ASTM D5149-02(2008)
(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
SIGNIFICANCE AND USE
Air quality standards for ozone have been promulgated by government authorities to protect the health and welfare of the public. Though ozone itself is a toxic material, it is often complex organic compounds that cause the symptoms of smog such as tearing and burning eyes. However, ozone is the predominant oxidant and is much more easily monitored than organic species. Since ozone concentrations are also correlated with other photochemical oxidant levels, it is the substance that is specified in air quality standards and regulations.
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 μg 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.
General Information
Relations
Buy Standard
Standards Content (Sample)
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation: D5149 − 02(Reapproved 2008)
Standard Test Method for
Ozone in the Atmosphere: Continuous Measurement by
Ethylene Chemiluminescence
This standard is issued under the fixed designation D5149; 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 (´) indicates an editorial change since the last revision or reapproval.
1. Scope IEEE/ASTM SI-10 Practice for Use of the International
System of Units (SI) (the Modernized Metric System)
1.1 This test method describes the sampling and continuous
analysis of the ozone content of the atmosphere at concentra- 2.2 U.S. Environmental Protection Agency Standards:
tions of 20 to 2000 µg of ozone/m (10 ppb (v) to 1 ppm (v)). EPA-600/4-79-056 Transfer Standards for Calibration ofAir
Monitoring Analyzers for Ozone (NTIS: PB80146871)
1.2 This test method is limited in application by its sensi-
EPA-600/4-79-057 Technical Assistance Document for the
tivity to interferences as described below. This test method is
Calibration of Ozone Monitors (NTIS: PB80149552)
not suitable for personal sampling because of instrument size
EPA-600/4-80-050 Evaluation of Ozone Calibration Tech-
and sensitivity to vibration and ambient temperature.
niques (NTIS: PB81118911)
1.3 This standard does not purport to address all of the
EPA-600/4-83-003 Performance Test Results and Compara-
safety concerns, if any, associated with its use. It is the
tive Data for Designated Reference and Equivalent Meth-
responsibility of the user of this standard to establish appro-
ods for Ozone (NTIS: PB83166686)
priate safety and health practices and determine the applica-
2.3 Code of Federal Regulations:
bility of regulatory limitations prior to use. Some specific
40-CFR-Part 53.20
precautionary statements are presented in Section 8.
3. Terminology
2. Referenced Documents
3.1 Definitions—For definitions of terms used in this test
2.1 ASTM Standards:
method, refer to Terminology D1356 and Practice D1914.An
D1356 Terminology Relating to Sampling and Analysis of
explanation of units, symbols and conversion factors may be
Atmospheres
found in Practice IEEE/ASTM SI-10.
D1357 Practice for Planning the Sampling of the Ambient
3.2 Definitions of Terms Specific to This Standard:
Atmosphere
3.2.1 absolute ultra-violet photometer—a photometer
D1914 PracticeforConversionUnitsandFactorsRelatingto
whose design, construction and maintenance is such that it can
Sampling and Analysis of Atmospheres
measure the absorbance caused by ozone mixtures without
D3249 Practice for General Ambient Air Analyzer Proce-
reference to external absorption standards. Given a value for
dures
the absorption coefficient of ozone at 253.7 nm and a reading
D3670 Guide for Determination of Precision and Bias of
from the absolute ultraviolet photometer, ozone concentrations
Methods of Committee D22
can be calculated with accuracy. Measurements by an absolute
D5011 Practices for Calibration of Ozone Monitors Using
ultraviolet photometer should be made on prepared ozone
Transfer Standards
mixtures free from interferences.
D5110 Practice for Calibration of Ozone Monitors and
Certification of OzoneTransfer Standards Using Ultravio-
3.2.2 primary standard—a standard directly defined and
let Photometry
established by some authority, against which all secondary
standards are compared.
3.2.3 secondary standard—a standard used as a means of
This test method is under the jurisdiction of ASTM Committee D22 on Air
comparison, but checked against a primary standard.
Quality and is the direct responsibility of Subcommittee D22.03 on Ambient
Atmospheres and Source Emissions.
3.2.4 standard—an accepted reference sample or device
Current edition approved April 1, 2008. Published July 2008. Originally
used for establishing measurement of a physical quantity.
approved in 1990. Last previous edition approved in 2002 as D5149 – 02. DOI:
10.1520/D5149-02R08.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on Available from National Technical Information Service (NTIS), 5285 Port
the ASTM website. Royal Rd., Springfield, VA 22161, http://www.ntis.gov.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D5149 − 02 (2008)
3.2.5 transfer standard—a type of secondary standard. It is
a transportable device or apparatus which, together with
operational procedures, is capable of reproducing a sample
concentration or producing acceptable assays of sample con-
centrations.
4. Significance and Use
4.1 Air quality standards for ozone have been promulgated
by government authorities to protect the health and welfare of
the public. Though ozone itself is a toxic material, it is often
complex organic compounds that cause the symptoms of smog
such as tearing and burning eyes. However, ozone is the
predominant oxidant and is much more easily monitored than
organic species. Since ozone concentrations are also correlated
withotherphotochemicaloxidantlevels,itisthesubstancethat
is specified in air quality standards and regulations.
FIG. 1 Schematic Diagram of a Chemiluminescence Ozone Ana-
lyzer
5. Interferences
5.1 Anyaerosolthatscatterslightorthatmaydepositonthe
photomultiplier window constitutes a negative interference to 7. Apparatus
this test method. Particulate matter can be removed with a
7.1 A schematic of the instrument is given in Fig. 1. The
poly-tetrafluoroethylene (PTFE) membrane filter; however,
chemiluminescentreactioncellisconstructedofmaterialsinert
this filter may become contaminated and scrub ozone. It is
to ozone, for example, PTFE-coated metal, borosilicate glass,
important to check the ozone-inertness of these filters periodi-
fused silica.
cally. (See Practice D5110.)
7.2 The input filter is installed in front of the sample line to
5.2 Atmospheric humidity constitutes a positive interfer-
prevent aerosols or particulate matter from entering the mea-
ence to this test method when calibrations are conducted with
suringsystem.PTFEfilterswithporesizesbetween0.5and5.0
dry span gas mixtures. The range of interference reported is
µm should be used. The filter should be kept clean since
tabulated in Annex A2 of this test method.
accumulated material on the filter may catalyze the breakdown
of ozone into oxygen. Depressed ozone responses have been
5.3 Reduced sulfur compounds have not been found to
5 observed immediately after filter changes for periods up to one
constitute positive interferences to this test method.
hour.
6. Measurement Principle 7.3 Internal lines and fittings in the sample stream prior to
the reaction call are made of PTFE or other ozone-inert
6.1 This measurement principle is based on the photometric
material.
detection of the chemiluminescence (light produced by a
7.4 Due to the flammability of ethylene, some manufactur-
chemical reaction) resulting from the flameless gas phase
ers suggest the use of ethylene-carbon dioxide blends instead
reaction of ethylene (C H ) with ozone (O ). The sample gas
2 4 3
of 100 % ethylene when the monitoring device is to be used in
containing ozone is mixed with excess ethylene (bottle gas,
a public facility. This blend is a liquefied, nonflammable
C.P. or better, supplied to the instrument) to generate excited
mixture of approximately 9 % ethylene and 91 % CO . The
formaldehyde (HCHO*) molecules. The excited formaldehyde 2
chemiluminescentreactionisthesame;however,gasconsump-
molecules decay immediately to the ground energy state,
tion is considerably higher as a result of the reduced ethylene
releasing energy in the form of light in the 300 to 600 nm
concentration. The proportions of ethylene and CO supplied
region, with maximum intensity at 430 nm. The light energy is 2
by the blend change as the mixture is consumed from the
measured by a photosensor (frequently a photomultiplier tube)
cylinder. Since this changes the sensitivity of the analyzer, the
that produces an output current proportional to the light
analyzer should be recalibrated periodically.The concentration
intensity. The current, converted to voltage and conditioned as
of ethylene supplied by the blend is also changed by the
necessary by the electronic circuits, becomes the analyzer’s
temperatureofthecylinder,whichmustbemaintainedconstant
output signal.
during use.
8. Safety Hazards
Kleindienst, T. E., Hudgens, E. E., Smith, D. F., McElroy, F. F., and Bufalini,
8.1 Beyondthenormalprecautionsnecessarywhenworking
J. J., “Comparison of Chemiluminescence and Ultraviolet Ozone Monitor Re-
sponses in the Presence of Humidity and Photochemical Pollutants,” Journal of Air
with any instrument that contains high voltages and flammable
and Waste Management Assoc., Vol 43, 1993, p 213.
gases, this test method raises the need for some special
Kleindienst, T.C., McIver, C.D., Ollison, W. M., “A Study of Interferences in
considerations. When calibrating the instrument, vent the
Ambient Ozone Monitors,” VIP-74, Measurement of Toxic and Related Air
Pollutants, Air & Waste Management Association, Pittsburgh, PA, p. 215. excessgasmixture,especiallyifitcontainshighconcentrations
D5149 − 02 (2008)
of ozone, through a charcoal filter. This will avoid contamina- 11. Procedures
tion of the work area around the instrument with ozone, which
11.1 Site
...
This document is not anASTM standard and is intended only to provide the user of anASTM standard an indication of what changes have been made to the previous version. Because
it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
Designation:D5149–95 Designation: D 5149 – 02 (Reapproved 2008)
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 (´) indicates an editorial change since the last revision or reapproval.
1. 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 µg of ozone/m (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.
2. Referenced Documents
2.1 ASTM Standards:
D 1356 Terminology Relating to Sampling and Analysis of Atmospheres
D 1357Practice for Planning the Sampling of the Ambient Atmosphere
D1605PracticeforSamplingAtmospheresforAnalysisofGasesandVapors PracticeforPlanningtheSamplingoftheAmbient
Atmosphere
D 1914 Practice for Conversion Units and Factors Relating to Sampling and Analysis of Atmospheres
D 3249 Practice for General Ambient Air Analyzer Procedures
D 3670 Guide for Determination of Precision and Bias of Methods of Committee D-22 D22
D 5011 Practices for Calibration of Ozone Monitors Using Transfer Standards
D 5110 PracticeforCalibrationofOzoneMonitorsandCertificationofOzoneTransferStandardsUsingUltravioletPhotometry
E380Practice for Use of the International System of Units (SI) (the Modernized Metric System)
E591Practice for Safety and Health Requirements Relating to Occupational Exposure to Ozone IEEE/ASTM SI-10 Practice for
Use of the International Sys-
tem of Units (SI) (the Mod-
ernized Metric System)
2.2 U.S. Environmental Protection Agency Standards:
EPA-600/4-79-056 Transfer Standards for Calibration of Air Monitoring Analyzers for Ozone (NTIS: PB80146871)
EPA-600/4-79-057 Technical Assistance Document for the Calibration of Ozone Monitors (NTIS: PB80149552)
EPA-600/4-80-050 Evaluation of Ozone Calibration Techniques (NTIS: PB81118911)
EPA-600/4-83-003 Performance Test Results and Comparative Data for Designated Reference and Equivalent Methods for
Ozone (NTIS: PB83166686)
2.3 Code of Federal Regulations:
40-CFR-Part 53.20
This test method is under the jurisdiction ofASTM Committee D-22 on Sampling andAnalysis ofAtmospheres and is the direct responsibility of Subcommittee D22.03
on Ambient Atmospheres and Source Emissions.
Current edition approved Sept. 10, 1995. Published November 1995. Originally published as D5149–90. Last previous edition D5149–90.
This test method is under the jurisdiction of ASTM Committee D22 on Air Quality and is the direct responsibility of Subcommittee D22.03 on Ambient Atmospheres
and Source Emissions.
Current edition approved April 1, 2008. Published July 2008. Originally approved in 1990. Last previous edition approved in 2002 as D 5149 - 02.
For referencedASTM standards, visit theASTM website, www.astm.org, or contactASTM Customer Service at service@astm.org. For Annual Book of ASTM Standards
, Vol 11.03.volume information, refer to the standard’s Document Summary page on the ASTM website.
Discontinued—See 1991 Annual Book of ASTM Standards, Vol 11.03.
Available from National Technical Information Service (NTIS), 5285 Port Royal Rd., Springfield, VA 22161, http://www.ntis.gov.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D 5149 – 02 (2008)
3. Terminology
3.1 Definitions—For definitions of terms used in this test method, refer to Terminology D 1356 and Practice D 1914. An
explanation of units, symbols and conversion factors may be found in Practice E 380.
3.2 Definitions of Terms Specific to This Standard:
3.2.1 absolute ultra-violet spectrometerphotometer—a spectrometerphotometer whose design, construction and maintenance is
suchthatitcanmeasuretheabsorbancecausedbyozonemixtureswithoutreferencetoexternalabsorptionstandards.Givenavalue
f+orfor the absorption coefficient of ozone at 253.7 nm and a reading from the absolute ultraviolet spectrometer,photometer, ozone
concentrations can be calculated with accuracy. Measurements by an absolute ultraviolet spectrometerphotometer should be made
on prepared ozone mixtures free from interferences.
3.2.2 primary standard—a standard directly defined and established by some authority, against which all secondary standards
are compared.
3.2.3 secondary standard—a standard used as a means of 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.
3.2.5 transfer standard—a type of secondary standard. It is a transportable device or apparatus which, together with operational
procedures, is capable of reproducing a sample concentration or producing acceptable assays of sample concentrations.
4. Significance and Use
4.1 Air quality standards for ozone have been promulgated by government authorities to protect the health and welfare of the
public. Though ozone itself is a toxic material, it is often complex organic compounds that cause the symptoms of smog such as
tearing and burning eyes. However, ozone is the predominant oxidant and is much more easily monitored than organic species.
Since ozone concentrations are also correlated with other photochemical oxidant levels, it is the substance that is specified in air
quality standards and regulations.
5. Interferences
5.1 Any aerosol that scatters light or that may deposit on the photomultiplier window constitutes a negative interference to this
test method. Particulate matter can be removed with a poly-tetrafluoroethylene (PTFE) membrane filter; however, this filter may
become contaminated and scrub ozone. It is important to check the ozone-inertness of these filters periodically. (See Practice
D5010.) D 5110.)
5.2 Atmospheric humidity constitutes a positive interference to this test method when calibrations are conducted with dry span
gas mixtures. The range of interference reported is tabulated in Annex A2 of this test method.
5.3Reduced sulfur compounds (H S and CS but not COS or SO ) may constitute positive interferences to this test method.
2 2 2
Part-per-million by volume levels of such gases reportedly enhance olefin chemiluminescence several hundred-fold in a study
using ozone chemiluminescence in reverse as an olefin-specific sensor. Moreover, the enhancement is proportional to sulfur
compound concentration. Since ambient concentrations of alkanes and NOx may reduce the magnitude of the sensitization,
estimated effects of such interferents should be determined under conditions of instrument use.
5.3 Reduced sulfur compounds have not been found to constitute positive interferences to this test method.
6. Measurement Principle
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 containing ozone
2 4 3
is mixed with excess ethylene (bottle gas, C.P. or better, supplied to the instrument) to generate excited formaldehyde (HCHO*)
molecules.Theexcitedformaldehydemoleculesdecayimmediatelytothegroundenergystate,releasingenergyintheformoflight
in the 300 to 600 nm region, with maximum intensity at 430 nm. The light energy is measured by a photosensor (frequently a
photomultiplier tube) that produces an output current proportional to the light intensity. The current, converted to voltage and
conditioned as necessary by the electronic circuits, becomes the analyzer’s output signal. (See 2.2.4.)
7. Apparatus
7.1 A schematic of the instrument is given in Fig. 1. The chemiluminescent reaction cell is constructed of materials inert to
ozone, for example, PTFE-coated metal, borosilicate glass, fused silica.
7.2 The input filter is installed in front of the sample line to prevent aerosols or particulate matter from entering the measuring
system. PTFE filters with pore sizes between 0.5 and 5.0 µm should be used. The filter should be kept clean since accumulated
Annual Book of ASTM Standards, Vol 14.02.
Kleindienst, T. E., Hudgens, E. E., Smith, D. F., McElroy, F. F., and Bufalini, J. J., “Comparison of Chemiluminescence and Ultraviolet Ozone Monitor Responses in
the Presence of Humidity and Photochemical Pollutants,” Journal of Air and Waste Management Assoc., Vol 43, 1993, p 213.
Discontinued; see 1990 Annual Book of ASTM Standards, Vol 11.03.
Kleindienst, T.C., McIver, C.D., Ollison, W. M., “AStudy of Interferences inAmbient Ozone Monitors,” VIP-74, Measurement of Toxic and Related Air Pollutants, Air
& Waste Management Association, Pittsburgh, PA, p. 215.
D 5149 – 02 (2008)
FIG. 1 Schematic Diagram of a Chemiluminescence Ozone
Analyzer
material on the filter may catalyze the breakdown of ozone into oxygen. Depressed ozone responses have been observed
immediately after filter changes for periods up to one hour.
7.3 Internal lines and fittings in the sample stream prior to the reaction call are made of PTFE or other ozone-inert material.
7.4 Duetotheflammabilityofethylene,somemanufacturerssuggesttheuseofethylene-carbondioxideblendsinsteadof100 %
ethylene when the monitoring device is to be used in a public facility. This blend is a liquefied, nonflammable mixture of
approximately9 %ethyleneand91 %CO .Thechemiluminescentreactionisthesame;however,gasconsumptionisconsiderably
higher as a result of the reduced ethylene concentration. The proportions of ethylene and CO supplied by the blend change as the
mixture is consumed from the cylinder. Since this changes the sensitivity of the analyzer, the analyzer should be recalibrated
periodically. The concentration of ethylene supplied by the blend is also changed by the temperature of the cylinder, which must
...
Questions, Comments and Discussion
Ask us and Technical Secretary will try to provide an answer. You can facilitate discussion about the standard in here.