6211
Methane
Approved by Standard Methods Committee, 2010. Editorial revisions, 2020.
6211
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 consumer’s
property, particularly where water is sprayed through poorly ven-
tilated 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 tem-
peratures, 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 pro-
portionately. In an atmosphere of N2 or other inert gas, at least
12.8% O2 must be present for there to be an explosion hazard.
6211 B. Combustible-Gas Indicator Method
1. General Discussion
a. Principle: An equilibrium according to Henry’s law is estab-
lished 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 com-
bustible 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 result-
ing imbalance of the electrical circuit causes deflection of a mil-
liammeter 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 associ-
ated 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 pro-
cedure. 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 interferences are of no practical
importance because primary interest is in calculating the explo-
sion 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.
https://doi.org/10.2105/SMWW.2882.119
A. Introduction
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 dif-
ferentiate between CH4 and other gases, as when a water supply
is contaminated by liquid petroleum gas or other volatile combus-
tible materials.
Methane also may be determined with the gas chromatograph
as described in Section 2720 C. This method permits differentia-
tion between H2 and CH4, and/or its higher homologs.
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
long enough to ensure sampling water coming directly from the
aquifer. Representative samples can be expected only when the
well is equipped with a pump operating at sufficient submergence
to ensure that no gas escapes from the water.
e. Quality control (QC): The QC practices considered to be
an integral part of each method are summarized in Table 6020:1.
2. Apparatus
a. Combustible-gas indicator: Connect a 3-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 instru-
ment at a rate of approximately 600 mL/min. See Figure 6211:1.
b. Laboratory filter pump.
c. Glass bottle, 4-L, fitted with a 2-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
1
 6211 METHANE - B. Combustible-Gas Indicator Method

where:
P = partial pressure of CH4 (kPa),
Vg = volume of gas phase (mL),
T = temperature (°C),
V1 = volume of liquid phase (mL), and
H = Henry’s law constant (kPa/mole CH4/mole of water).

Values for Henry’s constant are as follows:

Henry’s Henry’s
Temperature (°C) Constant, H* Temperature (°C) Constant, 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
Figure 6211:1. Combustible gas indicator circuit and flow diagram. 35 4.926 100 7.106
Multiply given values by 106.
*

of holding a low vacuum for several hours. Determine volume of

assembly by filling with water and measuring volume, or weight, For most determinations, it may be assumed that atmospheric
of water contained. pressure is 100 kPa, and that the temperature is 20 °C. The con-
centration of CH4 in the sample is then given by:
3. Reagent
 V − V1 
mg CH 4 /L = Rf 6.7 0 + 0.24
Sodium hydroxide (NaOH) pellets.  V1 

4. Procedure where:

a. Rough estimation of CH4 concentration: Fill bottle about R = scale reading,

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 approx-
imately 15 s and let stand for approximately 1 min. Sample
gas phase by withdrawing 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 CH 4-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 sampling
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 2 h.
Sample gas phase through outlet tube with inlet cock open. Take
reading as rapidly as possible before the entering air has diluted
sample appreciably. Measure volume of water sampled.
f = factor depending on instrument used,
V0 = total volume of sample bottle (mL), and
V1 = volume of water sampled (mL).
If the instrument reads directly in percentage of methane,
f = 1.00. If the instrument reads in percentage of the lower explo-
sive 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 baromet-
ric pressure is significantly <100 kPa, use the equation:
 V − V1 8900 
mg CH 4 /L = RBf 19.277 0 + 
 TV1 H 
where:
B = barometric pressure, kPa,

5. Calculation and other symbols are as above.

The weight of CH4 (w), in mg, in the sample is given by the 6. Accuracy
equation:
The accuracy of the determination is limited by the accuracy
1.928 Vg 890 V  of the instrument used. Errors of approximately 10% may be
w = p  + 1
 expected. Calibration of instrument on known CH4–air mixtures
 T + 273 H 
will improve accuracy.

https://doi.org/10.2105/SMWW.2882.119 2
 6211 METHANE - C. Volumetric Method
Bibliography
Rossum JR, Villarruz PA, Wade JA Jr. A new method for determining
methane in water. J Amer Water Works Assoc. 1950;42(4):413–415.
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 incandescence, 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 sub-
stantially 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 satis-
factory for determining CH4 in water where the concentration is
<2 mg/L.
d. Sampling: Collect sample as directed in 6211 B and
observe the same precautions to obtain representative samples
(6211 B.1d). Omit NaOH pellets and fill sample bottle with water
up to 90% of capacity.
e. Quality control (QC): The QC practices considered to be
an integral part of each method are summarized in Table 6020:1.
Published online: August 27, 2018
Revised: March 17, 2020
https://doi.org/10.2105/SMWW.2882.119
2. Methane Determination
See Section 2720 B 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 6211 B.5.
Bibliography
Dennis LM, Nichols ML. Gas analysis. New York (NY): Macmillan Co.,
1929.
Haldane JS, Graham JI. 1935. Methods of air analysis. London (UK):
Charles Griffin & Co.; 1935.
Buswell AM, Larson TE. Methane in ground waters. J Amer Water Works
Assoc. 1937;29:1978.
Berger LB, Schrenk HH. Bureau of Mines Haldane gas analysis apparatus.
U.S. Bureau of Mines Information Circ. No. 7017; 1938.
Larson TE. Properties and determination of methane in ground waters.
J Amer Water Works Assoc. 1938;30:1828.
3