employed for retrieving samples from behind seals or stoppings.
The sample pipe should extend far enough beyond the seal to prevent contamination by air
that has ‘breathed’ through the seal during preceding periods of rising barometric pressure.
Sufficient gas should be drawn from the pipe prior to sampling in order to ensure that the
captured gas is representative of the atmosphere beyond the seal. Care should be taken to
prevent loss or pollution of the sample as the container is subjected to pressure changes
during the journey to the surface. The gas seals on the containers should be well maintained
and samples should be transported to the laboratory for expeditious analysis.

Personal samplers are devices that are worn continuously by personnel while at work. The
simplest are badges that change colour in the presence of selected gases or radiation. More
sophisticated samplers for dust or gases draw power from either an internal battery or a
caplamp battery. Personal gas samplers emit audio—visual alarm signals when a
preselected concentration of gas is exceeded.

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Automatic And Remote Monitors

Permanent environmental monitors may be positioned at strategic locations throughout a

subsurface ventilation system. The gases most frequently subject to this type of monitoring
are methane, carbon monoxide and carbon dioxide. Other gases may be monitored in
workshops, repositories and for special applications such as hydrogen at the roofs of
battery charging stations. Environmental monitors in an underground repository for nuclear
waste must also be provided to detect airborne radionucide contamination.

Permanent monitors should be mounted at strategic locations chosen on a site specific

basis. However, it is prudent to site transducers at the intake and return ends of working
areas and at intervals along return routes. Carbon monoxide sensors mounted at intervals
along conveyor roads provide an earlier warning of fire than temperature-sensitive devices.
In addition to providing local audio-visual alarms, an environmental monitoring system
operates most efficiently when it is integrated into a telemetering network. The signals
from gas, airflow, pressure and temperature transducers are transmitted to a remote
computer and control station, usually on surface, where those signals are analysed for
trends, recorded on magnetic media, operate alarms when appropriate and, possibly,
generate feedback control signals to fans, doors or motorized regulators. Monitors at
critical locations such as booster fans should be installed as dual or, even, triple units to
safeguard against instrument failure. Rechargeable batteries can provide back–up in the
event of a cut in electrical power. A system of planned maintenance should be
implemented in order to ensure continuous and reliable operation. A computer-controlled
telemetering system should be capable of detecting and identifying failed monitors.

Machine-mounted gas monitors should be provided on rock breaking equipment to test for
methane in coal and other gassy mines. These devices must be particularly rugged in order
to remain operational when subjected to dust, water sprays, vibration and impact. Machine-
mounted methanometers should not only provide audio-visual warnings but also be
connected such that the electrical power supply to the machine is isolated when the
methane concentration reaches one percent or other concentration as required by the
relevant mining legislation). Here again, machine—mounted monitors may be integrated
into a mine telemetering system.
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Tube bundle systems are a slower alternative means of remote sampling. Air is drawn
through plastic tubing from chosen locations in the mine to monitoring stations, which may
be located, either underground or on surface. At a monitoring station, automatic valves on
the tubes are operated in a cyclic manner in order to draw samples from the tubes
sequentially, and to pass those samples into gas detection units. The latter are usually
infrared analysers connected in a series to monitor the concentrations of each of the
required gases. A gas pump on each tube maintains continuous flow. However, the main
disadvantage of the tube bundle system is the travel time of the gas between entering a tube
and analysis. While surface monitoring stations are preferred, workings distant from shaft
bottoms may necessitate local underground stations. Tube bundle systems are not suitable
for emergency situations that occur quickly such as an equipment fire. However, they have
proved valuable for the identification of longer-term trends including incipient spontaneous
combustion.
The tubes should be fitted with dust filters and water traps. Variations of temperature and
pressure may cause condensation as the air passes through the tubes. Care must be taken
during the installation of a tube bundle system, particularly at joints, as leaks are difficult to
detect and locate. An important advantage of the system is that it requires no electrical
power in the monitoring station. Hence, it remains operational when sampling from behind
seals or when no electrical supply is available.

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