State of California

Air Resources Board

Method 6
Determination of Sulfur Dioxide Emissions
from Stationary Sources

Adopted: June 29, 1983

Amended: July 1, 1999

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CARB Method 6 Page 0

METHOD 6 - DETERMINATION OF SULFUR DIOXIDE EMISSIONS FROM STATIONARY

SOURCES

Principle and Applicability

1.1

Principle

A gas sample is extracted from the sampling point in the stack. The sulfuric acid mist
(including sulfur trioxide) and the sulfur dioxide (SO2) are separated. The SO 2 fraction is
measured by the barium-thorin titration method.
1.2

Applicability

This method is applicable for the determination of SO 2 emissions from stationary sources.
The minimum detectable limit of the method has been determined to be 3.4 milligrams
(mg) of SO2/m3 (2.12 x 10 -7 lb/ft3). Although no upper limit has been established, tests
have shown that concentrations as high as 80,000 mg/m 3 of SO2 can be collected
efficiently in two midget impingers, each containing 15 milliliters of 3 percent hydrogen
peroxide, at a rate of 1.0 liter/min for 20 minutes. Based on theoretical calculations, the
upper concentration limit in a 20-liter sample is about 93,300 mg/m 3.
Possible interferents are free ammonia, water-soluble cations, and fluorides. The cations
and fluorides are removed by glass wool filters and an isopropanol bubbler, and hence do
not affect the SO2 analysis. When samples are being taken from a gas stream with high
concentrations of very fine metallic fumes (such as found in inlets to control devices), a
high-efficiency glass-fiber filter must be used in place of the glass wool plug (i.e., the one
in the probe) to remove the cation interferents.
Free ammonia interferes by reacting with SO 2 to form particulate sulfite and by reacting
with the indicator. If free ammonia is present (this can be determined by knowledge of
the process and noticing white particulate matter in the probe and isopropanol bubbler),
alternative methods subject to the approval of the Executive Officer, are required.
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.
2

Apparatus
2.1

Sampling

The sampling train is shown in figure 6-1, and component parts are discussed below.
The tester has the option of substituting sampling equipment described in Method 8 in
place of the midget impinger equipment of Method 6. However, the Method 8 train must
be modified to include a heated filter between the probe and isopropanol impinger, and
the operation of the sampling train and sample analysis must be at the flow rates and
solution volumes defined in Method 8.
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The tester also has the option of determining SO 2 simultaneously with particulate matter
and moisture determinations by (1) replacing the water in a Method 5 impinger system
with 3 percent peroxide solution, or (2) by replacing the Method 5 water impinger system
with a Method 8 isopropanol-filter-peroxide system. The analysis for SO 2 must be
consistent with the procedure of Method 8.
2.1.1 Probe
Borosilicate glass, or stainless steel (other materials of construction may be used,
subject to the approval of the Executive Officer), approximately 6-mm inside
diameter, with a heating system to prevent water condensation and a filter (either instack or heated out-stack) to remove particulate matter, including sulfuric acid mist.
A plug of glass wool is a satisfactory filter.
2.1.2 Bubbler and Impingers
One midget bubbler, with medium-coarse glass frit and borosilicate or quartz glass
wool packed in top (see Figure 6-1) to prevent sulfuric acid mist carryover, and
three 30-ml midget impingers. The bubbler and midget impingers must be
connected in series with leak-free glass connectors. Silicone grease may be used if
necessary to prevent leakage.
At the option of the tester, a midget impinger may be used in place of the midget
bubbler.
Other collection absorbers and flow rates may be used, subject to the approval of
the Executive Officer, but the collection efficiency must be shown to be at least 99
percent for each test run and must be documented in the report.
If the efficiency is found to be acceptable after a series of three tests, further
documentation is not required. To conduct the efficiency test, an extra absorber
must be added and analyzed separately. This extra absorber must not contain
more than 1 percent of the total SO 2.
2.1.3 Glass Wool
Borosilicate or quartz.
2.1.4 Stopcock Grease
Acetone-insoluble, heat-stable silicone grease may be used, if necessary.
2.l.5 Temperature Gauge
Dial thermometer, or equivalent, to measure temperature of gas leaving impinger
train to within 1C (2F).
2.1.6 Drying Tube

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Tube packed with 6- to 16-mesh indicating-type silica gel, or equivalent, to dry the
gas sample and to protect the meter and pump. If the silica gel has been used
previously, dry at 175 o C (350o F) for 2 hours. New silica gel may be used as
received. Alternatively, other types of desiccants (equivalent or better) may be
used, subject to approval of the Executive Officer.
2.1.7 Valve
Needle valve, to regulate sample gas flow rate.
2.1.8 Pump
Leak-free diaphragm pump, or equivalent, to pull gas through the train. Install a
small surge tank between the pump and rate meter to eliminate the pulsation effect
of the diaphragm pump on the rotameter.
2.1.9 Rate Meter
Rotameter, or equivalent, capable of measuring flow rate to within 2 percent of the
selected flow rate of about 1000 cc/min.
2.1.10 Volume Meter
Dry gas meter, sufficiently accurate to measure the sample volume to within 2
percent, calibrated at the selected flow rate and conditions actually encountered
during sampling, and equipped with a temperature gauge (dial thermometer, or
equivalent) capable of measuring temperature accurately to within 3C (5.4F).
2.1.11 Barometer
Mercury, aneroid, or other barometer capable of measuring atmospheric pressure to
within 2.5 mm (0.1 in.) Hg. In many cases, the barometric reading may be obtained
from a nearby national weather service station, in which case the station value
(which is the absolute barometric pressure) shall be requested and an adjustment
for evaluation differences between the weather station and sampling point shall be
applied at a rate of minus 2.5 mm Hg (0.1 in. Hg) for 30 m (100 ft) elevation
increase or vice versa for elevation decrease.
2.1.12 Vacuum Gauge and Rotameter
At least 760-mm (30-in.) Hg gauge and 0-40 cc/min rotameter, to be used for leakcheck of the sampling train.
2.2 Sample Recovery
2.2.1 Wash Bottles
Polyethylene or glass, 500-ml, two.
2.2.2 Storage Bottles
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Polyethylene, 100-ml, to store impinger samples (one per sample).

2.3 Analysis
2.3.1 Pipettes
Volumetric type, 5-ml, 20-ml (one per sample), and 25-ml sizes.
2.3.2 Volumetric Flasks
100-ml size (one per sample) and 1000-ml size.
2.3.3 Burettes
5- and 50-ml sizes.
2.3.4 Erlenmeyer Flasks
250-ml size (one for each sample, blank, and standard).
2.3.5 Dropping Bottle
125-ml size, to add indicator.
2.3.6 Graduated Cylinder
100-ml size.
2.3.7 Spectrophotometer
To measure absorbance at 352 nanometers.
3

REAGENTS

Unless otherwise indicated, all reagents must conform to the specifications established by the
Committee on Analytical Reagents of the American Chemical Society. Where such
specifications are not available, use the best available grade.
3.1 Sampling
3.1.1 Water
Deionized, distilled to conform to ASTM Specification D 1193-77, Type 3. At the
option of the analyst, the KMn0 4 test for oxidizable organic matter may be omitted
when high concentrations of organic matter are not expected to be present.
3.1.2 Isopropanol, 80 Percent
Mix 80 ml of isopropanol with 20 ml of water.
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3.1.2.1
Check each lot of isopropanol for peroxide impurities as follows: shake 10 ml
of isopropanol with 10 ml of freshly prepared 10 percent potassium iodide
solution. Prepare a blank by similarly treating 10 ml of distilled water. After 1
minute, read the absorbance at 352 nanometers on a spectrophotometer. If
absorbance exceeds 0.1, reject alcohol for use.
3.1.2.2
Peroxides may be removed from isopropanol by redistilling or by passage
through a column of activated alumina; however, reagent grade isopropanol
with suitably low peroxide levels may be obtained from commercial sources.
Rejection of contaminated lots may, therefore, be a more efficient procedure.
3.1.3 Hydrogen Peroxide, 3 Percent
Dilute 30 percent hydrogen peroxide 1:9 (v/v) with water (30 ml is needed per
sample). Prepare fresh daily.
3.1.4 Potassium Iodide Solution, 10 Percent
Dissolve 10.0 g of KI in water, and dilute to 100 ml. Prepare when needed.
3.2 Sample Recovery
3.2.1 Water
Same as in 3.1.1.
3.2.2 Isopropanol, 80 Percent
Same as in 3.1.2.
3.3 Analysis
3.3.1 Water
Same as in 3.1.1.
3.3.2 Isopropanol, 100 Percent
3.3.3 Thorin Indicator
1-(o-arsonophenylazo)-2-naphthol-3,6-disulfonic acid, disodium salt, or equivalent.
Dissolve 0.20 g in 100 ml of water.
3.3.4 Barium Standard Solution, 0.0100 N
Dissolve 1.95 g of barium perchlorate trihydrate [Ba(Cl0 4)2$3H20] in 200 ml water,
and dilute to 1 liter with isopropanol. Alternatively, 1.22 g of [BaCl 2$2H20] may be
used instead of the perchlorate. Standardize as in Section 5.5.
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3.3.5 Sulfuric Acid Standard, 0.0100 N

Purchase or standardize to 0.0002 N against 0.0100 N Na0H which has
previously been standardized against potassium acid phthalate (primary standard
grade).
3.3.6 Quality Assurance Audit Samples
Sulfate samples in glass vials. Each set will consist of two vials having solutions of
unknown concentrations. Only when making compliance determinations, obtain an
audit sample set from the appropriate EPA regional office or from the responsible
enforcement agency, or from another provider approved by the Executive Officer.
(Note: The tester should notify the EPA regional office or the responsible
enforcement agency at least 30 days prior to the test date to allow sufficient time for
delivery.)
4

PROCEDURE
4.1 Sampling
4.1.1 Preparation of Collection Train
Measure 15 ml of 80 percent isopropanol into the midget bubbler and 15 ml of 3
percent hydrogen peroxide into each of the first two midget impingers. Leave the
final midget impinger dry. Assemble the train as shown in Figure 6-1. Adjust the
probe heater to a temperature sufficient to prevent water condensation. Place
crushed ice and water around the impingers.
4.1.2 Leak-Check Procedure
A leak check prior to the sampling run is optional but strongly recommended; a leak
check after the sampling run is mandatory. The leak-check procedure is as follows:
Temporarily attach a suitable (e.g., 0- to 40-cc/min) rotameter to the outlet of the dry
gas meter, and place a vacuum gauge at or near the probe inlet. Plug the probe
inlet, pull a vacuum of at least 250 mm (10 in.) Hg and note the flow rate as
indicated by the rotameter. A leakage rate not in excess of 2 percent of the average
sampling rate is acceptable.
NOTE: Carefully release the probe inlet plug before turning off the pump.
It is suggested (not mandatory) that the pump be leak-checked separately, either
prior to or after the sampling run. If done prior to the sampling run, the pump leakcheck shall precede the leak-check of the sampling train described immediately
above; if done after the sampling run, the pump leak-check shall follow the train
leak-check. To leak-check the pump, proceed as follows: Disconnect the drying
tube from the probe-impinger assembly. Place a vacuum gauge at the inlet to either
the drying tube or the pump, pull a vacuum of 250 mm Hg (10 in. Hg), plug or pinch

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off the outlet of the flow meter, and then turn off the pump. The vacuum should
remain stable for at least 30 seconds.
Other leak-check procedures may be used, subject to the approval of the Executive
Officer. The procedure used in Method 5 is not suitable for diaphragm pumps.
4.1.3 Sample Collection
Record the initial dry gas meter reading and barometric pressure. To begin
sampling, position the tip of the probe at the sampling point, connect the probe to
the bubbler, and start the pump. Adjust the sample flow to a constant rate of
approximately 1.0 liter/min as indicated by the rotameter. Maintain this constant
rate (10 percent) during the entire sampling run. Take readings (dry gas meter,
temperatures at dry gas meter and at impinger outlet and rate meter) at least every
5 minutes. Add more ice during the run to keep the temperature of the gases
leaving the last impinger at 20 o C (68o F) or less. At the conclusion of each run, turn
off the pump, remove probe from the stack, and record the final readings. Conduct
a leak-check as in Section 4.1.2. (This leak-check is mandatory.) If a leak is found,
void the test run or use procedures acceptable to the Executive Officer to adjust the
sample volume for the leakage. Drain the ice bath, and purge the remaining part of
the train by drawing clean ambient air through the system for 15 minutes at the
sampling rate.
Clean ambient air can be provided by passing air through a charcoal filter or
through an extra midget impinger with 15 ml of 3 percent H202. The tester may opt
to use simply ambient air without purification.
4.2 Sample Recovery
Disconnect the impingers after purging. Discard the contents of the midget bubbler.
Pour the contents of the midget impingers into a leak-free polyethylene bottle for
shipment. Rinse the three midget impingers and the connecting tubes with water, and
add the washings to the same storage container. Mark the fluid level. Seal and identify
the sample container.
4.3 Sample Analysis
Note level of liquid in container, and confirm whether any sample was lost during
shipment; note this on analytical data sheet. If a noticeable amount of leakage has
occurred, either void the sample or use methods, subject to the approval of the Executive
Officer, to correct the final results.
Transfer the contents of the storage container to a 100-ml volumetric flask, and dilute to
exactly 100 ml with water. Pipette a 20-ml aliquot of this solution into a 250-ml
Erlenmeyer flask, add 80 ml of 100 percent isopropanol and two to four drops of thorin
indicator, and titrate to a pink endpoint using 0.0100 N barium standard solution. Repeat
and average the titration volumes. Run a blank with each series of samples. Replicate
titrations must agree within 1 percent or 0.2 ml, whichever is larger.
NOTE: Protect the 0.0100 N barium standard solution from evaporation at all times.
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4.4 Audit Sample Analysis

4.4.1
Concurrently analyze the two audit samples and a set of compliance samples
(Section 4.3) in the same manner to evaluate the technique of the analyst and the
standards preparation. (Note: It is recommended that known quality control
samples be analyzed prior to the compliance and audit sample analysis to optimize
the system accuracy and precision. One source of these samples is listed in
Section 3.3.6. )The same analysts, analytical reagents and analytical system shall
be used both for compliance samples and the EPA audit samples; if this condition is
met, auditing of subsequent compliance analyses for the same enforcement agency
within 30 days is not required. An audit sample set may not be used to validate
different sets of compliance samples under the jurisdiction of different enforcement
agencies, unless prior arrangements are made with both enforcement agencies.
4.4.2
Calculate the concentrations in mg/dscm using the specified sample volume in the
audit instructions. (Note: Indication of acceptable results may be obtained
immediately by reporting the audit results in mg/dscm and compliance results in
total mg SO2/sample by telephone to the responsible enforcement agency.) Include
the results of both audit samples, their identification numbers, and the analyst=s
name with the results of the compliance determination samples in appropriate
reports to the EPA regional office or the appropriate enforcement agency. Include
this information with subsequent compliance analyses for the same enforcement
agency during the 30-day period.
4.4.3
The concentrations of the audit samples obtained by the analyst shall agree within
5 percent of the actual concentrations. If the 5-percent specification is not met,
reanalyze the compliance samples and audit samples, and include initial and
reanalysis values in the test report (see Note in Section 4.4.1).
4.4.4
Failure to meet the 5-percent specification may require retests until the audit
problems are resolved. However, if the audit results do not affect the compliance or
non-compliance status of the affected facility, the Executive Officer may waive the
reanalysis requirement, further audits, or retests and accept the the results of the
compliance test. While steps are being taken to resolve audit analysis problems,
the Executive Officer may also choose to use the data to determine the compliance
or non-compliance of the affected facility.
5

CALIBRATION
5.1 Metering System
5.1.1 Initial Calibration

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Before its initial use in the field, first leak-check the metering system (drying tube,
needle valve, pump, rotameter, and dry gas meter) as follows: Place a vacuum
gauge at the inlet to the drying tube and pull a vacuum of 250 mm (10 in.) Hg; plug
or pinch off the outlet of the flow meter, and then turn off the pump. The vacuum
shall remain stable for at least 30 seconds. Carefully release the vacuum gauge
before releasing the flow meter end.
Next, calibrate the metering system (at the sampling flow rate specified by the
method) as follows: Connect an appropriately sized wet test meter (e.g., 1 liter per
revolution) to the inlet of the drying tube. Make three independent calibrations runs,
using at least five revolutions of the dry gas meter per run. Calculate the calibration
factor, Y (wet test meter calibration volume divided by the dry gas meter volume,
both volumes adjusted to the same reference temperature and pressure), for each
run, and average the results. If any Y-value deviates by more than 2 percent from
the average, the metering system is unacceptable for use. Otherwise, use the
average as the calibration factor for subsequent test runs.
5.1.2 Post-Test Calibration Check
After each field test series, conduct a calibration check as in Section 5.1.1 above,
except for the following variations: (a) the leak-check is not to be conducted, (b)
three, or more revolutions of the dry gas meter may be used, and (c) only two
independent runs need be made. If the calibration factor does not deviate by more
than 5 percent from the initial calibration factor (determined in Section 5.1.1), then
the dry gas meter volumes obtained during the test series are acceptable. If the
calibration factor deviates by more than 5 percent, recalibrate the metering system
as in Section 5.1.1, and for the calculations, use the calibration factor (initial or
recalibration) that yields the lower gas volume for each test run.
5.2 Thermometers
Calibrate against mercury-in-glass thermometers.
5.3 Rotameter
The rotameter need not be calibrated, but should be cleaned and maintained according
to the manufacturer's instruction.
5.4 Barometer
Calibrate against a mercury barometer.
5.5 Barium Standard Solution
Standardize the barium perchlorate or chloride solution against 25 ml of standard sulfuric
acid to which 100 ml of 100 percent isopropanol has been added. Run duplicate
analyses. Calculate the normality using the average of a pair of duplicate analyses where
the titrations agree within 1 percent or 0.2 ml, whichever is larger.
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CALCULATIONS

Carry out calculations, retaining at least one extra decimal figure beyond that of the acquired
data. Round off figures after final calculation.
6.1 Nomenclature
CSO2

Concentration of SO2, dry basis corrected to standard conditions, mg/dscm

(lb/dscf).

Normality of barium standard titrant, meq./ml.

Pbar

Barometric pressure at the exit orifice of the dry gas meter, mm Hg (in Hg).

Pstd

= Standard absolute pressure, 760 mm Hg (29.92 in. Hg).

Tm

Tstd

= Standard absolute temperature, 293K (528R).

Va

Vm

= Dry gas volume as measured by the dry gas meter, dcm (dcf).

Average dry gas meter absolute temperature, K (R).

Volume of sample aliquot titrated, ml.

Vm(std) =

Dry gas volume measured by the dry gas meter, corrected to standard
conditions, dscm (dscf).

Vsoln

Total volume of solution in which the SO 2 sample is contained, 100 ml.

Vt

Volume of barium standard titrant used for the sample, (average of replicate
titrations)ml.

Vtb

Volume of barium standard titrant used for the blank, ml.

Dry gas meter calibration factor.

32.03 =

Equivalent weight of sulfur dioxide.

6.2 Dry Sample Gas Volume, Corrected to Standard Conditions

Tstd

Tm

Vm(std) = Vm Y
where:
K1

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Pbar

= K1 Y Vm Pbar
Tm
Pstd

Equation 6-1

= 0.3858 K/mm Hg for metric units,

= 17.65 R/in. Hg for English units.
CARB Method 6 Page 10

6.3 SO2 Concentration

CSO2 = K 2 [( V t - V tb ) N ( V soln / V a )] / V m(std)

Equation 6-2

where:
K2 = 32.03 mg/meq. for metric units,
= 7.061 x 10-5 lb/meq. for English units.
6.4 Relative Error (RE) for QA Audit Samples. Percent
RE = 100 (Cd -Ca)/Ca
where:
Cd = determined audit sample concentration, mg/dscm.
Ca = Actual audit sample concentration, mg/dscm.
7. Alternative Procedures
7.1 Dry Gas Meter as a Calibration Standard
A dry gas meter may be used as a calibration standard for volume measurements in
place of the wet test meter specified in Section 5.1, provided that it is calibrated initially
and recalibrated periodically according to the procedures outlined in EPA Method 5,
Section 7.1, with the following exceptions: (1) the dry gas meter is calibrated against a
wet test meter having a capacity of 1 liter/rev or 3 liters/rev and having the capability of
measuring volume to within 1 percent; (2) the dry gas meter is calibrated at 1 liter/min (2
cfh); and (3) the meter box of the Method 6 sampling train is calibrated at the same flow
rate.
8. Bibliography
1.

EPA Method 6, Determination of Sulfur Dioxide Emissions from Stationary Sources,

CFR40, Part 60, Appendix A

2.

EPA Method 5, Determination of Particulate Matter Emissions from Stationary

Sources, CFR40, Part 60, Appendix A

3.

ARB Method 5, Determination of Particulate Matter Emissions from Stationary

Sources.

4.

ARB Method 8, Determination of Sulfuric Acid Mist and Sulfur Dioxide Emissions
from Stationary Sources.

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PROBE (END PACKED

STACK WALL

MIDGET IMPINGERS

WITH QUARTZ OR
PYREX WOOL)

MIDGET BUBBLER

THERMOMETER

GLASS WOOL

ICE
BATH
THERMOMETER

RATE METER

NEEDLE VALVE

DRY GAS
METER
PUMP
SURGE TANK

Figure 6-1. SO2 Sampling Train

SILICA GEL
DRYING TUBE