Appendix A to Subpart ZZZZ of Part 63 - Protocol for Using an Electrochemical Analyzer to Determine Oxygen and Carbon Monoxide Concentrations From Certain Engines

Appendix A to Subpart ZZZZ of Part 63 - Protocol for Using an Electrochemical Analyzer to Determine Oxygen and Carbon Monoxide Concentrations From Certain Engines

1.0 Scope and Application. What is this Protocol?

This protocol is a procedure for using portable electrochemical (EC) cells for measuring carbon monoxide (CO) and oxygen (O₂) concentrations in controlled and uncontrolled emissions from existing stationary 4-stroke lean burn and 4-stroke rich burn reciprocating internal combustion engines as specified in the applicable rule.

1.1 Analytes. What does this protocol determine?

This protocol measures the engine exhaust gas concentrations of carbon monoxide (CO) and oxygen (O₂).

Analyte	CAS No.	Sensitivity
Carbon monoxide (CO)	630-08-0	Minimum detectable limit should be 2 percent of the nominal range or 1 ppm, whichever is less restrictive.
Oxygen (O2)	7782-44-7

1.2 Applicability. When is this protocol acceptable?

This protocol is applicable to 40 CFR part 63, subpart ZZZZ. Because of inherent cross sensitivities of EC cells, you must not apply this protocol to other emissions sources without specific instruction to that effect.

1.3 Data Quality Objectives. How good must my collected data be?

Refer to Section 13 to verify and document acceptable analyzer performance.

1.4 Range. What is the targeted analytical range for this protocol?

The measurement system and EC cell design(s) conforming to this protocol will determine the analytical range for each gas component. The nominal ranges are defined by choosing up-scale calibration gas concentrations near the maximum anticipated flue gas concentrations for CO and O₂, or no more than twice the permitted CO level.

1.5 Sensitivity. What minimum detectable limit will this protocol yield for a particular gas component?

The minimum detectable limit depends on the nominal range and resolution of the specific EC cell used, and the signal to noise ratio of the measurement system. The minimum detectable limit should be 2 percent of the nominal range or 1 ppm, whichever is less restrictive.

2.0 Summary of Protocol

In this protocol, a gas sample is extracted from an engine exhaust system and then conveyed to a portable EC analyzer for measurement of CO and O₂ gas concentrations. This method provides measurement system performance specifications and sampling protocols to ensure reliable data. You may use additions to, or modifications of vendor supplied measurement systems (e.g., heated or unheated sample lines, thermocouples, flow meters, selective gas scrubbers, etc.) to meet the design specifications of this protocol. Do not make changes to the measurement system from the as-verified configuration (Section 3.12).

3.0 Definitions

3.1 Measurement System. The total equipment required for the measurement of CO and O₂ concentrations. The measurement system consists of the following major subsystems:

3.1.1 Data Recorder. A strip chart recorder, computer or digital recorder for logging measurement data from the analyzer output. You may record measurement data from the digital data display manually or electronically.

3.1.2 Electrochemical (EC) Cell. A device, similar to a fuel cell, used to sense the presence of a specific analyte and generate an electrical current output proportional to the analyte concentration.

3.1.3 Interference Gas Scrubber. A device used to remove or neutralize chemical compounds that may interfere with the selective operation of an EC cell.

3.1.4 Moisture Removal System. Any device used to reduce the concentration of moisture in the sample stream so as to protect the EC cells from the damaging effects of condensation and to minimize errors in measurements caused by the scrubbing of soluble gases.

3.1.5 Sample Interface. The portion of the system used for one or more of the following: sample acquisition; sample transport; sample conditioning or protection of the EC cell from any degrading effects of the engine exhaust effluent; removal of particulate matter and condensed moisture.

3.2 Nominal Range. The range of analyte concentrations over which each EC cell is operated (normally 25 percent to 150 percent of up-scale calibration gas value). Several nominal ranges can be used for any given cell so long as the calibration and repeatability checks for that range remain within specifications.

3.3 Calibration Gas. A vendor certified concentration of a specific analyte in an appropriate balance gas.

3.4 Zero Calibration Error. The analyte concentration output exhibited by the EC cell in response to zero-level calibration gas.

3.5 Up-Scale Calibration Error. The mean of the difference between the analyte concentration exhibited by the EC cell and the certified concentration of the up-scale calibration gas.

3.6 Interference Check. A procedure for quantifying analytical interference from components in the engine exhaust gas other than the targeted analytes.

3.7 Repeatability Check. A protocol for demonstrating that an EC cell operated over a given nominal analyte concentration range provides a stable and consistent response and is not significantly affected by repeated exposure to that gas.

3.8 Sample Flow Rate. The flow rate of the gas sample as it passes through the EC cell. In some situations, EC cells can experience drift with changes in flow rate. The flow rate must be monitored and documented during all phases of a sampling run.

3.9 Sampling Run. A timed three-phase event whereby an EC cell's response rises and plateaus in a sample conditioning phase, remains relatively constant during a measurement data phase, then declines during a refresh phase. The sample conditioning phase exposes the EC cell to the gas sample for a length of time sufficient to reach a constant response. The measurement data phase is the time interval during which gas sample measurements can be made that meet the acceptance criteria of this protocol. The refresh phase then purges the EC cells with CO-free air. The refresh phase replenishes requisite O₂ and moisture in the electrolyte reserve and provides a mechanism to de-gas or desorb any interference gas scrubbers or filters so as to enable a stable CO EC cell response. There are four primary types of sampling runs: pre- sampling calibrations; stack gas sampling; post-sampling calibration checks; and measurement system repeatability checks. Stack gas sampling runs can be chained together for extended evaluations, providing all other procedural specifications are met.

3.10 Sampling Day. A time not to exceed twelve hours from the time of the pre-sampling calibration to the post-sampling calibration check. During this time, stack gas sampling runs can be repeated without repeated recalibrations, providing all other sampling specifications have been met.

3.11 Pre-Sampling Calibration/Post-Sampling Calibration Check. The protocols executed at the beginning and end of each sampling day to bracket measurement readings with controlled performance checks.

3.12 Performance-Established Configuration. The EC cell and sampling system configuration that existed at the time that it initially met the performance requirements of this protocol.

4.0 Interferences.

When present in sufficient concentrations, NO and NO₂ are two gas species that have been reported to interfere with CO concentration measurements. In the likelihood of this occurrence, it is the protocol user's responsibility to employ and properly maintain an appropriate CO EC cell filter or scrubber for removal of these gases, as described in Section 6.2.12.

5.0 Safety. [Reserved]

6.0 Equipment and Supplies.

6.1 What equipment do I need for the measurement system?

The system must maintain the gas sample at conditions that will prevent moisture condensation in the sample transport lines, both before and as the sample gas contacts the EC cells. The essential components of the measurement system are described below.

6.2 Measurement System Components.

6.2.1 Sample Probe. A single extraction-point probe constructed of glass, stainless steel or other non-reactive material, and of length sufficient to reach any designated sampling point. The sample probe must be designed to prevent plugging due to condensation or particulate matter.

6.2.2 Sample Line. Non-reactive tubing to transport the effluent from the sample probe to the EC cell.

6.2.3 Calibration Assembly (optional). A three-way valve assembly or equivalent to introduce calibration gases at ambient pressure at the exit end of the sample probe during calibration checks. The assembly must be designed such that only stack gas or calibration gas flows in the sample line and all gases flow through any gas path filters.

6.2.4 Particulate Filter (optional). Filters before the inlet of the EC cell to prevent accumulation of particulate material in the measurement system and extend the useful life of the components. All filters must be fabricated of materials that are non-reactive to the gas mixtures being sampled.

6.2.5 Sample Pump. A leak-free pump to provide undiluted sample gas to the system at a flow rate sufficient to minimize the response time of the measurement system. If located upstream of the EC cells, the pump must be constructed of a material that is non-reactive to the gas mixtures being sampled.

6.2.8 Sample Flow Rate Monitoring. An adjustable rotameter or equivalent device used to adjust and maintain the sample flow rate through the analyzer as prescribed.

6.2.9 Sample Gas Manifold (optional). A manifold to divert a portion of the sample gas stream to the analyzer and the remainder to a by-pass discharge vent. The sample gas manifold may also include provisions for introducing calibration gases directly to the analyzer. The manifold must be constructed of a material that is non-reactive to the gas mixtures being sampled.

6.2.10 EC cell. A device containing one or more EC cells to determine the CO and O₂ concentrations in the sample gas stream. The EC cell(s) must meet the applicable performance specifications of Section 13 of this protocol.

6.2.11 Data Recorder. A strip chart recorder, computer or digital recorder to make a record of analyzer output data. The data recorder resolution (i.e., readability) must be no greater than 1 ppm for CO; 0.1 percent for O₂; and one degree (either °C or °F) for temperature. Alternatively, you may use a digital or analog meter having the same resolution to observe and manually record the analyzer responses.

6.2.12 Interference Gas Filter or Scrubber. A device to remove interfering compounds upstream of the CO EC cell. Specific interference gas filters or scrubbers used in the performance-established configuration of the analyzer must continue to be used. Such a filter or scrubber must have a means to determine when the removal agent is exhausted. Periodically replace or replenish it in accordance with the manufacturer's recommendations.

7.0 Reagents and Standards. What calibration gases are needed?

7.1 Calibration Gases. CO calibration gases for the EC cell must be CO in nitrogen or CO in a mixture of nitrogen and O₂. Use CO calibration gases with labeled concentration values certified by the manufacturer to be within ±5 percent of the label value. Dry ambient air (20.9 percent O₂) is acceptable for calibration of the O₂ cell. If needed, any lower percentage O₂ calibration gas must be a mixture of O₂ in nitrogen.

7.1.1 Up-Scale CO Calibration Gas Concentration. Choose one or more up-scale gas concentrations such that the average of the stack gas measurements for each stack gas sampling run are between 25 and 150 percent of those concentrations. Alternatively, choose an up-scale gas that does not exceed twice the concentration of the applicable outlet standard. If a measured gas value exceeds 150 percent of the up-scale CO calibration gas value at any time during the stack gas sampling run, the run must be discarded and repeated.

7.1.2 Up-Scale O₂ Calibration Gas Concentration.

Select an O₂ gas concentration such that the difference between the gas concentration and the average stack gas measurement or reading for each sample run is less than 15 percent O₂. When the average exhaust gas O₂ readings are above 6 percent, you may use dry ambient air (20.9 percent O₂) for the up-scale O₂ calibration gas.

7.1.3 Zero Gas. Use an inert gas that contains less than 0.25 percent of the up-scale CO calibration gas concentration. You may use dry air that is free from ambient CO and other combustion gas products (e.g., CO₂).

8.0 Sample Collection and Analysis

8.1 Selection of Sampling Sites.

8.1.1 Control Device Inlet. Select a sampling site sufficiently downstream of the engine so that the combustion gases should be well mixed. Use a single sampling extraction point near the center of the duct (e.g., within the 10 percent centroidal area), unless instructed otherwise.

8.1.2 Exhaust Gas Outlet. Select a sampling site located at least two stack diameters downstream of any disturbance (e.g., turbocharger exhaust, crossover junction or recirculation take-off) and at least one-half stack diameter upstream of the gas discharge to the atmosphere. Use a single sampling extraction point near the center of the duct (e.g., within the 10 percent centroidal area), unless instructed otherwise.

8.2 Stack Gas Collection and Analysis. Prior to the first stack gas sampling run, conduct that the pre-sampling calibration in accordance with Section 10.1. Use Figure 1 to record all data. Zero the analyzer with zero gas. Confirm and record that the scrubber media color is correct and not exhausted. Then position the probe at the sampling point and begin the sampling run at the same flow rate used during the up-scale calibration. Record the start time. Record all EC cell output responses and the flow rate during the “sample conditioning phase” once per minute until constant readings are obtained. Then begin the “measurement data phase” and record readings every 15 seconds for at least two minutes (or eight readings), or as otherwise required to achieve two continuous minutes of data that meet the specification given in Section 13.1. Finally, perform the “refresh phase” by introducing dry air, free from CO and other combustion gases, until several minute-to-minute readings of consistent value have been obtained. For each run use the “measurement data phase” readings to calculate the average stack gas CO and O₂ concentrations.

8.3 EC Cell Rate. Maintain the EC cell sample flow rate so that it does not vary by more than ±10 percent throughout the pre-sampling calibration, stack gas sampling and post-sampling calibration check. Alternatively, the EC cell sample flow rate can be maintained within a tolerance range that does not affect the gas concentration readings by more than ±3 percent, as instructed by the EC cell manufacturer.

9.0 Quality Control (Reserved)

10.0 Calibration and Standardization

10.1 Pre-Sampling Calibration. Conduct the following protocol once for each nominal range to be used on each EC cell before performing a stack gas sampling run on each field sampling day. Repeat the calibration if you replace an EC cell before completing all of the sampling runs. There is no prescribed order for calibration of the EC cells; however, each cell must complete the measurement data phase during calibration. Assemble the measurement system by following the manufacturer's recommended protocols including for preparing and preconditioning the EC cell. Assure the measurement system has no leaks and verify the gas scrubbing agent is not depleted. Use Figure 1 to record all data.

10.1.1 Zero Calibration. For both the O₂ and CO cells, introduce zero gas to the measurement system (e.g., at the calibration assembly) and record the concentration reading every minute until readings are constant for at least two consecutive minutes. Include the time and sample flow rate. Repeat the steps in this section at least once to verify the zero calibration for each component gas.

10.1.2 Zero Calibration Tolerance. For each zero gas introduction, the zero level output must be less than or equal to ±3 percent of the up-scale gas value or ±1 ppm, whichever is less restrictive, for the CO channel and less than or equal to ±0.3 percent O₂ for the O₂ channel.

10.1.3 Up-Scale Calibration. Individually introduce each calibration gas to the measurement system (e.g., at the calibration assembly) and record the start time. Record all EC cell output responses and the flow rate during this “sample conditioning phase” once per minute until readings are constant for at least two minutes. Then begin the “measurement data phase” and record readings every 15 seconds for a total of two minutes, or as otherwise required. Finally, perform the “refresh phase” by introducing dry air, free from CO and other combustion gases, until readings are constant for at least two consecutive minutes. Then repeat the steps in this section at least once to verify the calibration for each component gas. Introduce all gases to flow through the entire sample handling system (i.e., at the exit end of the sampling probe or the calibration assembly).

10.1.4 Up-Scale Calibration Error. The mean of the difference of the “measurement data phase” readings from the reported standard gas value must be less than or equal to ±5 percent or ±1 ppm for CO or ±0.5 percent O₂, whichever is less restrictive, respectively. The maximum allowable deviation from the mean measured value of any single “measurement data phase” reading must be less than or equal to ±2 percent or ±1 ppm for CO or ±0.5 percent O₂, whichever is less restrictive, respectively.

10.2 Post-Sampling Calibration Check. Conduct a stack gas post-sampling calibration check after the stack gas sampling run or set of runs and within 12 hours of the initial calibration. Conduct up-scale and zero calibration checks using the protocol in Section 10.1. Make no changes to the sampling system or EC cell calibration until all post-sampling calibration checks have been recorded. If either the zero or up-scale calibration error exceeds the respective specification in Sections 10.1.2 and 10.1.4 then all measurement data collected since the previous successful calibrations are invalid and re-calibration and re-sampling are required. If the sampling system is disassembled or the EC cell calibration is adjusted, repeat the calibration check before conducting the next analyzer sampling run.

11.0 Analytical Procedure

The analytical procedure is fully discussed in Section 8.

12.0 Calculations and Data Analysis

Determine the CO and O₂ concentrations for each stack gas sampling run by calculating the mean gas concentrations of the data recorded during the “measurement data phase”.

13.0 Protocol Performance

Use the following protocols to verify consistent analyzer performance during each field sampling day.

13.1 Measurement Data Phase Performance Check. Calculate the mean of the readings from the “measurement data phase”. The maximum allowable deviation from the mean for each of the individual readings is ±2 percent, or ±1 ppm, whichever is less restrictive. Record the mean value and maximum deviation for each gas monitored. Data must conform to Section 10.1.4. The EC cell flow rate must conform to the specification in Section 8.3.

Example:

A measurement data phase is invalid if the maximum deviation of any single reading comprising that mean is greater than ±2 percent or ±1 ppm (the default criteria). For example, if the mean = 30 ppm, single readings of below 29 ppm and above 31 ppm are disallowed).

13.2 Interference Check. Before the initial use of the EC cell and interference gas scrubber in the field, and semi-annually thereafter, challenge the interference gas scrubber with NO and NO₂ gas standards that are generally recognized as representative of diesel-fueled engine NO and NO₂ emission values. Record the responses displayed by the CO EC cell and other pertinent data on Figure 1 or a similar form.

13.2.1 Interference Response. The combined NO and NO₂ interference response should be less than or equal to ±5 percent of the up-scale CO calibration gas concentration.

13.3 Repeatability Check. Conduct the following check once for each nominal range that is to be used on the CO EC cell within 5 days prior to each field sampling program. If a field sampling program lasts longer than 5 days, repeat this check every 5 days. Immediately repeat the check if the EC cell is replaced or if the EC cell is exposed to gas concentrations greater than 150 percent of the highest up-scale gas concentration.

13.3.1 Repeatability Check Procedure. Perform a complete EC cell sampling run (all three phases) by introducing the CO calibration gas to the measurement system and record the response. Follow Section 10.1.3. Use Figure 1 to record all data. Repeat the run three times for a total of four complete runs. During the four repeatability check runs, do not adjust the system except where necessary to achieve the correct calibration gas flow rate at the analyzer.

13.3.2 Repeatability Check Calculations. Determine the highest and lowest average “measurement data phase” CO concentrations from the four repeatability check runs and record the results on Figure 1 or a similar form. The absolute value of the difference between the maximum and minimum average values recorded must not vary more than ±3 percent or ±1 ppm of the up-scale gas value, whichever is less restrictive.

14.0 Pollution Prevention (Reserved)

15.0 Waste Management (Reserved)

16.0 Alternative Procedures (Reserved)

17.0 References

(1) “Development of an Electrochemical Cell Emission Analyzer Test Protocol” , Topical Report, Phil Juneau, Emission Monitoring, Inc., July 1997.

(2) “Determination of Nitrogen Oxides, Carbon Monoxide, and Oxygen Emissions from Natural Gas-Fired Engines, Boilers, and Process Heaters Using Portable Analyzers” , EMC Conditional Test Protocol 30 (CTM-30), Gas Research Institute Protocol GRI-96/0008, Revision 7, October 13, 1997.

(3) “ICAC Test Protocol for Periodic Monitoring” , EMC Conditional Test Protocol 34 (CTM-034), The Institute of Clean Air Companies, September 8, 1999.

(4) “Code of Federal Regulations” , Protection of Environment, 40 CFR, Part 60, Appendix A, Methods 1-4; 10.

Table 1: Appendix A - Sampling Run Data.

Facility__________ Engine I.D.__________ Date______
Run Type:	(_)	(_)	(_)	(_)
(X)	Pre-Sample Calibration	Stack Gas Sample	Post-Sample Cal. Check	Repeatability Check

Run #	1	1	2	2	3	3	4	4	Time	Scrub. OK	Flow- Rate
Gas	O2	CO	O2	CO	O2	CO	O2	CO
Sample Cond. Phase
″
″
″
″
Measurement Data Phase
″
″
″
″
″
″
″
″
″
″
Mean
Refresh Phase
″
″
″
″

[78 FR 6721, Jan. 30, 2013]