ASTM D5011-92(2003)

Standard Practices for Calibration of Ozone Monitors Using Transfer Standards

SCOPE
1.1 These practices describe means for calibrating ambient, workplace or indoor ozone monitors, using transfer standards.
1.2 These practices describe five types of transfer standards: (A) Analytical instruments (B) Boric acid potassium iodide (BAKI) manual analytical procedure (C) Gas phase titration with excess nitric oxide (D) Gas phase titration with excess ozone (E) Ozone generator device.
1.3 These practices describe procedures to establish the authority of transfer standards: qualification, certification, and periodic recertification.
1.4  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.  See Section 8 for specific precautionary statements.

General Information

• Status: Historical
• Publication Date: 09-Apr-2003
• ICS: 13.040.01 - Air quality in general
• Technical Committee: D22 - Air Quality
• Drafting Committee: D22.03 - Ambient Atmospheres and Source Emissions

Relations

• Replaces: ASTM D5011-92(1997)e1 - Standard Practices for Calibration of Ozone Monitors Using Transfer Standards
• Effective Date: 10-Apr-2003
• Replaced By: ASTM D5011-92(2009) - Standard Practices for Calibration of Ozone Monitors Using Transfer Standards
• Effective Date: 01-Mar-2009
• Referred By: ASTM D1356-20a - Standard Terminology Relating to Sampling and Analysis of Atmospheres
• Effective Date: 10-Apr-2003
• Referred By: ASTM D5149-02(2016) - Standard Test Method for Ozone in the Atmosphere: Continuous Measurement by Ethylene Chemiluminescence
• Effective Date: 10-Apr-2003
• Referred By: ASTM D5110-22a - Standard Practice for Calibration of Ozone Monitors and Certification of Ozone Transfer Standards Using Ultraviolet Photometry
• Effective Date: 10-Apr-2003
• Referred By: ASTM D5156-22 - Standard Test Methods for Continuous Measurement of Ozone in Ambient, Workplace, and Indoor Atmospheres (Ultraviolet Absorption)
• Effective Date: 10-Apr-2003
• Referred By: ASTM D7439-21 - Standard Test Method for Determination of Elements in Airborne Particulate Matter by Inductively Coupled Plasma–Mass Spectrometry
• Effective Date: 10-Apr-2003
• Referred By: ASTM D8406-22 - Standard Practice for Performance Evaluation of Ambient Outdoor Air Quality Sensors and Sensor-based Instruments for Portable and Fixed-point Measurement
• Effective Date: 10-Apr-2003

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: D 5011 – 92 (Reapproved 2003)
Standard Practices for
Calibration of Ozone Monitors Using Transfer Standards
This standard is issued under the fixed designation D5011; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.
1. Scope Certification of Ozone Transfer Standards Using Ultravio-
let Photometry
1.1 These practices describe means for calibrating ambient,
E591 PracticeforSafetyandHealthRequirementsRelating
workplace or indoor ozone monitors, using transfer standards.
to Occupational Exposure to Ozone
1.2 Thesepracticesdescribefivetypesoftransferstandards:
2.2 Other Documents:
(A) Analytical instruments
40 CFR Part 50, Environmental ProtectionAgency Regula-
(B) Boric acid potassium iodide (BAKI) manual analytical
tions on Ambient Air Monitoring Reference Methods
procedure
(C) Gas phase titration with excess nitric oxide
3. Terminology
(D) Gas phase titration with excess ozone
3.1 For definitions of terms used in this standard, see
(E) Ozone generator device.
Terminology D1356.
1.3 These practices describe procedures to establish the
3.2 Definitions of Terms Specific to This Standard:
authority of transfer standards: qualification, certification, and
3.2.1 primary standard—a standard directly defined and
periodic recertification.
established by some authority, against which all secondary
1.4 This standard does not purport to address all of the
standards are compared.
safety concerns, if any, associated with its use. It is the
3.2.2 secondary standard—a standard used as a means of
responsibility of the user of this standard to establish appro-
comparison, but checked against a primary standard.
priate safety and health practices and determine the applica-
3.2.3 standard—an accepted reference sample or device
bility of regulatory limitations prior to use. See Section 8 for
used for establishing measurement of a physical quantity.
specific precautionary statements.
3.2.4 transfer standard—a type of secondary standard. It is
2. Referenced Documents a transportable device or apparatus, which, together with
2 operational procedures, is capable of reproducing pollutant
2.1 ASTM Standards:
concentration or producing acceptable assays of pollutant
D1071 Test Methods for Volumetric Measurement of Gas-
concentrations.
eous Fuel Samples
3.2.5 zero air—purified air that does not contain ozone and
D1193 Specification for Reagent Water
does not contain any other component that may interfere with
D1356 Terminology Relating to Sampling andAnalysis of
the measurement. See 7.1.
Atmospheres
3.3 Symbols:
D3195 Practice for Rotameter Calibration
D3249 Practice for General Ambient Air Analyzer Proce-
dures
b = Spectrophotometer cell path length, cm. See
D3631 Test Methods for Measuring Surface Atmospheric
Annex A2.
Pressure
d = Average of discrete single point compari-
avg
D5110 Practice for Calibration of Ozone Monitors and
sons. See Annex A1.
d = Single point comparison. See Annex A1.
i
F = Diluent air flow, mL/min.
D
These practices are under the jurisdiction of ASTM Committee D22 on Air F 8 = New diluent air flow, mL/min.
D
Quality and are the direct responsibility of Subcommittee D22.03 on Ambient
F = NO flow, mL/min.
NO
Atmospheres and Source Emissions.
F = Flow through the O generator, mL/min.
O 3
Current edition approved April 10, 2003. Published June 2003. Originally
e1
approved in 1989. Last previous edition approved in 1997 as D5011–92 (1997) .
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on Available from the Superintendent of Documents, U.S. Government Printing
the ASTM website. Office, Washington, DC20402.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D 5011 – 92 (2003)
F = Flowrate corrected to reference conditions S = Slope of KI calibration curve, mL/mol/cm.
R c
(25°C and 101.3 kPa), mL/min. See Annex See Annex A2.
A2. s = Standard deviation of single point compari-
d
F = Flowrate at sampling conditions, mL/min. sons. See Annex A1.
S
See Annex A2. s = Relative standard deviation of the six inter-
i
F = The total flow required at the output mani- cepts. See Annex A1.
T
s = Relative standard deviation of the six slopes.
fold (monitors demand plus 10 to 50%
m
See Annex A1.
excess), mL/min.
t = Residence time in reaction chamber, min.
I = The intensity of light which passes through
R
t = Sampling time, min. See Annex A2.
the photometer absorption cell and is sensed
s
T = Temperature at sampling conditions, °C. See
by the detector when the cell contains an O S
Annex A2
sample. See Annex A4.
URL = UpperrangelimitofO orNOmonitor,ppm.
[I ] = Concentration of each I standard, mol I /L. 3
2 i 2 2
V = Volume of I solution, mL. See Annex A2
i 2
See Annex A2.
VO = Volume of O absorbed, µL. See Annex A2.
3 3
I = Average intercept. See Annex A1.
avg
V = Volume of air sampled, corrected to 25°C
R
I = Individual intercepts. See Annex A1.
i
and 101.3 kPa (1 atm), mL. See Annex A2.
I = The intensity of light which passes through
O
V = Volume of the reaction chamber, mL.
RC
the photometer absorption cell and is sensed
y =O concentration indicated by the transfer
i 3
by the detector when the cell contains zero
standard, ppm. See 10.6.2.
air. See Annex A4.
Z = Recorder response with zero air, % scale.
m = Average slope. See Annex A1.
avg
m = Individual slopes. See Annex A1.
i
4. Summary of Practices
mol I =I released, mols. See Annex A2.
2 2
4.1 These practices describe the procedures necessary to
N = NormalityofKIO ,equivalent/L.SeeAnnex
KIO 3
establish the authority of ozone transfer standards: qualifica-
A2.
tion, certification, and periodic recertification. Qualification
[NO] = Diluted NO concentration, ppm. See Annex
consists of demonstrating that a candidate transfer standard is
A4.
sufficiently stable (repeatable) to be useful as a transfer
[NO] = Original NO concentration, ppm. SeeAnnex
ORIG
standard. Repeatability is necessary over a range of variables
A3.
(suchastemperature,linevoltage,barometricpressure,elapsed
[NO] = Highest NO concentration required at the
OUT
time, operator adjustments, relocation, etc.), any of which may
output manifold, ppm. It is approximately
be encountered during use of the transfer standard. Tests and
equal to 90% of the upper range limit of the
possible compensation techniques for several such common
O concentration to be determined. See An-
variables are described. Detailed certification procedures are
nex A3.
provided, and the quantitative specifications necessary to
[NO] = NO concentration (approximate) in the reac-
RC
maintain continuous certification of the transfer standard are
tion chamber, ppm. See Annex A3.
[NO] = NOconcentrationremainingafteradditionof also provided.
REM
4.2 Method A—A dedicated ozone monitor is tested as
O , ppm. See Annex A3.
[NO] = Concentration of the undiluted NO standard, described in 4.1 to demonstrate its authority as a transfer
STD
ppm. standard.
n = Number of comparisons. See Eq 4
4.3 Method B—This method (1) is based on the reaction
[O ] = Certified O concentration, ppm.
between ozone (O ) and potassium iodide (KI) to release
3 CERT 3
[O ] = Diluted certified O concentration, ppm.
3 CERT8 3 iodine (I ) in accordance with the following stoichiometric
[O ] =O concentrationproducedbytheO genera-
3 GEN 3 3
equation (2):
tor, ppm. See Annex A4.
2 1
O 12I 12H 5 I 1 H O 1 O (1)
3 2 2 2
[O ] = Indicated O concentration, ppm. SeeAnnex
3 OUT 3
The stoichiometry is such that the amount of I released is
A2.
[O ] = Diluted O concentration, ppm.
equaltotheamountofO absorbed.Ozoneisabsorbedina0.1
3 OUT8 3 3
[O ] =O concentration(approximate)attheoutput
N boric acid solution containing 1% KI, and the I released
3 RC 3
− −
manifold, ppm.
reacts with excess iodide ion (I ) to form triiodide ion (I ),
P = Vapor pressure of HOat T , kPa, wet
which is measured spectrophotometrically at a wavelength of
H O 2 S
volume standard. (For a dry standard,
352 nm. The output of a stable O generator is assayed in this
P =0.) (See Test Method D4230 for
manner, and the O generator is immediately used to calibrate
H O
tables of saturation vapor pressure of water.)
the O monitor.
See Annex A2.
4.4 Method C—This procedure is based on the rapid gas
P = Dynamic specification, determined empiri-
R
phase reaction between nitric oxide (NO) and O , as described
cally, to ensure complete reaction of O or
3 by the following equation (3):
NO, ppm/min.
P = Barometric pressure at sampling conditions,
S
The boldface numbers in parentheses refer to the references at the end of these
kPa. See Annex A2.
practices.
D 5011 – 92 (2003)
NO 1 O 5 NO 1 O (2)
and precludes direct certification of O concentrations as
3 2
SRM’s. Moreover, there is no available SRM that can be
When O is added to excess NO in a dynamic system, the
readily and directly adapted to the generation of O standards
decrease in NO response is equivalent to the concentration of 3
analogoustopermeationdevicesandstandardgascylindersfor
O added. The NO is obtained from a standard NO cylinder,
sulfur dioxide and nitrogen oxides. Dynamic generation of O
and the O is produced by a stable O generator. A chemilu-
3 3
concentrations is relatively easy with a source of ultraviolet
minescence NO analyzer is used to measure the change in NO
(UV) radiation. However, accurately certifying an O concen-
concentration.TheconcentrationofO addedmaybevariedto
tration as a primary standard requires assay of the concentra-
obtain calibration concentrations over the range desired. The
tion by a comprehensively specified analytical procedure,
dynamic system is designed to produce locally high concen-
which must be performed every time a standard is needed.
trationsofNOandO inthereactionchamber,withsubsequent
5.2 The primary UV standard photometers, which are usu-
dilution, to effect complete O reaction with relatively small
ally used at a fixed location under controlled conditions, are
chamber volumes.
usedtocertifytransferstandardsthatarethentransportedtothe
4.5 Method D—This procedure is based on the rapid gas
field sites where the ambient ozone monitors are being used.
phase reaction between O and nitric oxide (NO) as described
See PracticeD5110.
by the following equation (3):
5.3 The advantages of this procedure are:
NO 1 O 5 NO 1 O (3)
3 2 2
5.3.1 All O monitors in a given network or region may be
When NO is added to excess O in a dynamic system, the
traced to a single primary standard.
decrease in O response observed on an uncalibrated O
3 3
5.3.2 The primary standard is used at only one location,
monitor is equivalent to the concentration of NO added. By
under controlled conditions.
measuring this decrease in response and the initial response,
5.3.3 Transfer standards are more rugged and more easily
the O concentration can be determined. Additional O con-
3 3
portable than primary standards.
centrations are generated by dilution. The gas phase titration
5.3.4 Transfer standards may be used to intercompare vari-
(GPT) system is used under predetermined flow conditions to
ous primary standards.
insure that the reaction of NO is complete and that further
reaction of the resultant nitrogen dioxide (NO ) with residual
6. Apparatus
O is negligible.
6.1 Apparatus Common to Methods A Through E:
4.6 Method E—A dedicated ozone generator is tested as
6.1.1 UV Photometric calibration system, as shown in Fig.
described in 4.1 to demonstrate its authority as a transfer
1, consisting of the following:
standard.
6.1.1.1 Primary Ozone Standard—a UV photometer, con-
5. Significance and Use
sisting of a low-pressure mercury discharge lamp, collimation
5.1 ThereactivityandinstabilityofO precludesthestorage optics (optional), an absorption cell, a detector, and signal-
of O concentration standards for any practical length of time, processing electronics. It shall be capable of measuring the
FIG. 1 Schematic Diagram of a Typical UV Photometric Calibration System
D 5011 – 92 (2003)
transmittance, I/I , at a wavelength of 253.7 nm with sufficient barometric pressure reading can then be used for the pressure
precision that the standard deviation of the concentration correction. If the cell pressure is different than the local
measurementsdoesnotexceedthegreaterof0.005ppmor3% barometric pressure, some means of accurately measuring the
of the concentration. It shall incorporate means to assure that cell pressure (manometer, pressure gage, or pressure trans-
noO isgeneratedinthecellbytheUVlamp.Thisisgenerally ducer) is required. This device shall be calibrated against a
accomplishedbyfilteringoutthe184.9nmHglinewithahigh suitable pressure standard, in accordance with Test Methods
silica filter. In addition, at least 99.5% of the radiation sensed D3631.
bythedetectorshallbe253.7nm.Thisisusuallyaccomplished
6.1.2 Output Indicating Device, such as Continuous Strip
by using a solar blind photodiode tube. The length of the light
Chart Recorder or Digital Volt Meter—If a recorder is used, it
path through the absorption cell shall be known with an
shall have the following specifications:
accuracy within at least 99.5%. In addition the cell and
Accuracy 60.25 % of span
Chart width no less than 150 mm
associated plumbing shall be designed to minimize loss of O
Time for full-scale travel 1 s
from contact with surfaces (4). See PracticeD5110.
6.1.1.2 AirFlowController—capableofregulatingairflows 6.1.2.1 If a digital voltmeter is used, it shall have an
accuracy of 60.25% of range.
as necessary to meet the output stability and photometer
precision requirements.
6.1.2.2 Method A output indicating device shall be consid-
6.1.1.3 Flowmeters—calibrated in accordance with Practice ered as part of the transfer standard, and employed during
qualification, certification, and use.
D3195.
6.1.2.3 Methods C, D, and E require two output indicating
6.1.1.4 Ozone Generator—capableofgeneratingstablelev-
devices.
els of O over the required concentration range. It shall be
stableovershortperiodstoallowforstabilityofthemonitoror 6.1.3 Variable Autotransformer.
transfer standard connected to the output manifold. Conven-
6.1.4 AC Voltmeter—Accurate to 61%.
tionalUV-photolytictypegeneratorsmaybeadequatebutshall
6.2 Apparatus Common to Methods A and
...