Page images
PDF
EPUB

APPENDIX C-MEASUREMENT PRINCIPLE

AND CALIBRATION PROCEDURE FOR THE MEASUREMENT OF CARBON MONOXIDE IN THE ATMosphere (NON-DISPERSIVE INFRARED PHOTOMETRY)

Measurement Principle

1. Measurements are based on the absorption of infrared radiation by carbon monoxide (CO) in a non-dispersive photometer. Infrared energy from a source is passed through a cell containing the gas sample to be analyzed, and the quantitative absorption of energy by CO in the sample cell is measured by a suitable detector. The photometer is sensitized to CO by employing CO gas in either the detector or in a filter cell in the optical path, thereby limiting the measured absorption to one or more of the characteristic wavelengths at which CO strongly absorbs. Optical filters or other means may also be used to limit sensitivity of the photometer to a narrow band of interest. Various schemes may be used to provide a suitable zero reference for the photometer. The measured absorption is converted to an electrical output signal, which is related to the concentration of CO in the measurement cell.

2. An analyzer based on this principle will be considered a reference method only if it has been designated as a reference method in accordance with Part 53 of this chapter. 3. Sampling considerations.

The use of a particle filter on the sample inlet line of an NDIR CO analyzer is optional and left to the discretion of the user or the manufacturer. Use of filter should depend on the analyzer's susceptibility to interference, malfunction, or damage due to particles.

Calibration Procedure

1. Principle. Either of two methods may be used for dynamic multipoint calibration of CO analyzers: (1) One method uses a single certified standard cylinder of CO, diluted as necessary with zero air, to obtain the various calibration concentrations needed. (2) The other method uses individual certified standard cylinders of CO for each concentration needed. Additional information on calibration may be found in Section 2.0.9 of Reference 1.

2. Apparatus. The major components and typical configurations of the calibration systems for the two calibration methods are shown in Figures 1 and 2.

2.1 Flow controller(s). Device capable of adjusting and regulating flow rates. Flow rates for the dilution method (Figure 1) must be regulated to +1%.

2.2 Flow meter(s). Calibrated flow meter capable of measuring and monitoring flow

rates. Flow rates for the dilution method (Figure 1) must be measured with an accuracy of 2% of the measured value.

2.3 Pressure regulator(s) for standard CO cylinder(s). Regulator must have nonreactive diaphragm and internal parts and a suitable delivery pressure.

2.4 Mixing chamber. A chamber designed to provide thorough mixing of CO and diluent air for the dilution method.

2.5 Output manifold. The output manifold should be of sufficient diameter to insure an insignificant pressure drop at the analyzer connection. The system must have a vent designed to insure atmospheric pressure at the manifold and to prevent ambient air from entering the manifold. 3. Reagents. 3.1 CO concentration standard(s). Cylinder(s) of CO in air containing appropriate concentrations(s) of CO suitable for the selected operating range of the analyzer under calibration; CO standards for the dilution method may be contained in a nitrogen matrix if the zero air dilution ratio is not less than 100:1. The assay of the cylinder(s) must be traceable either to a National Bureau of Standards (NBS) CO in air Standard Reference Material (SRM) or to an NBS/EPA-approved commercially available Certified Reference Material (CRM). CRM's are described in Reference 2, and a list of CRM sources is available from the address shown for Reference 2. A recommended protocol for certifying CO gas cylinders against either a CO SRM or a CRM is given in Reference 1. CO gas cylinders should be recertified on a regular basis as determined by the local quality control program.

3.2 Dilution gas (zero air). Air, free of contaminants which will cause a detectable response on the CO analyzer. The zero air should contain <0.1 ppm CO. A procedure for generating zero air is given in Reference 1.

4. Procedure Using Dynamic Dilution Method.

4.1 Assemble a dynamic calibration system such as the one shown in Figure 1. All calibration gases including zero air must be introduced into the sample inlet of the analyzer system. For specific operating instructions refer to the manufacturer's manual.

4.2 Insure that all flowmeters are properly calibrated, under the conditions of use, if appropriate, against an authoritative standard such as a soap-bubble meter or wet-test meter. All volumetric flowrates should be corrected to 25° C and 760 mm Hg (101 kPa). A discussion on calibration of flowmeters is given in Reference 1.

4.3 Select the operating range of the CO analyzer to be calibrated.

4.4 Connect the signal output of the CO analyzer to the input of the strip chart re

corder or other data collection device. All adjustments to the analyzer should be based on the appropriate strip chart or data device readings. References to analyzer responses in the procedure given below refer to recorder or data device responses.

4.5 Adjust the calibration system to deliver zero air to the output manifold. The total air flow must exceed the total demand of the analyzer(s) connected to the output manifold to insure that no ambient air is pulled into the manifold vent. Allow the analyzer to sample zero air until a stable respose is obtained. After the response has stabilized, adjust the analyzer zero control. Offsetting the analyzer zero adjustments to +5 percent of scale is recommended to facilitate observing negative zero drift. Record the stable zero air response as Zco.

4.6 Adjust the zero air flow and the CO flow from the standard CO cylinder to provide a diluted CO concentration of approximately 80 percent of the upper range limit (URL) of the operating range of the analyzer. The total air flow must exceed the total demand of the analyzer(s) connected to the output manifold to insure that no ambient air is pulled into the manifold vent. The exact CO concentration is calculated from:

[merged small][merged small][merged small][merged small][merged small][merged small][merged small][merged small][ocr errors][merged small][merged small][merged small]

Where:

URL=nominal upper range limit of the analyzer's operating range, and

Zco analyzer response to zero air, % scale.

If substantial adjustment of the analyzer span control is required, it may be necessary to recheck the zero and span adjustments by repeating Steps 4.5 and 4.6. Record the CO concentration and the analyzer's response. 4.7 Generate several additional concentrations (at least three evenly spaced points across the remaining scale are suggested to verify linearity) by decreasing Fco or increasing F. Be sure the total flow exceeds the analyzer's total flow demand. For each concentration generated, calculate the exact CO concentration using Equation (1). Record the concentration and the analyzer's response for each concentration. Plot the analyzer responses versus the corresponding CO concentrations and draw or calculate the calibration curve.

5. Procedure Using Multiple Cylinder Method. Use the procedure for the dynamic dilution method with the following changes: 5.1 Use a multi-cylinder system such as the typical one shown in Figure 2.

5.2 The flowmeter need not be accurately calibrated, provided the flow in the output manifold exceeds the analyzer's flow demand.

5.3 The various CO calibration concentrations required in Steps 4.6 and 4.7 are obtained without dilution by selecting the appropriate certified standard cylinder.

REFERENCES

1. Quality Assurance Handbook for Air Pollution Measurement Systems, Volume II-Ambient Air Specific Methods, EPA600/4-77-027a, U.S. Environmental Protection Agency, Environmental Monitoring Systems Laboratory, Research Triangle Park, North Carolina 27711, 1977.

2. A procedure for Establishing Traceability of Gas Mixtures to Certain National Bureau of Standards Standard Reference Materials. EPA-600/7-81-010, U.S. Environmental Protection Agency, Environmental Monitoring Systems Laboratory (MD-77), Research Triangle Park, North Carolina 27711, January 1981.

[blocks in formation]

Figure 1. Dilution method for calibration of CO analyzers.

[graphic][subsumed][subsumed][subsumed][subsumed][subsumed][subsumed][subsumed][subsumed][subsumed][subsumed][merged small][subsumed][subsumed][subsumed][merged small]

Figure 2. Multiple cylinder method for calibration of CO analyzers.

[47 FR 54922, Dec. 6, 1982; 48 FR 17355, Apr. 22, 1983]

APPENDIX D-MEASUREMENT PRINCIPLE AND CALIBRATION PROCEDURE FOR THE MEASUREMENT OF OZONE IN THE ATMOSPHERE

MEASUREMENT PRINCIPLE

1. Ambient air and ethylene are delivered simultaneously to a mixing zone where the ozone in the air reacts with the ethylene to emit light, which is detected by a photomultiplier tube. The resulting photocurrent is amplified and is either read directly or displayed on a recorder.

2. An analyzer based on this principle will be considered a reference method only if it has been designated as a reference method in accordance with Part 53 of this chapter and calibrated as follows:

CALIBRATION PROCEDURE

1. Principle. The calibration procedure is based on the photometric assay of ozone (O) concentrations in a dynamic flow system. The concentration of O, 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 (a) of O, at 254 nm, (2) the optical path length (1) through the sample, (3) the transmittance of the sample at a wavelength of 254 nm, and (4) the temperature (T) and pressure (P) of the sample. The transmittance is defined as the ratio I/I.. where I is the intensity of light which passes through the cell and is sensed by the detector when the cell contains an O, sample, and I, 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 I.. The quantities defined above are related by the Beer-Lambert absorption law,

[blocks in formation]
[blocks in formation]

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

2. Applicability. This procedure is applicable to the calibration of ambient air O, 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 8.

3. Apparatus. A complete UV calibration system consists of an ozone 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 ozone concentration at the system output and allow the photometer to accurately assay the output concentration to the precision specified for the photometer (3.1). Figure 1 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 O, generator should be of glass, Teflon, or other relatively inert materials. Additional information regarding the assembly of a UV photometric calibration apparatus is given in Reference 9. For certification of transfer standards which provide their own source of O., the transfer standard may replace the O, generator and possibly other components shown in Figure 1; see Reference 8 for guid

ance.

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 1. It must be capable of measuring the transmittance, I/I.. 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. Be

« PreviousContinue »