METHANE (6211)/Combustible-Gas Indicator Method
6211 METHANE*
6211 A. Introduction
1. Occurrence and Significance
Methane (CH4) is a colorless, odorless, tasteless combustible
gas occasionally found in groundwaters. Escape of this gas from
water may cause an explosive atmosphere not only in a utility’s
tanks, pumphouses, and other facilities, but also on the consum-
er’s property, particularly where water is sprayed through poorly
ventilated spaces such as public showers.
The explosive limits of CH4 in air are 5 to 15% by volume. At
sea level, a 3.95% CH4 concentration in air theoretically could be
reached in a poorly ventilated space sprayed with hot (68°C)
water having a CH4 concentration of only 0.7 mg/L. At higher
water temperatures, the vapor pressure of water is so great that
no explosive mixture can form. At lower barometric pressures,
the theoretical hazardous concentration of methane in water will
be reduced proportionately. In an atmosphere of N2 or other inert
* Approved by Standard Methods Committee, 2000.
6211 B. Combustible-Gas Indicator Method
1. General Discussion
a. Principle: An equilibrium according to Henry’s law is
established between CH4 in solution and the partial pressure of
CH4 in the gas phase above the solution. The partial pressure of
CH4 can be determined with a combustible-gas indicator. The
operation of the instrument is based on the catalytic oxidation of
a combustible gas on a heated platinum filament that is made a
part of a Wheatstone bridge. The heat generated by the oxidation
of the gas increases the electrical resistance of the filament. The
resulting imbalance of the electrical circuit causes deflection of
a milliammeter that may be calibrated in terms of percentage of CH4
or percentage of the lower explosive limit of the gas sampled.
b. Interference: Small amounts of ethane usually are asso-
ciated with CH4 in natural gas and presumably would be
present in water that contains methane. Hydrogen gas has
been observed in well waters and would behave similarly to
CH4 in this procedure. Hydrogen sulfide may interfere if the
pH of the water is low enough for an appreciable fraction of
the total sulfide to exist in the un-ionized form. The vapors of
combustible oils also may interfere. In general, these inter-
ferences are of no practical importance because primary interest
is in calculating the explosion hazard to which all combustible gases
and vapors contribute.
Interference due to H2S can be reduced by the addition of solid
NaOH to the container before sampling.
c. Minimum detectable concentration: The limit of sensitivity
of the test is approximately 0.2 mg/L.
d. Sampling: If the water is supersaturated with CH4, a rep-
resentative sample cannot be obtained unless the water is under
sufficient pressure to keep all of the gas dissolved. Operate wells
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gas, at least 12.8% O2 must be present for there to be an
explosion hazard.
Methane also is produced from wastewater and may be present
in sewers and wastewater treatment plants (see Section 2720).
2. Selection of Method
The combustible-gas indicator method (B) offers the advan-
tages of simplicity, speed, and great sensitivity. The volumetric
method (C) can be made more accurate for concentrations of 4 to
5 mg/L and higher, but will not be satisfactory for very low
concentrations. The volumetric method also can be applied to
differentiate between CH4 and other gases, as when a water
supply is contaminated by liquid petroleum gas or other volatile
combustible materials.
Methane also may be determined with the gas chromatograph
as described in Sludge Digester Gas, Section 2720. This method
permits differentiation between H2 and CH4, and/or its higher
homologs.
long enough to insure sampling water coming directly from the
aquifer. Representative samples can be expected only when the
well is equipped with a pump operating at sufficient submer-
gence to assure that no gas escapes from the water.
2. Apparatus
a. Combustible-gas indicator:* Connect a three-way stopcock to
the inlet to zero instrument on atmospheric air immediately before
obtaining sample reading. For laboratory use, replace the suction
bulb with a filter pump throttled to draw gas through the instrument
at a rate of approximately 600 mL/min. See Figure 6211:1.
b. Laboratory filter pump.
c. Glass bottle, 4-L, fitted with a two-hole rubber stopper.
Extend inlet tube to within 1 cm of bottom. End outlet tube
approximately 1 cm below stopper. Use metal or glass tubes,
each fitted with stopcocks or with short (approximately 5-cm)
lengths of rubber tubing and pinchcocks. The entire assembly
should be capable of holding a low vacuum for several hours.
Determine volume of assembly by filling with water and mea-
suring volume, or weight, of water contained.
3. Reagent
Sodium hydroxide, NaOH, pellets.
* Marketed under the following trade names: “Explosimeter,” “Methane Gas
Detector,” and “Methane Tester,” all manufactured by Mine Safety Appliance
Co., Pittsburgh, PA 15235, and “J-W Combustible Gas Indicator,” manufactured
by Bacharach Instrument Co., Mountain View, CA 94043, or equivalent.
6-36 INDIVIDUAL ORGANIC COMPOUNDS (6000)

Henry’s
Temperature Henry’s Constant Temperature Constant
°C H* °C H*

0 2.265 40 5.261
5 2.625 45 5.577
10 3.010 50 5.846
15 3.413 60 6.342
20 3.804 70 6.749
25 4.181 80 6.911
30 4.544 90 7.013
35 4.926 100 7.106
* Multiply given values by 106.

For most determinations, it may be assumed that atmospheric

pressure is 100 kPa, and that the temperature is 20°C. The
concentration of CH4 in the sample is then given by:

冉 冊
Figure 6211:1. Combustible gas indicator circuit and flow diagram.
V0 ⫺ V1
mg CH4/L ⫽ Rf 6.7 ⫹ 0.24
V1

4. Procedure
a. Rough estimation of CH4 concentration: Fill bottle about
half full of water, using a rubber tube connecting sampling tap
and inlet tube, with outlet tube open. With both inlet and outlet
tubes closed, shake bottle vigorously for approximately 15 s and
let stand for approximately 1 min. Sample gas phase by with-
drawing gas from the outlet, leaving inlet open to admit air. If the
needle swings rapidly to a high level on the meter and then drops
to zero, the CH4-air mixture is too rich to burn; take a smaller
sample for the final test. If needle deflection is too small to be
read accurately, take a larger volume of water.
b. Accurate determination: If the water contains H2S, add
approximately 0.5 g NaOH pellets to empty bottle to suppress
interference. Evacuate bottle, using filter pump. Fill bottle not
more than three-quarters full by connecting inlet tube to sam-
pling cock, with outlet tube closed. After collecting desired
volume of water, let bottle fill with air through inlet tube. Close
inlet cock, shake bottle vigorously for 60 s, and let stand for at least
where:
R ⫽ scale reading,
V0 ⫽ total volume of sample bottle, mL,
V1 ⫽ volume of water sampled, mL, and
f ⫽ factor depending on instrument used.
If the instrument reads directly in percentage of methane, f ⫽
1.00. If the instrument reads in percentage of the lower explosive
limit of CH4, f ⫽ 0.05. For instruments that require additional
factors, consult the manufacturer. For example, one commercial
instrument with a scale that reads in percentage of the lower
explosive limit of combustible gases requires an additional factor
of 0.77 for CH4. Hence, the value of f in the above equation
would be 0.77 ⫻ 0.05, or 0.0385.
For more accurate work, or in locations where normal baro-
metric pressure is significantly lower than 100 kPa, use the
equation:

冉 冊
2 h. Sample gas phase through outlet tube with inlet cock open.
Take reading as rapidly as possible before the entering air has V 0 ⫺ V 1 8900
mg CH4/L ⫽ RBf 19.277 ⫹
diluted sample appreciably. Measure volume of water sampled. TV 1 H

5. Calculation
where:
The weight of CH4 (w), in mg, in the sample is given by the B ⫽ barometric pressure, kPa,
equation: and other symbols are as above.

冉
1.928 V g 890 V 1
w ⫽ P T ⫹ 273 ⫹ H 冊 6. Accuracy

The accuracy of the determination is limited by the accuracy

where: of the instrument used. Errors of approximately 10% may be
P ⫽ partial pressure of CH4, kPa, expected. Calibration of instrument on known CH4-air mixtures
T ⫽ temperature, °C, will improve accuracy.
Vg ⫽ volume of gas phase, mL,
V1 ⫽ volume of liquid phase, mL, and 7. Bibliography
H ⫽ Henry’s law constant, kPa/mole CH4/mole of water.
ROSSUM, J.R., P.A. VILLARRUZ & J.A. WADE. 1950. A new method for
Values for Henry’s constant are as follows: determining methane in water. J. Amer. Water Works Assoc. 42:413.
EDB AND DBCP (6231)/Liquid-Liquid Extraction GC Method
6211 C. Volumetric Method
1. General Discussion
a. Principle: If CH4 is slowly mixed with an excess of O2
in the presence of a platinum coil heated to yellow incandes-
cence, most of the CH4 will be converted to CO2 and H2O in
a smooth reaction. Several passes of the mixed gases may be
needed to burn substantially all the CH4. An excess of O2 is
mixed with the sample before passage through the assembly.
By differential absorption and volumetric changes the product
CO2 is measured.
b. Interference: Low-boiling hydrocarbons other than ethane
and vapors from combustible oils interfere. These substances,
however, are not likely to be present in water in sufficiently high
concentration to affect the results significantly.
c. Minimum detectable concentration: This method is not
satisfactory for determining CH4 in water where the concentra-
tion is less than 2 mg/L.
d. Sampling: Collect sample as directed in Method B and
observe the same precautions to obtain representative samples
(Section 6211B.1d). Omit NaOH pellets and fill sample bottle
with water up to 90% of capacity.
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2. Methane Determination
See Section 2720B for a description of apparatus, reagents,
procedure, calculation, and precision and bias.
Use percentage of CH4 found by this method with Henry’s law
to obtain the CH4 concentration in original sample. Substitute
CH4 percentage for R (scale reading) and f ⫽ 1 in the calculation
given under Section 6211B.5 preceding.
3. Bibliography
DENNIS, L.M. & M.L. NICHOLS. 1929. Gas Analysis. Macmillan Co.,
New York, N.Y.
HALDANE, J.S. & J.I. GRAHAM. 1935. Methods of Air Analysis. Charles
Griffin & Co., London.
BUSWELL, A.M. & T.E. LARSON. 1937. Methane in ground waters.
J. Amer. Water Works Assoc. 29:1978.
BERGER, L.B. & H.H. SCHRENK. 1938. Bureau of Mines Haldane gas
analysis apparatus. U.S. Bur. Mines Information Circ. No. 7017.
LARSON, T.E. 1938. Properties and determination of methane in ground
waters. J. Amer. Water Works Assoc. 30:1828.