Title 40

Appendix D to Part 50 - Reference Measurement Principle and Calibration Procedure for the Measurement of Ozone in the Atmosphere (Chemiluminescence Method)

40:2.0.1.1.1.0.1.20.5 : Appendix D

Appendix D to Part 50 - Reference Measurement Principle and Calibration Procedure for the Measurement of Ozone in the Atmosphere (Chemiluminescence Method)

1.0 Applicability.

1.1 This chemiluminescence method provides reference measurements of the concentration of ozone (O3) in ambient air for determining compliance with the national primary and secondary ambient air quality standards for O3 as specified in 40 CFR part 50. This automated method is applicable to the measurement of ambient O3 concentrations using continuous (real-time) sampling and analysis. Additional quality assurance procedures and guidance are provided in 40 CFR part 58, appendix A, and in Reference 14.

2.0 Measurement Principle.

2.1 This reference method is based on continuous automated measurement of the intensity of the characteristic chemiluminescence released by the gas phase reaction of O3 in sampled air with either ethylene (C2H4) or nitric oxide (NO) gas. An ambient air sample stream and a specific flowing concentration of either C2H4 (ET-CL method) or NO (NO-CL method) are mixed in a measurement cell, where the resulting chemiluminescence is quantitatively measured by a sensitive photo-detector. References 8-11 describe the chemiluminescence measurement principle.

2.2 The measurement system is calibrated by referencing the instrumental chemiluminescence measurements to certified O3 standard concentrations generated in a dynamic flow system and assayed by photometry to be traceable to a National Institute of Standards and Technology (NIST) standard reference photometer for O3 (see Section 4, Calibration Procedure, below).

2.3 An analyzer implementing this measurement principle is shown schematically in Figure 1. Designs implementing this measurement principle must include: an appropriately designed mixing and measurement cell; a suitable quantitative photometric measurement system with adequate sensitivity and wavelength specificity for O3; a pump, flow control, and sample conditioning system for sampling the ambient air and moving it into and through the measurement cell; a sample air dryer as necessary to meet the water vapor interference limit requirement specified in subpart B of part 53 of this chapter; a means to supply, meter, and mix a constant, flowing stream of either C2H4 or NO gas of fixed concentration with the sample air flow in the measurement cell; suitable electronic control and measurement processing capability; and other associated apparatus as may be necessary. The analyzer must be designed and constructed to provide accurate, repeatable, and continuous measurements of O3 concentrations in ambient air, with measurement performance that meets the requirements specified in subpart B of part 53 of this chapter.

2.4 An analyzer implementing this measurement principle and calibration procedure will be considered a federal reference method (FRM) only if it has been designated as a reference method in accordance with part 53 of this chapter.

2.5 Sampling considerations. The use of a particle filter on the sample inlet line of a chemiluminescence O3 FRM analyzer is required to prevent buildup of particulate matter in the measurement cell and inlet components. This filter must be changed weekly (or at least often as specified in the manufacturer's operation/instruction manual), and the sample inlet system used with the analyzer must be kept clean, to avoid loss of O3 in the O3 sample air prior to the concentration measurement.

3.0 Interferences.

3.1 Except as described in 3.2 below, the chemiluminescence measurement system is inherently free of significant interferences from other pollutant substances that may be present in ambient air.

3.2 A small sensitivity to variations in the humidity of the sample air is minimized by a sample air dryer. Potential loss of O3 in the inlet air filter and in the air sample handling components of the analyzer and associated exterior air sampling components due to buildup of airborne particulate matter is minimized by filter replacement and cleaning of the other inlet components.

4.0 Calibration Procedure.

4.1 Principle. The calibration procedure is based on the photometric assay of O3 concentrations in a dynamic flow system. The concentration of O3 in an absorption cell is determined from a measurement of the amount of 254 nm light absorbed by the sample. This determination requires knowledge of (1) the absorption coefficient (α) of O3 at 254 nm, (2) the optical path length (l) through the sample, (3) the transmittance of the sample at a nominal wavelength of 254 nm, and (4) the temperature (T) and pressure (P) of the sample. The transmittance is defined as the ratio I/I0, where I is the intensity of light which passes through the cell and is sensed by the detector when the cell contains an O3 sample, and I0 is the intensity of light which passes through the cell and is sensed by the detector when the cell contains zero air. It is assumed that all conditions of the system, except for the contents of the absorption cell, are identical during measurement of I and I0. The quantities defined above are related by the Beer-Lambert absorption law,

Where: α = absorption coefficient of O3 at 254 nm = 308 ±4 atm−1 cm−1 at 0 °C and 760 torr, 1 2 3 4 5 6 7 c = O3 concentration in atmospheres, and l = optical path length in cm.

A stable O3 generator is used to produce O3 concentrations over the required calibration concentration range. Each O3 concentration is determined from the measurement of the transmittance (I/I0) of the sample at 254 nm with a photometer of path length l and calculated from the equation,

The calculated O3 concentrations must be corrected for O3 losses, which may occur in the photometer, and for the temperature and pressure of the sample.

4.2 Applicability. This procedure is applicable to the calibration of ambient air O3 analyzers, either directly or by means of a transfer standard certified by this procedure. Transfer standards must meet the requirements and specifications set forth in Reference 12.

4.3 Apparatus. A complete UV calibration system consists of an O3 generator, an output port or manifold, a photometer, an appropriate source of zero air, and other components as necessary. The configuration must provide a stable O3 concentration at the system output and allow the photometer to accurately assay the output concentration to the precision specified for the photometer (4.3.1). Figure 2 shows a commonly used configuration and serves to illustrate the calibration procedure, which follows. Other configurations may require appropriate variations in the procedural steps. All connections between components in the calibration system downstream of the O3 generator must be of glass, Teflon, or other relatively inert materials. Additional information regarding the assembly of a UV photometric calibration apparatus is given in Reference 13. For certification of transfer standards which provide their own source of O3, the transfer standard may replace the O3 generator and possibly other components shown in Figure 2; see Reference 12 for guidance.

4.3.1 UV photometer. The photometer consists of a low-pressure mercury discharge lamp, (optional) collimation optics, an absorption cell, a detector, and signal-processing electronics, as illustrated in Figure 2. It must be capable of measuring the transmittance, I/I0, at a wavelength of 254 nm with sufficient precision such that the standard deviation of the concentration measurements does not exceed the greater of 0.005 ppm or 3% of the concentration. Because the low-pressure mercury lamp radiates at several wavelengths, the photometer must incorporate suitable means to assure that no O3 is generated in the cell by the lamp, and that at least 99.5% of the radiation sensed by the detector is 254 nm radiation. (This can be readily achieved by prudent selection of optical filter and detector response characteristics.) The length of the light path through the absorption cell must be known with an accuracy of at least 99.5%. In addition, the cell and associated plumbing must be designed to minimize loss of O3 from contact with cell walls and gas handling components. See Reference 13 for additional information.

4.3.2 Air flow controllers. Air flow controllers are devices capable of regulating air flows as necessary to meet the output stability and photometer precision requirements.

4.3.3 Ozone generator. The ozone generator used must be capable of generating stable levels of O3 over the required concentration range.

4.3.4 Output manifold. The output manifold must be constructed of glass, Teflon, or other relatively inert material, and should be of sufficient diameter to insure a negligible pressure drop at the photometer connection and other output ports. The system must have a vent designed to insure atmospheric pressure in the manifold and to prevent ambient air from entering the manifold.

4.3.5 Two-way valve. A manual or automatic two-way valve, or other means is used to switch the photometer flow between zero air and the O3 concentration.

4.3.6 Temperature indicator. A device to indicate temperature must be used that is accurate to ±1 °C.

4.3.7 Barometer or pressure indicator. A device to indicate barometric pressure must be used that is accurate to ±2 torr.

4.4 Reagents.

4.4.1 Zero air. The zero air must be free of contaminants which would cause a detectable response from the O3 analyzer, and it must be free of NO, C2H4, and other species which react with O3. A procedure for generating suitable zero air is given in Reference 13. As shown in Figure 2, the zero air supplied to the photometer cell for the I0 reference measurement must be derived from the same source as the zero air used for generation of the O3 concentration to be assayed (I measurement). When using the photometer to certify a transfer standard having its own source of O3, see Reference 12 for guidance on meeting this requirement.

4.5 Procedure.

4.5.1 General operation. The calibration photometer must be dedicated exclusively to use as a calibration standard. It must always be used with clean, filtered calibration gases, and never used for ambient air sampling. A number of advantages are realized by locating the calibration photometer in a clean laboratory where it can be stationary, protected from the physical shock of transportation, operated by a responsible analyst, and used as a common standard for all field calibrations via transfer standards.

4.5.2 Preparation. Proper operation of the photometer is of critical importance to the accuracy of this procedure. Upon initial operation of the photometer, the following steps must be carried out with all quantitative results or indications recorded in a chronological record, either in tabular form or plotted on a graphical chart. As the performance and stability record of the photometer is established, the frequency of these steps may be reduced to be consistent with the documented stability of the photometer and the guidance provided in Reference 12.

4.5.2.1 Instruction manual. Carry out all set up and adjustment procedures or checks as described in the operation or instruction manual associated with the photometer.

4.5.2.2 System check. Check the photometer system for integrity, leaks, cleanliness, proper flow rates, etc. Service or replace filters and zero air scrubbers or other consumable materials, as necessary.

4.5.2.3 Linearity. Verify that the photometer manufacturer has adequately established that the linearity error of the photometer is less than 3%, or test the linearity by dilution as follows: Generate and assay an O3 concentration near the upper range limit of the system or appropriate calibration scale for the instrument, then accurately dilute that concentration with zero air and re-assay it. Repeat at several different dilution ratios. Compare the assay of the original concentration with the assay of the diluted concentration divided by the dilution ratio, as follows

Where: E = linearity error, percent A1 = assay of the original concentration A2 = assay of the diluted concentration R = dilution ratio = flow of original concentration divided by the total flow

The linearity error must be less than 5%. Since the accuracy of the measured flow-rates will affect the linearity error as measured this way, the test is not necessarily conclusive. Additional information on verifying linearity is contained in Reference 13.

4.5.2.4 Inter-comparison. The photometer must be inter-compared annually, either directly or via transfer standards, with a NIST standard reference photometer (SRP) or calibration photometers used by other agencies or laboratories.

4.5.2.5 Ozone losses. Some portion of the O3 may be lost upon contact with the photometer cell walls and gas handling components. The magnitude of this loss must be determined and used to correct the calculated O3 concentration. This loss must not exceed 5%. Some guidelines for quantitatively determining this loss are discussed in Reference 13.

4.5.3 Assay of O3 concentrations. The operator must carry out the following steps to properly assay O3 concentrations.

4.5.3.1 Allow the photometer system to warm up and stabilize.

4.5.3.2 Verify that the flow rate through the photometer absorption cell, F, allows the cell to be flushed in a reasonably short period of time (2 liter/min is a typical flow). The precision of the measurements is inversely related to the time required for flushing, since the photometer drift error increases with time.

4.5.3.3 Ensure that the flow rate into the output manifold is at least 1 liter/min greater than the total flow rate required by the photometer and any other flow demand connected to the manifold.

4.5.3.4 Ensure that the flow rate of zero air, Fz, is at least 1 liter/min greater than the flow rate required by the photometer.

4.5.3.5 With zero air flowing in the output manifold, actuate the two-way valve to allow the photometer to sample first the manifold zero air, then Fz. The two photometer readings must be equal (I = I0).

Note:

In some commercially available photometers, the operation of the two-way valve and various other operations in section 4.5.3 may be carried out automatically by the photometer.

4.5.3.6 Adjust the O3 generator to produce an O3 concentration as needed.

4.5.3.7 Actuate the two-way valve to allow the photometer to sample zero air until the absorption cell is thoroughly flushed and record the stable measured value of Io.

4.5.3.8 Actuate the two-way valve to allow the photometer to sample the O3 concentration until the absorption cell is thoroughly flushed and record the stable measured value of I.

4.5.3.9 Record the temperature and pressure of the sample in the photometer absorption cell. (See Reference 13 for guidance.)

4.5.3.10 Calculate the O3 concentration from equation 4. An average of several determinations will provide better precision.

Where: [O3]OUT = O3 concentration, ppm α = absorption coefficient of O3 at 254 nm = 308 atm−1 cm−1 at 0 °C and 760 torr l = optical path length, cm T = sample temperature, K P = sample pressure, torr L = correction factor for O3 losses from 4.5.2.5 = (1−fraction of O3 lost). Note:

Some commercial photometers may automatically evaluate all or part of equation 4. It is the operator's responsibility to verify that all of the information required for equation 4 is obtained, either automatically by the photometer or manually. For “automatic” photometers which evaluate the first term of equation 4 based on a linear approximation, a manual correction may be required, particularly at higher O3 levels. See the photometer instruction manual and Reference 13 for guidance.

4.5.3.11 Obtain additional O3 concentration standards as necessary by repeating steps 4.5.3.6 to 4.5.3.10 or by Option 1.

4.5.4 Certification of transfer standards. A transfer standard is certified by relating the output of the transfer standard to one or more O3 calibration standards as determined according to section 4.5.3. The exact procedure varies depending on the nature and design of the transfer standard. Consult Reference 12 for guidance.

4.5.5 Calibration of ozone analyzers. Ozone analyzers must be calibrated as follows, using O3 standards obtained directly according to section 4.5.3 or by means of a certified transfer standard.

4.5.5.1 Allow sufficient time for the O3 analyzer and the photometer or transfer standard to warm-up and stabilize.

4.5.5.2 Allow the O3 analyzer to sample zero air until a stable response is obtained and then adjust the O3 analyzer's zero control. Offsetting the analyzer's zero adjustment to +5% of scale is recommended to facilitate observing negative zero drift (if any). Record the stable zero air response as “Z”.

4.5.5.3 Generate an O3 concentration standard of approximately 80% of the desired upper range limit (URL) of the O3 analyzer. Allow the O3 analyzer to sample this O3 concentration standard until a stable response is obtained.

4.5.5.4 Adjust the O3 analyzer's span control to obtain the desired response equivalent to the calculated standard concentration. Record the O3 concentration and the corresponding analyzer response. If substantial adjustment of the span control is necessary, recheck the zero and span adjustments by repeating steps 4.5.5.2 to 4.5.5.4.

4.5.5.5 Generate additional O3 concentration standards (a minimum of 5 are recommended) over the calibration scale of the O3 analyzer by adjusting the O3 source or by Option 1. For each O3 concentration standard, record the O3 concentration and the corresponding analyzer response.

4.5.5.6 Plot the O3 analyzer responses (vertical or Y-axis) versus the corresponding O3 standard concentrations (horizontal or X-axis). Compute the linear regression slope and intercept and plot the regression line to verify that no point deviates from this line by more than 2 percent of the maximum concentration tested.

4.5.5.7 Option 1: The various O3 concentrations required in steps 4.5.3.11 and 4.5.5.5 may be obtained by dilution of the O3 concentration generated in steps 4.5.3.6 and 4.5.5.3. With this option, accurate flow measurements are required. The dynamic calibration system may be modified as shown in Figure 3 to allow for dilution air to be metered in downstream of the O3 generator. A mixing chamber between the O3 generator and the output manifold is also required. The flow rate through the O3 generator (Fo) and the dilution air flow rate (FD) are measured with a flow or volume standard that is traceable to a NIST flow or volume calibration standard. Each O3 concentration generated by dilution is calculated from:

Where: [O3]′OUT = diluted O3 concentration, ppm FO = flow rate through the O3 generator, liter/min FD = diluent air flow rate, liter/min Note:

Additional information on calibration and pollutant standards is provided in Section 12 of Reference 14.

5.0 Frequency of Calibration.

5.1 The frequency of calibration, as well as the number of points necessary to establish the calibration curve, and the frequency of other performance checking will vary by analyzer; however, the minimum frequency, acceptance criteria, and subsequent actions are specified in Appendix D of Reference 14: Measurement Quality Objectives and Validation Templates. The user's quality control program shall provide guidelines for initial establishment of these variables and for subsequent alteration as operational experience is accumulated. Manufacturers of analyzers should include in their instruction/operation manuals information and guidance as to these variables and on other matters of operation, calibration, routine maintenance, and quality control.

6.0 References.

1. E.C.Y. Inn and Y. Tanaka, “Absorption coefficient of Ozone in the Ultraviolet and Visible Regions”, J. Opt. Soc. Am., 43, 870 (1953). 2. A. G. Hearn, “Absorption of Ozone in the Ultraviolet and Visible Regions of the Spectrum”, Proc. Phys. Soc. (London), 78, 932 (1961). 3. W. B. DeMore and O. Raper, “Hartley Band Extinction Coefficients of Ozone in the Gas Phase and in Liquid Nitrogen, Carbon Monoxide, and Argon”, J. Phys. Chem., 68, 412 (1964). 4. M. Griggs, “Absorption Coefficients of Ozone in the Ultraviolet and Visible Regions”, J. Chem. Phys., 49, 857 (1968). 5. K. H. Becker, U. Schurath, and H. Seitz, “Ozone Olefin Reactions in the Gas Phase. 1. Rate Constants and Activation Energies”, Int'l Jour. of Chem. Kinetics, VI, 725 (1974). 6. M. A. A. Clyne and J. A. Coxom, “Kinetic Studies of Oxy-halogen Radical Systems”, Proc. Roy. Soc., A303, 207 (1968). 7. J. W. Simons, R. J. Paur, H. A. Webster, and E. J. Bair, “Ozone Ultraviolet Photolysis. VI. The Ultraviolet Spectrum”, J. Chem. Phys., 59, 1203 (1973). 8. Ollison, W.M.; Crow, W.; Spicer, C.W. “Field testing of new-technology ambient air ozone monitors.” J. Air Waste Manage. Assoc., 63 (7), 855-863 (2013). 9. Parrish, D.D.; Fehsenfeld, F.C. “Methods for gas-phase measurements of ozone, ozone precursors and aerosol precursors.” Atmos. Environ., 34 (12-14), 1921-1957(2000). 10. Ridley, B.A.; Grahek, F.E.; Walega, J.G. “A small, high-sensitivity, medium-response ozone detector suitable for measurements from light aircraft.” J. Atmos. Oceanic Technol., 9 (2), 142-148(1992). 11. Boylan, P., Helmig, D., and Park, J.H. “Characterization and mitigation of water vapor effects in the measurement of ozone by chemiluminescence with nitric oxide.” Atmos. Meas. Tech. 7, 1231-1244 (2014). 12. Transfer Standards for Calibration of Ambient Air Monitoring Analyzers for Ozone, EPA publication number EPA-454/B-13-004, October 2013. EPA, Office of Air Quality Planning and Standards, Research Triangle Park, NC 27711. [Available at www.epa.gov/ttnamti1/files/ambient/qaqc/OzoneTransferStandardGuidance.pdf.] 13. Technical Assistance Document for the Calibration of Ambient Ozone Monitors, EPA publication number EPA-600/4-79-057, September, 1979. [Available at www.epa.gov/ttnamti1/files/ambient/criteria/4-79-057.pdf.] 14. QA Handbook for Air Pollution Measurement Systems - Volume II. Ambient Air Quality Monitoring Program. EPA-454/B-13-003, May 2013. [Available at http://www.epa.gov/ttnamti1/files/ambient/pm25/qa/QA-Handbook-Vol-II.pdf.] [80 FR 65453, Oct. 26, 2015]