ASTM D5149-95
(Test Method)Standard Test Method for Ozone in the Atmosphere: Continuous Measurement by Ethylene Chemiluminescence
Standard Test Method for Ozone in the Atmosphere: Continuous Measurement by Ethylene Chemiluminescence
SCOPE
1.1 This test method describes the sampling and continuous analysis of the ozone content of the atmosphere at concentrations of 20 to 2000 [mu]g of ozone/m3 (10 ppb (v) to 1 ppm (v)).
1.2 This test method is limited in application by its sensitivity to interferences as described below. This test method is not suitable for personal sampling because of instrument size and sensitivity to vibration and ambient temperature.
1.3 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. Some specific precautionary statements are presented in Section 8.
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NOTICE: This standard has either been superseded and replaced by a new version or discontinued.
Contact ASTM International (www.astm.org) for the latest information.
Designation: D 5149 – 95
Standard Test Method for
Ozone in the Atmosphere: Continuous Measurement by
Ethylene Chemiluminescence
This standard is issued under the fixed designation D 5149; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.
1. Scope (SI) (the Modernized Metric System)
E 591 Practice for Safety and Health Requirements Relating
1.1 This test method describes the sampling and continuous
to Occupational Exposure to Ozone
analysis of the ozone content of the atmosphere at concentra-
2.2 U.S. Environmental Protection Agency Standards:
tions of 20 to 2000μ g of ozone/m (10 ppb (v) to 1 ppm (v)).
EPA-600/4-79-056 Transfer Standards for Calibration of Air
1.2 This test method is limited in application by its sensi-
Monitoring Analyzers for Ozone (NTIS: PB80146871)
tivity to interferences as described below. This test method is
EPA-600/4-79-057 Technical Assistance Document for the
not suitable for personal sampling because of instrument size
Calibration of Ozone Monitors (NTIS: PB80149552)
and sensitivity to vibration and ambient temperature.
EPA-600/4-80-050 Evaluation of Ozone Calibration Tech-
1.3 This standard does not purport to address all of the
niques (NTIS: PB81118911)
safety concerns, if any, associated with its use. It is the
EPA-600/4-83-003 Performance Test Results and Compara-
responsibility of the user of this standard to establish appro-
tive Data for Designated Reference and Equivalent Meth-
priate safety and health practices and determine the applica-
ods for Ozone (NTIS: PB83166686)
bility of regulatory limitations prior to use. Some specific
2.3 Code of Federal Regulations:
precautionary statements are presented in Section 8.
40-CFR-Part 53.20
2. Referenced Documents
3. Terminology
2.1 ASTM Standards:
3.1 Definitions—For definitions of terms used in this test
D 1356 Terminology Relating to Sampling and Analysis of
method, refer to Terminology D 1356 and Practice D 1914. An
Atmospheres
explanation of units, symbols and conversion factors may be
D 1357 Practice for Planning the Sampling of the Ambient
found in Practice E 380.
Atmosphere
3.2 Definitions of Terms Specific to This Standard:
D 1605 Practice for Sampling Atmospheres for Analysis of
3.2.1 absolute ultra-violet spectrometer—a spectrometer
Gases and Vapors
whose design, construction and maintenance is such that it can
D 1914 Practice for Conversion Units and Factors Relating
measure the absorbance caused by ozone mixtures without
to Sampling and Analysis of Atmospheres
reference to external absorption standards. Given a value f+or
D 3249 Practice for General Ambient Air Analyzer Proce-
the absorption coefficient of ozone at 253.7 nm and a reading
dures
from the absolute ultraviolet spectrometer, ozone concentra-
D 3670 Guide for Determination of Precision and Bias of
2 tions can be calculated with accuracy. Measurements by an
Methods of Committee D-22
absolute ultraviolet spectrometer should be made on prepared
D 5011 Practices for Calibration of Ozone Monitors Using
2 ozone mixtures free from interferences.
Transfer Standards
3.2.2 primary standard—a standard directly defined and
D 5110 Practice for Calibration of Ozone Monitors and
established by some authority, against which all secondary
Certification of Ozone Transfer Standards Using Ultravio-
standards are compared.
let Photometry
3.2.3 secondary standard—a standard used as a means of
E 380 Practice for Use of the International System of Units
comparison, but checked against a primary standard.
3.2.4 standard—an accepted reference sample or device
used for establishing measurement of a physical quantity.
This test method is under the jurisdiction of ASTM Committee D-22 on 3.2.5 transfer standard—a type of secondary standard. It is
Sampling and Analysis of Atmospheres and is the direct responsibility of Subcom-
mittee D22.03 on Ambient Atmospheres and Source Emissions.
Current edition approved Sept. 10, 1995. Published November 1995. Originally Annual Book of ASTM Standards, Vol 14.02.
published as D 5149 – 90. Last previous edition D 5149 – 90. Discontinued; see 1990 Annual Book of ASTM Standards, Vol 11.03.
2 6
Annual Book of ASTM Standards, Vol 11.03. Available from the National Technical Information Service, Springfield, VA
Discontinued—See 1991 Annual Book of ASTM Standards, Vol 11.03. 22161.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
NOTICE: This standard has either been superseded and replaced by a new version or discontinued.
Contact ASTM International (www.astm.org) for the latest information.
D 5149
a transportable device or apparatus which, together with in the form of light in the 300 to 600 nm region, with maximum
operational procedures, is capable of reproducing sample intensity at 430 nm. The light energy is measured by a
concentration or producing acceptable assays of sample con- photosensor (frequently a photomultiplier tube) that produces
centrations. an output current proportional to the light intensity. The
current, converted to voltage and conditioned as necessary by
4. Significance and Use
the electronic circuits, becomes the analyzer’s output signal.
4.1 Air quality standards for ozone have been promulgated (See 2.2.4.)
by government authorities to protect the health and welfare of
7. Apparatus
the public. Though ozone itself is a toxic material, it is often
7.1 A schematic of the instrument is given in Fig. 1. The
complex organic compounds that cause the symptoms of smog
chemiluminescent reaction cell is constructed of materials inert
such as tearing and burning eyes. However, ozone is the
to ozone, for example, PTFE-coated metal, borosilicate glass,
predominant oxidant and is much more easily monitored than
fused silica.
organic species. Since ozone concentrations are also correlated
7.2 The input filter is installed in front of the sample line to
with other photochemical oxidant levels, it is the substance that
prevent aerosols or particulate matter from entering the mea-
is specified in air quality standards and regulations.
suring system. PTFE filters with pore sizes between 0.5 and 5.0
5. Interferences μm should be used. The filter should be kept clean since
accumulated material on the filter may catalyze the breakdown
5.1 Any aerosol that scatters light or that may deposit on the
of ozone into oxygen. Depressed ozone responses have been
photomultiplier window constitutes a negative interference to
observed immediately after filter changes for periods up to one
this test method. Particulate matter can be removed with a
hour.
poly-tetrafluoroethylene (PTFE) membrane filter; however,
7.3 Internal lines and fittings in the sample stream prior to
this filter may become contaminated and scrub ozone. It is
the reaction call are made of PTFE or other ozone-inert
important to check the ozone-inertness of these filters. (See
material.
Practice D 5010.)
7.4 Due to the flammability of ethylene, some manufactur-
5.2 Atmospheric humidity constitutes a positive interfer-
ers suggest the use of ethylene-carbon dioxide blends instead
ence to this test method when calibrations are conducted with
of 100 % ethylene when the monitoring device is to be used in
dry span gas mixtures. The range of interference reported is
7 a public facility. This blend is a liquefied, nonflammable
tabulated in Annex A2 of this test method.
mixture of approximately 9 % ethylene and 91 % CO . The
5.3 Reduced sulfur compounds (H S and CS but not COS
2 2
chemiluminescent reaction is the same; however, gas consump-
or SO ) may constitute positive interferences to this test
tion is considerably higher as a result of the reduced ethylene
method. Part-per-million by volume levels of such gases
concentration. The proportions of ethylene and CO supplied
reportedly enhance olefin chemiluminescence several hundred- 2
by the blend change as the mixture is consumed from the
fold in a study using ozone chemiluminescence in reverse as an
8 cylinder. Since this changes the sensitivity of the analyzer, the
olefin-specific sensor . Moreover, the enhancement is propor-
analyzer should be recalibrated. The concentration of ethylene
tional to sulfur compound concentration. Since ambient con-
supplied by the blend is also changed by the temperature of the
centrations of alkanes and NOx may reduce the magnitude of
cylinder, which must be maintained constant during use. (See
the sensitization, estimated effects of such interferents should
2.2.4.)
be determined under conditions of instrument use.
8. Safety Hazards
6. Measurement Principle
8.1 Beyond the normal precautions necessary when working
6.1 This measurement principle is based on the photometric
detection of the chemiluminescence (light produced by a
chemical reaction) resulting from the flameless gas phase
reaction of ethylene (C H ) with ozone (O ). The sample gas
2 4 3
containing ozone is mixed with excess ethylene (bottle gas
supplied to the instrument) to generate excited formaldehyde
(HCHO*) molecules. The excited formaldehyde molecules
decay immediately to the ground energy state, releasing energy
Kleindienst, T. E., Hudgens, E. E., Smith, D. F., McElroy, F. F., and Bufalini,
J. J., “Comparison of Chemiluminescence and Ultraviolet Ozone Monitor Re-
sponses in the Presence of Humidity and Photochemical Pollutants,” Journal of of
Air and Waste Management Assoc., Vol 43, 1993, p 213.
Weise, A. H., Henrich, K. K., and Schurath, U., “Sensitivity Enhancement of a
Chemiluminescent Olefin Analyzer by Sulfur-Containing Gases,” Environmental
Science and Technology, Vol 13, 1979, p. 85.
Leston, A. and Ollison, W. M., “Estimated Accuracy of Ozone Design Values:
Are They Compromised by Method Interferences?”, TR-23, Tropospheric Ozone:
FIG. 1 Schematic Diagram of a Chemiluminescence Ozone
Nonattainment and Design Values Issues, AWMA, Pittsburg, PA, October 27–
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