California Environmental Protection Agency __Air Resources Board METHOD 100. Procedures
for Continuous Gaseous Emission Stack Sampling Adopted: June 29, 1983 Amended: July 28, 1997Method 100 Table of Contents

Page I OVERVIEW

I 1.1 PRINCIPLE

1 1.2 APPLICABILITY

1 1.3 SAFETY

1 1.4 ALTERNATIVE TEST PROCEDURES

I 1.5 DEFINITIONS

2 1.6 SOURCE TEST PERFORMANCE SPECIFICATIONS

3 2 EQUIPMENT

3 2.1 SAMPLETRANSFERSYSTEM

3 2.2 GAS ANALYZERS AND DATA ACQUISITION

C) 2.3 MEASUREMENT

OF STACK FLOWRATE, MOISTURE, AND OTHER PARAMETERS

6 3 CALIBRATION GASES

7 3.1 CALIBRATION GASES

7 3.2 GAS DILUTION SYSTEM

8 4 ON-SITE PREPARATION FOR SAMPLING

8 4.1 CLEANING/ASSEMBLY

OF SAMPLE TRAIN

8 4.2 CALIBRATION

OF CONTINUOUS ANALYZERS

8 4.3 PRETEST LEAK CHECK

9 4.4 SAMPLE SYSTEM BIAS CHECK

9 4.5 DETERMINATION

OF SAMPLING TRAVERSE POINTS

9 July 1997

CARB Method 100

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i5SAMPLECOLLECTION.96POSTTESTPERFORMANCECHECKS106.1ZEROANDCALIBRATIONDRIFT106.2SAMPLINGSYSTEMBIAS117CALCULATIONS117.1POLLUTANTCONCENTRATION117.2MASSEMISSIONRATE127.3POLLUTANTCONCENTRATIONFOR12%Co2OR3%0212TABLE100.1GASANALYZERSPECIFICATIONS13FIGURE100.1METHOD100SAMPLETRAINASSEMBLY14July1997CARBMethod100PageiiMETHOD 100 Procedures
for Continuous Gaseous Emission Stack Sampling I OVERVIEW 1.1 PRINCIPLE A sample
of an exhaust gas stream

is extracted, conditioned and analyzed continuously

by instruments. The measurements made by the continuous analyzers are used to determine average emission concentrations.

By measuring the stack gas flowrate and moisture, and using this information with the average emission concentration, mass emission rates can be determined. 1.2 APPLICABILITY This method is.applicable
for determining emissions

of oxides of nitrogen, carbon monoxide, carbon dioxide, sulfur dioxide, total hydrocarbons,
and oxygen from stationary source flowing gas streams

in ducts, stacks and flues. This procedure does not supersede the New Source Performance Standards requirement
for permanently installed continuous emissions monitoring instruments. This test procedure

is an alternative method
to appropriate U.S. EPA reference methods,

in particular, EPA methods 3A, 6C, 7E, 10, and 25A and B. This procedure should be used only on those sources where equivalency

to the reference methods has been established

or the specific regulations
for the source specify this procedure. 1.3 SAFETY This method does not address the safety problems associated with its use.

It is the responsibility

of the user of this method
to establish appropriate safety and health practices including the safe handling
of compressed gases, flammable gases and any hazardous compounds and to determine the applicability

of regulatory limitations prior to use of this method. 1.4 ALTERNATIVE TEST PROCEDURES Any modification

of this method beyond those expressly permitted shall be subject
to approval
by the Executive Officer of the Air Resources Board or his or her authorized representative. July 1997

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11.5 DEFINITIONS 1.5.1 Range The upper limit of the gas concentration measurement range displayed
on the data recorder. The range

is selected
so that the sample gas concentration

is between

10 and 95 percent
of the range for each pollutant
of interest. 1.5.2 Calibration Gas A known concentration

of a gas in an inert diluent gas. 1.5.3 Analyzer Calibration Error The difference between the known concentration

of a calibration gas and the concentration measured

by the gas analyzer when the calibration gas is introduced directly
to the gas analyzer. 1.5.4 Sampling System Bias The difference between the concentration measured

by a gas analyzer when a known concentration calibration gas is introduced

at the sampling probe and when the same gas is introduced directly
to the analyzer. 1.5.5 Zero Drift The difference between the concentration measured

by the gas analyzer for zero gas before the sample run and the concentration measured

by the analyzer for zero gas after

a stated period of operation during which no unscheduled maintenance, repair, or adjustment took place. 1.5.6 Calibration Drift The difference between the concentration measured
by the gas analyzer for a calibration gas before the sample run and the concentration measured

by the analyzer for that same calibration gas after

a stated period of operation during which no unscheduled maintenance, repair, or adjustment took place. 1.5.7 Response Time The time required for the data recorder

to display 95% of the difference

in gas concentration

on the data recorder after

a step change

in gas concentration, such as a switch from zero gas to calibration gas. July 1997

CARB Method 100

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21.5.8InterferenceCheckDeterminationoftheconcentrationmeasuredforaknownconcentrationofacomponentinthesamplegasotherthanthetargetgascomponentbeingmeasuredbythegasanalyzer.1.6SOURCETESTPERFORMANCESPECIFICATIONSThefollowingspecificationsmustbemetfordatafromatestruntobeconsideredvalid:1.6.1AnalyzerCalibrationError±2percentorlessoftherangewhenintroducingzeroorcalibrationgas.1.6.2ZeroDrift±3percentorlessoftherangeduringatestrun.1.6.3SpanDrift±3percentorlessoftherangeduringatestrun.1.6.4SamplingSystemBias±5percentorlessoftherangewhenintroducingzeroorcalibrationgas.1.6.5InterferenceCheckForeachanalyzer,±5percentorlessoftherange.2EQUIPMENT2.1SAMPLETRANSFERSYSTEMAschematicofthesamplingtrainisshowninFigure100.1.2.1.1ProbeNozzleQuartz,borosilicateglass,stainlesssteel,porcelainoraluminumoxidemaybeusedfortheprobenozzle.July1997CARBMethod100Page32.1.2 Probe Filter An internal
or external probe filter may be used. As necessary, provisions should be made for back flushing the filter to remove particulate build-up. 2.1.3 Probe The probe shall have an inside diameter
of 6 mm or larger and shall be constructed

of quartz, borosilicate glass, stainless steel, aluminum oxide or porcelain. 2.1.4 Sample Line The sample line is constructed

of teflon or other material which does not absorb or otherwise alter the sample gas. 2.1.5 Probe Calibration System Calibration gases for a sampling system bias check are introduced

at the probe. Depending

on the configuration

of the probe, calibration gas is injected

at an internal probe filter, at the probe tip, or directly behind the probe outlet. ( 2.1.6 Sample Conditioner The sample conditioner shall be capable
of reducing the sample gas temperature

to 15 °C (60 °F), or to 11 °C (20 °F) lower than the ambient temperature, whichever

is lower. All parts of the conditioner exposed

to the sample shall be glass, stainless steel or teflon. The sample gas shall not be bubbled
or dispersed through the condensate such that minimum contact shall be maintained between any condensate and the sample gas. A temperature gauge shall be used to determine the temperature

of the condenser outlet. If needed,

a glass filter is used at the inlet or the outlet of the conditioner

to prevent the accumulation

of particulate material. 2.1.7 Sample System Heaters If needed
to prevent condensation

of water or hydrocarbons,

or the reaction of other stack constituents,

a probe heater may be used.

If necessary, use
a heated sample line, heated filters, and
a heated analyzer. Heaters shall heat the sample
to a minimum

of 120°C (248°F)
or to a temperature above the dewpoint

of the target constituent, whichever

is greater. Perform
no sample conditioning that lowers the sample temperature. July 1997

CARB Method 100

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42.2GASANALYZERSANDDATAACQUISITION2.2.1SpecificationsSpecificationsfortheacceptanceofgasanalyzersforuseofMethod100arelistedinTable100.1.Thevendormustprovidetestdatademonstratingthatthefollowingperformancerequirementsaremet:minimumdetectionlimit,noiselevel,responsetime,repeatability,linearity,interference,sensitivitytotemperaturechange,and24-hourzeroandcalibrationdriftlimits.Theanalyzersshallbehousedinatemperature-controlled,vibration-freeenvironment.2.2.2CarbonDioxideandCarbonMonoxideNondispersiveinfraredanalyzersareacceptable.2.2.3OxygenAparamagneticanalyzeroranelectrochemical(fuelcell)analyzerisacceptable.2.2.4TotalHydrocarbonsAnanalyzerusingaflameionizationdetector(FID)oranondispersiveinfraredanalyzer(NDIR)isacceptable.Propaneormethaneisusuallyusedasaspangas.Thehydrocarbonspeciesshouldbecharacterizedpriortothesourcetesttodeterminethatthedetectorwillrespondpredictablytotheorganiccompoundspresent.Compound-specificcalibrationcurvesmustbedeterminedforuseofeithertheFIDortheNDIRanalyzertomeasurespecificorganiccompounds.2.2.5OxidesofNitrogenAnanalyzerusingchemiluminescenceisacceptable.TheNO2toNOconvertermusthaveatleasta90%efficiencyinconvertingnitrogendioxide(NO2)inthesamplegastonitricoxide(NO).AnNO2toNOconverterisnotnecessaryifdataarepresentedtodemonstratethattheNO2portionoftheexhaustgasislessthan5percentofthetotalNOconcentration.Alowtemperature(maximum350°C)convertermustbeusedwhenNH3ispresent.Ahightemperature(650°C)stainlesssteelconvertermaybeusedwhennoNH3ispresent.July1997CARBMethod100Page5If data are not available

to demonstrate that the concentration

of NO 2 in the sample gas is less than 5% of the total NO concentration,

a test of the efficiency

of the NO 2 converter must be conducted prior to each source test. 2.2.6 Sulfur Dioxide An analyzer using infrared
or ultraviolet absorption

or fluorescence

is acceptable. 2.2.7 Other Analyzers An analyzer operating
by measurement principles not listed
in Table 100.1 may be used,

if its performance meets the requirements

of Table 100.1. 2.2.8 Data Acquisition System/Data Recorder Provide

a permanent record of gas analyzer data using

a strip chart recorder. A data logger or other electronic data acquisition system may also be used. Any electronic data acquisition system must be capable
of integration

at a ten second interval. The strip chart, as well as the data acquisition system, must have

a resolution

of 0.5 percent
of the analyzer range. Data reporting includes the following information: pollutant, source, analyzer range, date, time, zero offsets, person operating instruments, and any other pertinent data. 2.3 MEASUREMENT

OF STACK FLOWRATE, MOISTURE, AND OTHER PARAMETERS 2.3.1 Stack Gas Flowrate and Moisture Measurement Stack gas flowrate and moisture content can be determined using equipment specified
by ARB Test Methods

1 through

4. Stack gas velocity can be determined from

a pitot tube measurement

as outlined
by Methods

I and 2. Two possible alternatives are: (1) A simultaneous traverse
of stack gas concentration
and velocity, (2) A pre and
a post test velocity traverse. (Repeat the velocity traverse whenever aware of a change

in process conditions which may affect emissions.) Note:

If the pitot tube and the sampling probe are used
in combination

in a testing assembly, care must be taken that any aerodynamic effects on the pitot tube are eliminated. Otherwise, the pitot tube must be calibrated with the other components

of the test assembly

in place. (See ARB Method

2, Section 4.1.1.) July 1997

CARB Method 100

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6Alternate methods
of flowrate measurement, including consideration

of fuel rate, combustion stoichiometry
and oxygen concentration

in the stack gas and applicable F-factors listed
in 40 CFR Part 60 Appendix

A, Method 19, must be approved
by the Executive Officer of the Air Resources Board or his or her authorized representative. 2.3.2 Barometer A mercury, aneroid,
or other barometer capable
of measuring atmospheric pressure

to within 2.5 mm Hg. shall be used. 2.3.3 Vacuum Gauge
or Flowmeter Use
a vacuum gauge or a flowmeter
for leak check of the sampling train. 3 CALIBRATION GASES 3.1 Calibration Gases The calibration gases must be certified according

to EPA Traceability Protocol 1 . Alternately the calibration gases must be certified

to an analytical accuracy

of ±2 percent, traceable

to a reference material approved
by the National Institute
of

( Standards and Technology (NIST), and recertified annually. Multi-component

gas mixtures certified according

to EPA Protocol are acceptable. Multi-component

gas mixtures which meet the following requirements
are also acceptable:
the concentration

of each component gas must be certified

to an analytical accuracy

of ±2 percent, each component must be traceable

to a NIST standard, and the mixture must be recertified semi annually. A permeation tube may be used as a calibration standard

in place of the calibration gas, provided the following requirements

of EPA Method
16 (CFR 60 Appendix

A) are met for use of permeation tubes: Section 5.5 for the calibration system, Section 6.5 for the calibration gases, Sections 8.2 and 8.3 on pretest calibration, and Sections 10.2 and 10.3 on post test calibration. For each pollutant

to be measured, use the following three calibration gases:EPATraceabilityProtocolforAssayandCertificationofGaseousCalibrationStandards,EPA-600/R93/224,RevisedSeptember1993. July 1997

CARB Method 100

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73.1.1 High-Range Gas The concentration should be between
80 and 100 percent
of the analyzer range. 3.1.2 Mid-range Gas The concentration should be between
40 and 60 percent
of the analyzer range. 3.1.3 Zero Gas Purified air or, if appropriate, nitrogen with

a contaminant concentration
less than 0.25% of the analyzer range for the appropriate pollutant gas may be used. 3.2 GAS DILUTION SYSTEM A gas dilution system which meets the requirements

of EPA Method 205, Verification

of Gas Dilution Systems for Field Instrument Calibrations, CFR 40, Part 51, Appendix

M, may be used to provide low-level calibration gases from

a high-level calibration gas. The calibration gas used with

a gas dilution system should be an EPA Protocol gas. A gas dilution system which meets the requirements

of EPA Method 205 may be used for all analyzer calibrations and sampling system bias checks. 4 ON-SITE PREPARATION FOR SAMPLING 4.1 CLEANING/ASSEMBLY

OF SAMPLE TRAIN The sample train may be cleaned prior to being transported

to the field. When
at the testing site, assemble the cleaned sample train as shown
in Figure 100.1. 4.2 CALIBRATION

OF CONTINUOUS ANALYZERS Allow analyzers

to warm up according

to manufacturer’s instructions. Adjust system components

to achieve the individual analyzer sampling rates recommended

by the instrument manufacturer. Alternately introduce zero and calibration gases to the instruments and make all necessary adjustments

to calibrate the analyzer and the data recorder. Conduct the analyzer calibration error check by sequentially introducing the three calibration gases (high-range, mid-range and zero gas) and recording the analyzer response

to each calibration gas. Make no adjustments

to the sampling/analysis system except those necessary

to achieve the proper July 1997

CARB Method 100

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8calibration gas flowrate. The test run will be considered invalid

if the analyzer calibration error for any calibration gas exceeds
±2 percent
of the range.

If needed, take corrective action until acceptable performance

is achieved. 4.3 PRETEST LEAK CHECK Perform

a leak check on the vacuum side of the assembly

at the maximum pump vacuum. Correct any leaks found and repeat the leak check and correction procedure until no leak is detected. 4.4 SAMPLE SYSTEM BIAS CHECK A pretest sampling system bias check

is required for each gas analyzer. Perform the sampling system bias check by alternately introducing

at the probe the zero gas and either the high-range

or mid-range calibration gas, whichever calibration gas is closest

in concentration

to the sample gas. Record the gas concentrations displayed
by the analyzer. During the sampling system bias check operate the system
at the normal sampling rate and make no adjustments to the measurement system other than those necessary

to achieve proper calibration gas flow rate. Determine the sampling system response time. If the difference between the gas concentrations

for the analyzer calibration error C: check and the sample system bias check exceeds ±5% of the range for eitherV the zero or upscale calibration gas, the bias check

is invalid,

If needed, take corrective action before repeating the sample system bias check.

If the analyzer is adjusted, repeat the analyzer calibration error check before repeating the bias check. 4.5 DETERMINATION

OF SAMPLING TRAVERSE POINTS Select gas sampling traverse points according

to the guidelines given
in ARB Methods

I and
2 for velocity traverses. Multipoint gas sampling must be performed unless data are available

to demonstrate that the mean pollutant concentration

is less than 10% different from that at any single point. 5 SAMPLE COLLECTION Insert the sample probe assembly into the stack and block off the remainder

of the sample port opening. Set the probe at the predetermined position and begin data acquisition.

If a traverse

is required, the sampling time at each traverse point
is constant. Sample for at least the sampling system response time plus one minute, allowing enough time for the system
to be flushed and the instruments

to respond fully. Move probe to next position and repeat. Continue until the stack has been fully traversed. July 1997

CARB Method 100

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9A test shall include
at least three sample runs. Each sample run shall be the length of time specified

in the applicable emission limit regulation.
As a minimum, the sampling time must be such that the emission test is conducted during representative operating conditions

of the source. For
a sample run exceeding two hours, conduct sampling system bias checks every two hours. Record performance check data. As necessary, back flush through the probe to prevent particulate build up on the probe filter. Periodically check the sample conditioner and remove condensate

as needed. If adjustments

to the sampling train are necessary during the sample run, conduct

a system bias check before any adjustments
are made. After any adjustments
are made to the analyzer, the analyzer calibration error check shall be conducted. After all adjustments
are made to the sampling system, the sampling system bias check shall be performed prior to continuation

of the test run. 6 POST TEST PERFORMANCE CHECKS At the end of the sample run, conduct

a sampling system bias check for all analyzers. Perform the sampling system bias check by alternately introducing the zero gas and the calibration gas at the probe. During the sampling system check operate the system
at the normal sampling rate and make no adjustments

to the measurement system other than those necessary

to achieve proper calibration gas flow rates through the sampling system
to the gas analyzer. 6.1 ZERO AND CALIBRATION DRIFT The test run shall be considered invalid

if the difference

of zero or calibration gas measured
for the post run sampling system bias check and zero or calibration gas measured
for the initial sampling system bias check of the first test run (Section 4.5) exceeds
±3 percent
of the range. Use Equation 100-1, below: Drift cibCm)x 100

Eq. 100-1 Where: cm

= analyzer response for the zero or upscale calibration gas for post run sampling system bias check Cib

= analyzer response for the zero or upscale calibration gas for initial sampling system bias check r

= analyzer range July 1997

CARB Method 100

Page 106.2 SAMPLING SYSTEM BIAS The test run shall be considered invalid

if the difference

of zero or calibration gas measured
for the post run sampling system bias check and zero or calibration gas measured
for the initial analyzer calibration (Section 4.2) exceeds
±5 percent of the range. Calculate bias using Equation 100-2: Bias=cxlOO

Eq. 100-2 Where:

= analyzer response for the zero or upscale calibration gas for post run sampling system bias check ca

= analyzer response for the zero or upscale calibration gas for initial analyzer calibration r

= analyzer range 7 CALCULATION

OF POLLUTANT CONCENTRATION
AND MASS EMISSION RATE 7.1 POLLUTANT CONCENTRATION Determine the average concentration, Cgas, of each stack gas constituent using Equation 100-3: Cgas (Cavg -C 0 )x(CbcaICo)

Eq. 100-3 Where: Cgas

= Effluent gas concentration, ppm or % by volume Cavg

= Average gas concentration indicated
by gas analyzer, ppm or % by volume C 0

= Average
of initial(clb) and final(Ct) system bias responses
for zero gas, ppm or % by volumeC1= Actual concentration

of the calibration gas used for the bias check, ppm or % by volume July 1997

CARB Method 100

Page
11Cbcal

= Average
of initial (Cb) and final (Cth) sampling system bias responses
for the calibration gas, ppm or % by volume 7.2 MASS EMISSION RATE The emission rate in pounds per hour of pollutant

is E in Equation 100-4: E=CdgasX 385 M 1 Q 6 xQx6O

Eq. 100-4 Where: Cdgas effluent gas concentration corrected

to dry basis, ppm M

= molecular weight

in lb/lb-mole 385

= standard volume

in cubic feet of one lb-mole (at 528°
R and

1 atmosphere) Q

= Stack flowrate

in standard dry cubic feet per minute of stack effluents, determined from ARB Methods

2 and 4, or alternative determinations

of flow rate and moisture content 7.3 POLLUTANT CONCENTRATION
FOR 12% CO 2 OR 3% 02 The pollutant concentration Cdgas
is adjusted for 12% CO 2 in Equation 100-5: 12% C 120 , =C

x

Eq. 100-5oCO2
gas %C0 2 during test For correction

to 3% 02 (using 02 in air as 20.9%), use Equation 100-6: 209-30 C 0 , =C

x
Eq.100-6 3°2 dgas 20.9- /‘002 during test July 1997

CARB Method 100

Page 12

# HYDRO CARBONS OXYGEN

2 Other types will also be acceptable provided that the criteria listed below are met. 3 1% of the analyzer range is the maximum absolute difference between replicate results which may be expected with a probability of 95%. 4 When sampling zero or span gas, the analyzer response shall not change more than ± 

# 2% of range when the ambient temperature changes ± 

# 10 °C from 25 °C. 5 Maximum deviation between a mid-range calibration reading and the reading predicted by a straight line drawn between high-range and zero gas calibration points, as a percent of the range. 

# July 1997 CARB Method 100 Page 13 

# Table 100 Gas Analyzer Specifications

SULFUR OXIDES OF CARBON DIOXIDE NITROGEN MONOXIDE CARBON DIOXIDE Ultraviolet or infrared Flame ionization Paramagnetic or Typical Principle of Operation 2 absorption or Chemilumine Infrared Infrared or infrared electrochemical scence absorption absorption fluorescence absorption cell Typical Concentration Ranges 10- 2500 ppm 10- 1000 10- 1000 5-20% 50 ppm

- 

# 50% 5-25% PPM or % by volume ppm ppm Minimum detection limit, % of full scale for lowest range. 2% 2% 2% 2% 2% as Propane 2% NoiseLevel%ofrange <±1% <±1% <±1% <±1% <±1% <±1% Response Timeto 95% of steady state after a step change in < 

# 30 secs. <30 secs. < 

# 60 secs. < 

# 60 secs. < 

# 30 secs. < 

# 60 secs. concentration Repeatability, % of range 3 1% 1% 1% 1% 1% 1% Zero Drift after 24 hours of unadjusted continuous operation, % range < 

# ± 

# 1% < 

# ± 

# 1% < 

# ± 

# 1% < 

# ± 

# 1% < 

# ± 

# 1% < 

# ± 

# 1% Span Drift after 24 hours of unadjusted continuous operation, % range < 

# ± 

# 1% < 

# ± 

# 1% < 

# ± 

# 1% < 

# ± 

# 1% < 

# ± 

# 1% < 

# ± 

# 1% Interferenceofacomponentotherthanthetargetcomponent <±5% <±5% <±5% <±5% <±5% <±5% measured by the gas analyzer, % of range Analyzer response to temperature variation 4 

# % % % % 

# % % % % % % % A change in ambient temperature of ± 200 

# C from 25°C shall not cause a permanent change to the zero or span response of analyzer Linearity 5 <±1% <±1% <±1% <±1% <±1% <±1%

# C— 

# C 

# Co CD



# C-) > w CD 0 0.

— 

# Q 0



# -o 0) (0 CD 

# fl
FIGURE 100.1 Method 100 Sample Train Assembly to data to strip 

# chart

zero as 

# by-pass How control

sample 

# gas manifold

probe pump 

# sack calibration gas
fitter

* 

# Details not shown include calibration gas plumbing, heated

hydrocarbon sample line, optional gas dilution system, analyzer exhaust plumbing, and optional pitot and thermocouple arrangements. temperature gauge

caltb gC0C