METHOD 100.

Procedures for Continuous Gaseous

Emission Stack Sampling

Adopted: June 29, 1983

Amended: July 28, 1997
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 Page i
6.2 SAMPLING SYSTEM BIAS 11

7 CALCULATIONS 11

7.1 POLLUTANT CONCENTRATION 11

7.2 MASS EMISSION RATE 12

7.3 POLLUTANT CONCENTRATION FOR 12% Co 2 OR 3% 02 12

TABLE 100.1 GAS ANALYZER SPECIFICATIONS 13

FIGURE 100.1 METHOD 100 SAMPLE TRAIN ASSEMBLY 14

July 1997 CARB Method 100 Page ii
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 monitoringinstruments.

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 CARB Method 100 Page 1
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 Page 2
The following specifications must be met for data from a test run to be

considered valid:

1.6.1 Analyzer Calibration Error

±2 percent or less of the range when introducing zero or calibration gas.

1.6.2 Zero Drift

±3 percent or less of the range during a test run.

1.6.3 Span Drift

±3 percent or less of the range during a test run.

1.6.4 Sampling System Bias

±5 percent or less of the range when introducing zero or calibration gas.

1.6.5 Interference Check

For each analyzer, ±5 percent or less of the range.

2 EQUIPMENT

2.1 SAMPLE TRANSFER SYSTEM

A schematic of the sampling train is shown in Figure 100.1.

2.1.1 Probe Nozzle

Quartz, borosilicate glass, stainless steel, porcelain or aluminum oxide may

be used for the probe nozzle.

July 1997 CARB Method 100 Page 3
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 Page 4
the following performance requirements are met: minimum detection limit,

noise level, response time, repeatability, linearity, interference, sensitivity to

temperature change, and 24-hour zero and calibration drift limits.

The analyzers shall be housed in a temperature-controlled, vibration-free

environment.

2.2.2 Carbon Dioxide and Carbon Monoxide

Nondispersive infrared analyzers are acceptable.

2.2.3 Oxygen

A paramagnetic analyzer or an electrochemical (fuel cell) analyzer is

acceptable.

2.2.4 Total Hydrocarbons

An analyzer using a flame ionization detector (FID) or a nondispersive

infrared analyzer (N DIR) is acceptable. Propane or methane is usually used

as a span gas. The hydrocarbon species should be characterized prior to thesource test to determine that the detector will respond predictably to the

organic compounds present. Compound-specific calibration curves must bedetermined for use of either the FID or the NDIR analyzer to measure specific

organic compounds.

2.2.5 Oxides of Nitrogen

An analyzer using chemiluminescence is acceptable. The NO2to NO

converter must have at least a 90% efficiency in converting nitrogen dioxide

(NO 2)in the sample gas to nitric oxide (NO). An NO2to NO converter is not

necessary if data are presented to demonstrate that the NO2portion of the

exhaust gas is less than 5 percent of the total NO concentration. A low

temperature (maximum 350°C) converter must be used when NH3is present.

A high temperature (650°C) stainless steel converter may be used when no

NH3is present.

July 1997 CARB Method 100 Page 5
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 onthe 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 Page 6
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

Alternately

The calibration

the calibration

gases must

gases

be certified

must be

according

certified

to

to

EPA

an

Traceability Protocol 1.

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 gasmust 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 pretestcalibration, and Sections 10.2 and 10.3 on post test calibration.

For each pollutant to be measured, use the following three calibration gases:

EPA Traceability Protocol for Assay and Certification of Gaseous Calibration Standards, EPA-600/R93/224, Revised September 1993.

July 1997 CARB Method 100 Page 7
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 Page 8
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 gasconcentrations 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 either V

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 dataacquisition. 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 beenfully traversed.

July 1997 CARB Method 100 Page 9
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 10
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 -C0)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

C0 = Average of initial (clb) and final (Ct) system bias responses for

zero gas, ppm or % by volume

C1 = Actual concentration of the calibration gas used for the bias

check, ppm or % by volume

July 1997 CARB Method 100 Page 11
E=CdgasX 385M1Q6xQx6O Eq. 100-4

Where:

Cdgas effluent gas concentration corrected to dry basis, ppmM = 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% CO2 OR 3% 02

The pollutant concentration Cdgas is adjusted for 12% CO2in Equation 100-5:

C 12% 120 ,oCO 2 =C gas x Eq. 100-5 %C0 2during test

For correction to 3% 02 (using 02 in air as 20.9%), use Equation 100-6:

209-30 C0,3 =C x Eq.100-6 °2 dgas 20.9

-

/‘002 during test

July 1997 CARB Method 100 Page 12
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 

5 Maximum deviation between a mid-range calibration reading and the reading predicted by a straight line drawn between high-range and zero 

percent of the range.

July 1997 CARB Method 100 

Table 100

Gas Analyzer Specifications

SULFUR OXIDES OF CARBON

DIOXIDE NITROGEN MONOXIDE

CARBON

DIOXIDE

Ultraviolet or infrared Fla

Typical Principle of Operation 2 absorption or Chemilumine Infrared Infrared or 

scence absorption absorption fluorescence abs

Typical Concentration Ranges 10- 2500 ppm 10- 1000 10- 1000 5-20% 50 

PPM or % by volume ppm ppm

Minimum detection limit, % of full scale for lowest range. 2% 2% 2% 2% 2% 

NoiseLevel%ofrange <±1% <±1% <±1% <±1% <±

Response Timeto 95% of steady state after a step change in < 30 secs. <30 secs. < 60 secs. < 60 secs. < 3

concentration

Repeatability, % of range 3 1% 1% 1% 1% 1% 

Zero Drift after 24 hours of unadjusted continuous operation, % range < ± 1% < ± 1% < ± 1% < ± 1% < ± 

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

Interferenceofacomponentotherthanthetargetcomponent <±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% <±
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 

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 g
0

C