State of California

AIR RESOURCES BOARD

METHOD 3

Gas Analysis for Carbon Dioxide,

Oxygen, Excess Air, and Dry Molecular Weight

Adopted: June 29, 1983

Amended: March 28, 1986
Amended: July 1, 1999
 METHOD 3

Gas Analysis for Carbon Dioxide,

Oxygen, Excess Air, and Dry Molecular Weight

1 Principle and Applicability

1.1 Principle

A gas sample is extracted from a stack, by one of the following methods: (1) single-point,
grab sampling; (2) single-point, integrated sampling; or (3) multi-point, integrated
sampling. The gas sample is analyzed for percent carbon dioxide (CO 2), percent oxygen
(O2), and, if necessary, percent carbon monoxide (CO). For dry molecular weight
determination, either an Orsat or a Fyrite analyzer or other analyzers specified in Method
100 may be used for the analysis; for excess air or emission rate correction factor
determination, an Orsat analyzer or analyzers specified in Method 100 must be used.

1.2 Applicability

1.2.1

This method is applicable for determining CO 2 and O2 concentrations, excess air, and dry
molecular weight of a sample from a gas stream of a fossil-fuel combustion process. The
method may also be applicable to other processes where it has been determined that
compounds other than CO2, O2, CO, and nitrogen (N2) are not present in concentration
sufficient to affect the results.

1.2.2

Other methods, as well as modifications to the procedure described herein, are also
applicable for some or all of the above determinations. Any modification of this method
beyond those expressly permitted shall be considered a major modification subject to the
approval of the Executive Officer. The term Executive Officer as used in this document
shall mean the Executive Officer of the Air Resources Board (ARB), or his or her
authorized representative. Examples of specific methods and modifications include: (1)
a multi-point sampling method using an Orsat analyzer to analyze individual grab
samples obtained at each point; (2) a method using CO 2 or O2 and stoichiometric
calculations to determine dry molecular weight and excess air; (3) assigning a value of
30.0 for dry molecular weight, in lieu of actual measurements, for processes burning
natural gas, coal, or oil. These methods and modifications may be used, but are subject
to the approval of the Executive Officer.

1.2.3

July 1999 CARB Method 3 Page 1

 Note. Mention of trade names or specific products does not constitute endorsement by
the Air Resources Board.

2 Apparatus

As an alternative to the sampling apparatus and systems described herein, other sampling
systems (e.g., liquid displacement) may be used provided such systems are capable of
obtaining a representative sample and maintaining a constant sampling rate, and are
otherwise capable of yielding acceptable results. Use of such systems is subject to the
approval of the Executive Officer.

2.1 Grab Sampling (Figure 3-1)

2.1.1 Probe

Stainless steel or borosilicate glass tubing equipped with an in-stack or out-stack

filter to remove particulate matter (a plug of glass wool is satisfactory for this
purpose). Any other material inert to O2, CO2, CO, and N2 and resistant to
temperature at sampling conditions may be used for the probe; examples of such
material are aluminum, copper, quartz glass and Teflon.

2.1.1 Pump

A one-way squeeze bulb, or equivalent, to transport the gas sample to the analyzer.

2.2 Integrated Sampling (Figure 3.2)

2.2.1 Probe

Same as in Section 2.1.1.

2.2.2 Condenser

An air-cooled or water-cooled condenser, or other condenser no greater than 250

ml that will not remove O2, CO2, CO, and N2, to remove excess moisture which
would interfere with the operation of the pump and flow meter.

2.2.3 Valve

A needle valve, to adjust sample gas flow rate.

2.2.4 Pump

A leak-free, diaphragm-type pump, or equivalent, to transport sample gas to the

flexible bag. Install a small surge tank between the pump and rate meter to
eliminate the pulsation effect of the diaphragm pump on the rotameter.

July 1999 CARB Method 3 Page 2

 2.2.5 Rate Meter

A rotameter, or equivalent rate meter, capable of measuring flow rate to within 2

percent of the selected flow rate. A flow rate range of 500 to 1000 cc/min is
suggested.

2.2.6 Flexible Bag

Any leak-free plastic (e.g., Tedlar, Mylar, Teflon) or plastic-coated aluminum (e.g.,
aluminized Mylar) bag, or equivalent, having a capacity consistent with the selected
flow rate and time length of the test run. A capacity in the range of 55 to 90 liters is
suggested.

To leak-check the bag, connect it to a water manometer and pressurize the bag to 5
to 10 cm H2O (2 to 4 in H2O). Allow to stand for for 10 minutes. Any displacement
of the water manometer indicates a leak. An alternative method is to pressurize the
bag to 5 to 10 cm (2 to 4 in.) H2O and allow to stand overnight. A deflated bag
indicates a leak.

2.2.7 Pressure Gauge

A water-filled U-tube manometer, or equivalent, of about 30 cm (12 in), for the

flexible bag leak-check.

2.2.8 Vacuum Gauge

A mercury manometer, or equivalent, of at least 760 mm (30 in.) Hg is used for the
sampling train leak-check.

2.3 Analysis

For Orsat and Fyrite analyzer maintenance and operation procedures, follow the
instructions recommended by the manufacturer, unless otherwise specified herein.

2.3.1 Dry Molecular Weight Determination

An Orsat analyzer or Fyrite-type combustion gas analyzer may be used.

2.3.2 Emission Rate Correction Factor or Excess Air Determination

An Orsat analyzer must be used. For low CO2 (less than 4.0 percent) or high O2
(greater than 15.0 percent) concentrations, the measuring burette of the Orsat must
have at least 0.1 percent subdivisions.

3 Dry Molecular Weight Determination

July 1999 CARB Method 3 Page 3

Any of the three sampling and analytical procedures described below may be used for
determining the dry molecular weight.

3.1 Single-Point, Grab Sampling and Analytical Procedure

3.1.1

The sampling point in the duct shall either be at the centroid of the cross section or
at a point no closer to the walls than 1.00 m (3.3 ft), unless otherwise specified by
the Executive Officer.

3.1.2

Set up the equipment as shown in Figure 3-1, making sure all connnections ahead
of the analyzer are tight. If an Orsat analyzer is used, it is recommended that the
analyzer be leak-checked by following the procedure in Section 5; however, the
leak check is optional.

3.1.3

Place the probe in the stack, with the tip of the probe positioned at the sampling
point; purge the sampling line long enough to allow at least 5 exchanges. Draw a
sample into the analyzer and immediately analyze it for percent CO 2 and percent
O2. Determine the percentage of the gas that is N2 and CO by subtracting the sum
of the percent CO2 and percent O2 from 100 percent. Calculate the dry molecular
weight as indicated in Section 6.3.

3.1.4

Repeat the sampling, analysis, and calculation procedures, until the dry molecular
weights of any three grab samples differ from their mean by no more than 0.3 g/g-
mole (0.3 lb/lb-mole). Average these three molecular weights, and report the
results to the nearest 0.1 g/g-mole (lb/lb-mole).

3.2 Single-Point, Integrated Sampling and Analytical Procedure

3.2.1

The sampling point in the duct shall be located as specified in Section 3.1.1.

3.2.2

Leak-check (optional) the flexible bag as in Section 2.2.6. Set up the equipment as
shown in Figure 3-2. Just prior to sampling, leak-check (optional) the train by

July 1999 CARB Method 3 Page 4

 placing a vacuum gauge at the condenser inlet, pulling a vacuum of at least 250
mm Hg (10 in Hg), plugged the outlet at the quick disconnect, and then turning off
the pump. The vacuum should remain stable for at least 0.5 minute. Evacuate the
flexible bag. Connect the probe and place it in the stack, with the tip of the probe
positioned at the sampling point; purge the sampling line. Next, connect the bag
and make sure that all connections are tight.

3.2.3

Sample at a constant rate. The sampling run should be simultaneous with, and for
the same total length of time as, the pollutant emission rate determination.
Collection of at least 30 liters (1.00 ft 3) of sample gas is recommended; however,
smaller volumes may be collected, if desired.

3.2.4

Obtain one integrated flue gas sample during each pollutant emission rate
determination. Within 8 hours after the sample is taken, analyze it for percent CO 2
and percent O2 using either an Orsat analyzer or a Fyrite-type combustion gas
analyzer. If an Orsat analyzer is used, it is recommended that the Orsat leak-check
described in Section 5 be performed before this determination; however the check
is optional. Determine the percentage of the gas that is N 2 and CO by subtracting
the sum of percent CO2 and percent O2 from 100 percent. Calculate the dry
molecular weight as indicated in Section 6.3.

3.2.5

Repeat the analysis and calculation procedures until the individual dry molecular
weights for any three analyses differ from their mean by no more than 0.3 g/g-mole
(0.3 lb/lb-mole).

Average these three molecular weights, and report the results to the nearest 0.1
g/g-mole (0.1 lb/lb-mole).

3.3 Multi-Point, Integrated Sampling and Analytical Procedure

3.3.1

Unless otherwise specified by the Executive Officer, a minimum of eight traverse

points shall be used for circular stacks having diameters less than 0.61 m (24 in.), a
minimum of nine shall be used for rectangular stacks having equivalent diameters
less than 0.61 m (24 in), and a minimum of twelve traverse points shall be used for
all other cases. The traverse points shall be located according to Method 1. The
use of fewer points is subject to approval of the Executive Officer.

July 1999 CARB Method 3 Page 5

 3.3.2

Follow the procedures outlined in Sections 3.2.2 through 3.2.5, except for the
following: traverse all sampling points and sample at each point for an equal length
of time. Record sampling data as shown in Figure 3-3.

4 Emission Rate Correction Factor or Excess Air Determination

NOTE: A Fyrite-type combustion gas analyzer is not acceptable for excess air or
emission rate correction factor determination, unless approved by the Executive Officer.
If both percent CO2 and percent O2 are measured, the analytical results of any of the
three procedures given below may also be used for calculating the dry molecular weight.

Each of the three procedures below shall be used only when specified in an applicable
subpart of the standards. The use of these procedures for other purposes must have
specific prior approval of the Executive Officer.

4.1 Single Point, Grab Sampling and Analytical Procedure

4.1.1

The Sampling point in the duct shall either be at the centroid of the cross section or
at a point no closer to the walls than 1.00 m (3.3 ft), unless otherwise specified by
the Executive Officer.

4.1.2

Set up the equipment as shown in Figure 3-1, making sure all connections ahead of
the analyzer are tight and leak-free. Leak check the Orsat analyzer according to
the procedure described in Section 5. This leak check is mandatory.

4.1.3

Place the probe in the stack, with the tip of the probe positioned at the sampling
point; purge the sampling line long enough to allow at least 5 exchanges. Draw a
sample into the analyzer. For emission rate correction factor determination,
immediately analyze the sample, as outlined in Sections 4.1.4 and 4.1.5, for percent
CO2 or percent O2. If excess air is desired, proceed as follows: (1) immediately
analyze the sample, as in Sections 4.1.4 and 4.1.5, for percent CO 2, O2 and CO; (2)
determine the percentage of the gas that is N 2 by subtracting the percent CO2,
percent O2 and percent CO from 100 percent; and (3) calculate percent excess air
as outlined in Section 6.2.

4.1.4

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 To ensure complete absorption of the CO 2, O2, or if applicable, CO, make repeated
passes through each absorbing solution until two consecutive readings are the
same. Several passes (three or four) shall be made between the readings. If
constant readings cannot be obtained after three consecutive readings replace the
absorbing solution.

4.1.5

After the analysis is completed, leak check (mandatory) the Orsat analyzer once
again, as described in Section 5. For the results of the analysis to be valid, the
Orsat analyzer must pass this leak test before and after the analysis. Note: Since
this single-point, grab sampling and analytical procedure is normally conducted in
connection with a single-point, grab-sampling and analytical procedure for a
pollutant, only one analysis is ordinarily conducted. Therefore, great care must be
taken to obtain a valid sample and analysis. Although in most cases only CO 2 or O2
is required, is recommended that both CO 2 and O2 be measured and that Section
4.4 be used to validate the analytical data.

4.2 Single-Point, Integrated Sampling and Analytical Procedure

4.2.1

The sampling point in the duct shall be located as specified in Section 4.1.1.

4.2.2

Leak check (mandatory) the flexible bag as in Section 2.2.6. Set up the equipment
as shown in Figure 3-2. Just prior to sampling, leak check (mandatory) the train by
placing a vacuum gauge at the condenser inlet, pulling a vacuum of at least 250
mm Hg (10 in. Hg), plugging the outlet at the quick disconnect, and then turning off
the pump. The vacuum shall remain stable for at least 0.5 minute. Evacuate the
flexible bag. Connect the probe and place it in the stack, with the tip of the probe
positioned at the sampling point; purge the sampling line. Next, connect the bag,
and make sure that all connections are tight.

4.2.3

Sample at a constant rate or as specified by the Executive Officer. The sampling

run must be simultaneous with, and for the same total length of time as, the
pollutant emission rate determination. Collection of at least 30 liters (1.00 ft 3) of
sample gas is recommended; however, smaller volumes may be collected if
desired.

4.2.4

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 Obtain one integrated flue gas sample during each pollutant emission rate
determination. For emission rate correction factor detrmination, analyze the sample
within 4 hours after it is taken for percent CO2 or percent O2 (as outlined in Sections
4.2.5 through 4.2.7). The Orsat analyzer must be leak-checked (see Section 5)
before the analysis. If excess air is desired, proceed as follows: (1) within 4 hours
after the sample is taken, analyze it (as in Sections 4.2.5 through 4.2.7) for percent
CO2, O2, and CO; (2) determine the percentage of the gas that is N 2 by subtracting
the sum of the percent CO2, percent O2 and percent CO from 100 percent; (3)
calculate percent excess air, as outlined in Section 6.2.

4.2.5

To ensure complete absorption of the CO 2, O2, or if applicable, CO, make repeated

passes through each absorbing solution until two consecutive readings are the
same. Several passes (three or four) should be made between readings. (If
constant readings cannot be obtained after 3 consecutive readings, replace the
absorbing solution.)

4.2.6

Repeat the analysis until the following criteria are met:

4.2.6.1

For percent CO2, repeat the analytical procedure until the results of any three
analyses differ by no more than (a) 0.3 percent by volume when CO 2 is
greater than 4.0 percent or (b) 0.2 percent by volume when CO 2 is less than or
equal to 4.0 percent. Average the three acceptable values of percent CO 2
and report the results to the nearest 0.1 percent.

4.2.6.2

For percent O2, repeat the analytical procedure until the results of any three
analyses differ by no more than (a) 0.3 percent by volume when O 2 is less
than 15.0 percent or (b) 0.2 percent by volume when O 2 is greater than or
equal to 15.0 percent. Average the three acceptable values of percent O 2 and
report the results to the nearest 0.1 percent.

July 1999 CARB Method 3 Page 8

 4.2.6.3

For percent CO, repeat the analytical procedure until the results of any three
analyses differ by no more than 0.3. Average the three acceptable values of
percent CO and report the results to the nearest 0.1 percent.

4.2.7

After the analysis is completed, leak-check the Orsat Analyzer once again, as
described in Section 5. For the results of the analysis to be valid, the Orsat
analyzer must pass this leak test before and after the analysis. Note: Although in
most cases only CO2 or O2 is required, it is recommended that both CO 2 and O2 be
measured, and that carbon balance calculations considering the composition of the
fuel be used to validate the analytical data.

4.3 Multi-Point, Integrated Sampling and Analytical Procedure

4.3.1

Both the minimum number of sampling points and the sampling point location shall
be as specified in Section 3.3.1 of this method. The use of fewer points is subject
to the approval of the Executive Officer.

4.3.2

Follow the procedures outlined in Sections 4.2.2 through 4.2.7, except for the
following: Traverse all sampling points, and sample at each point for an equal
length of time. Record sampling data as shown in Figure 3-3.

4.4 Quality Control Procedures

4.4.1 Data Validation when Both CO 2 and O2 are measured

Although in most instances, only CO2 or O2 measurement is required, it is

recommended that both CO2 and O2 be measured to provide a check on the quality
of the data. The following quality control procedure is suggested. Note: Since the
method for validating the CO2 and O2 analyses is based on combustion of organic
and fossil fuels and dilution of the gas stream with air, this method does not apply to
sources that (1) remove CO2 or O2 through processes other than combustion (2)
add O2 (e.g. oxygen enrichment) and N2 in proportions different from that of air, (3)
add CO2 (e.g. cement or lime kilns), or (4) have no fuel factor, F o values obtainable
(e.g., extremely variable waste mixtures). This method validates the measured
proportions of CO2 and O2 for the fuel type, but the method does not detect sample
dilution resulting from leaks during or after sample collection. This method is
applicable for samples collected downstream of most lime or limestone flue-gas
desulfurization units as the CO 2 added or removed from the gas stream is not
significant in relation to the total CO2 concentration. The CO2 concentrations from
other types of scrubbers using only water or basic slurry can be significantly
affected and would render the Fo check minimally useful.

4.4.1.1

Calculate a fuel factor, Fo using the following equation:

Fo = (20.9 - %O2) / (%CO2) Eq. 3-3

Where:
%O2 = Percent O2 by volume (dry basis).
%CO2 = Percent CO2 by volume (dry basis).
20.9 = Percent O2 by volume in ambient air.

If CO is present in quantities measurable by this method, adjust the O 2 and

CO2 values before performing the calculation for Fo as follows:

%CO2 (adj) = %CO2 + %CO

%O2 (adj) = %O2 - 0.5 %CO

Where:
%CO = Percent CO by volume (dry basis).

4.4.1.2

Compare the calculated Fo factor with the expected Fo values. The following
table may be used in establishing acceptable ranges for the expected F o if the
fuel being burned is known. When fuels are burned in combination, calculate
the combined fuel Fd and Fc factors (as defined in EPA Method 19, 40 CFR 60
Appendix A) according to the procedure in EPA Method 19 Section 3. Then
calculate the F factor as follows:

Fo = 0.209 Fd / Fc Equation 3-4

___________________________________________________

Fuel Type Fo range

Coal:
Anthracite and Lignite 1.016 - 1.130
Bituminous 1.083 - 1.230
Oil
Distillate 1.260 - 1.413
Residual 1.210 - 1.370
Gas
Natural 1.600 - 1.838
Propane 1.434 - 1.586
Butane 1.405 - 1.553

Wood 1.000 - 1.120

Wood Bark 1.003 - 1.130
 ___________________________________________________

Calculated Fo values beyond the acceptable ranges shown in this table should
be investigated before accepting the test results. For example, the strength of
the solutions in the gas analyzer and the analyzing technique should be
checked by sampling and anayzing a known concentration, such as air, the
fuel factor should be reviewed and verified. An acceptability range of +/- 12
percent is appropriate for the Fo factor of mixed fuels with variable fuel ratios.
The level of the emission rate relative to the compliance level should be
considered in determining if a retest is appropriate, i.e., if the measured
emissions are much lower or much greater than the compliance limit repetition
of this test would not significantly change the compliance status of the source
and would be unnecessarily time consuming and costly.

5. LEAK-CHECK PROCEDURE FOR ORSAT ANALYZER

Moving an Orsat analyzer frequently causes it to leak. Therefore, an Orsat analyzer should be
thoroughly leak checked on site before the flue gas sample is introduced into it. The
procedure for leak checking an Orsat analyzer is as follows:

5.1

Bring the liquid level in each pipette up to the reference mark on the capillary tubing, and
then close the pipette stopcock.

5.2

Raise the leveling bulb sufficiently to bring the confining liquid meniscus onto the
graduated portion of the burette and then close the manifold stopcock.

5.3

Record the meniscus position.

5.4

Observe the meniscus in the burette and the liquid level in the pipette for movement over
the next 4 minutes.

5.5

For the Orsat analyzer to pass the leak check, two conditions must be met:

5.5.1

The liquid level in each pipette must not fall below the bottom of the capillary tubing
during this 4-minute interval.
 5.5.2

The meniscus in the burette must not change by more than 0.2 ml during this 4-
minute interval.

5.6

If the analyzer fails the leak-check procedure, check all rubber connections and
stopcocks to determine whether they might be the cause of the leak. Disassemble, clean
and regrease leaking stopcocks. Replace leaking rubber connections. After the analyzer
is reassembled, repeat the leak-check procedure.

6. Calculations

6.1 Nomenclature

Md = Dry molecular weight, g/g-mole (lb/lb-mole).

%EA = Percent Excess Air.

%CO2 = Percent CO2 by volume, (dry basis).

%O2 = Percent O2 by volume, (dry basis).

%CO = Percent CO by volume, (dry basis).

%N2 = Percent N2 by volume, (dry basis).

0.264 = Ratio of O2 to N2 in air, v/v

0.280 = Molecular weight of N2 or CO, divided by 100.

0.320 = Molecular weight of O2 divided by 100.

0.440 = Molecular weight of CO2 divided by 100.

6.2 Percent Excess Air

Calculate the percent excess air (if applicable), by substituting the appropriate values of
percent O2, CO and N2 (obtained from Section 4.1.3 or 4.2.4) into Equation 3-1.

%EA = [(%O2) - 0.5(%CO)] x100/ [0.264(%N2) - (%O2)+ 0.5(%CO)] Equation 3-1

Note: The equation above assumes that ambient air is used as the source of O 2 and that
the fuel does not contain appreciable amounts of N2 (as do coke or blast furnace gases).
For those cases when appreciable amounts of N2 are present ( coal, oil and natural gas
 do not contain appreciable amounts of N2 ) or when oxygen enrichment is used, alternate
methods, subject to approval of the Executive Officer, are required.

6.3 Dry Molecular Weight

Use Equation 3-2 to calculate the dry molecular weight of the stack gas.

Md = 0.440(%CO2) + 0.320(%O 2) + 0.280(%N2 + %CO) Equation 3-2

Note: The above equation does not consider argon in air (about 0.9 percent, molecular
weight of 39.9). A negative error of about 0.4 percent is introduced. The tester may
choose to include argon in the analysis using procedures subject to approval of the
Executive Officer.

7. Bibliography

1. EPA Method 3, Gas Analysis for Determination of Dry Molecular Weight, CFR40,
Part 60, Appendix A
 Filter
(Glass Wool)
Flexible Tubing ToAnalyzer

Probe

Squeeze Bulb

Figure 3-1 Grab Sampling Train

 Rate Meter

Surge
Filter Tank
(Glass Wool) Valve

Probe
Quick
Disconnect

Air-Tight
Pump
Air-Cooled
Condenser

Bag

Valve Rigid Container

Figure 3-2 – Integrated Gas Sampling Train

 Figure 3-3. Sampling Rate Data.

Time Traverse Pt. Q, liter/min % dev.a

Average
a
% dev. = (Q - Qavg)/Qavg * 100 (Must be  10%)