ISO 10313:1993

Ambient air - Determination of the mass concentration of ozone - Chemiluminescence method

The method specified is based on drawing continuously, at a constant flow rate, an air sample through a particle filter before it enters the chemiluminescence analyser. It then flows into a reaction chamber where it is mixed with an excess flow of ethylene. Ozone and ethylene react instantaneously to produce light in the visible region (maximum at about 400 nm). The emitted light intensity is proportional to the concentration of ozone in the air sample and is measured by a photomultiplier tube. Applies to determination of the mass concentration of ozone between 2 µg/m^3 and 10 mg/m^3 at the reference conditions.

Air ambiant — Détermination de la concentration en masse d'ozone — Méthode par chimiluminescence

Okoljski zrak - Ugotavljanje masne koncentracije ozona - Kemiluminiscenčna metoda

General Information

• Status: Published
• Publication Date: 21-Apr-1993
• ICS: 13.040.20 - Ambient atmospheres
• Technical Committee: ISO/TC 146/SC 3 - Ambient atmospheres
• Drafting Committee: ISO/TC 146/SC 3 - Ambient atmospheres
• Current Stage: 9093 - International Standard confirmed
• Start Date: 15-Jun-2023
• Completion Date: 13-Dec-2025
• Ref Project: SIST ISO 10313:1997 - Ambient air -- Determination of the mass concentration of ozone -- Chemiluminescence method

Relations

• Amended By: ISO 10313:1993/Amd 1:2024 - Ambient air - Determination of the mass concentration of ozone - Chemiluminescence method - Amendment 1: Consensus value for the ozone absorption cross-section at room temperature at the mercury-line wavelength (253,65 nm air)
• Effective Date: 17-Jun-2023

Overview

ISO 10313:1993 - Ambient air: Determination of the mass concentration of ozone - Chemiluminescence method specifies a standardized chemiluminescence technique for measuring ozone in ambient air. The method draws a continuous, constant-flow air sample through a particle filter into a reaction chamber where it mixes with excess ethylene. Ozone + ethylene react instantly to emit visible light (maximum near 400 nm); the emitted light, measured by a photomultiplier, is proportional to ozone concentration. The standard applies to mass concentrations from 2 µg/m³ to 10 mg/m³ at reference conditions (25 °C, 101.3 kPa).

Key topics and technical requirements

• Measurement principle: chemiluminescence (ozone + ethylene → visible emission ≈ 400 nm) with photomultiplier detection.
• Calibration: ultraviolet (UV) photometry (primary method) using a low‑pressure mercury lamp (253.7 nm) is specified for primary calibration. Transfer standards may be used if annually traceable to the UV standard.
• Sampling system:
  • Particle filter (ozone‑inert materials such as fluorocarbon polymer) to prevent particulate-induced ozone loss or optical scattering.
  • Sampling line of ozone‑inert material (glass or fluorocarbon polymer) kept as short as possible; recommended residence time <0.5 s (routine up to 5 s).
• Reagents & gases:
  • Ethylene of minimum purity 99.5% for the chemiluminescent reaction.
  • Zero air used for calibration must be free of ozone and NOx; if synthetic air is used its oxygen content should be within ±2% of 20.9%.
• Apparatus: chemiluminescence analyser with reaction chamber, photomultiplier, signal processing electronics, flowmeters and pumps; ozone generator and UV photometer for calibration systems.
• Performance & quality:
  • Overall precision for generation and UV-photometric measurement better than ±5% (UV-photometric calibrations can be within ±1% with careful operation).
  • Recommended multipoint calibration every 3 months; routine zero/span checks (weekly).
• Safety notes: Ethylene is flammable (lower explosive limit noted in the standard). Ozone is toxic - excess exhaust must be vented or scrubbed.

Practical applications

• Ambient air quality monitoring networks for regulatory compliance and trend assessment.
• Field and laboratory ozone measurement, instrument validation and intercomparisons.
• Calibration and service laboratories using transfer standards or primary UV photometric systems.
• Research studies requiring accurate ozone concentration data (health, atmospheric chemistry, exposure assessment).

Who uses this standard

• Environmental and air quality monitoring agencies
• Calibration laboratories and instrument manufacturers
• Field technicians and researchers conducting ambient ozone measurements
• Quality managers establishing traceable ozone measurement programs

Related standards

• Other ISO air‑quality standards and guidance produced by ISO/TC 146 (Air quality, Sub‑Committee SC 3 - Ambient atmospheres) and methods referenced for calibration and zero‑air generation (see ISO 10313 annexes).

Standards Content (Sample)

SLOVENSKI STANDARD
01-januar-1997
2NROMVNL]UDN8JRWDYOMDQMHPDVQHNRQFHQWUDFLMHR]RQD.HPLOXPLQLVFHQþQD
PHWRGD
Ambient air -- Determination of the mass concentration of ozone -- Chemiluminescence
method
Air ambiant -- Détermination de la concentration en masse d'ozone -- Méthode par
chimiluminescence
Ta slovenski standard je istoveten z: ISO 10313:1993
ICS:
13.040.20 Kakovost okoljskega zraka Ambient atmospheres
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

INTERNATIONAL ISO
STANDARD 10313
First edition
1993-04-15
Ambient air - Determination of the mass
concentration of ozone -
Chemiluminescence method
Air ambian t - Dhtermination de Ia concentration en mass d ’ozone -
Methode par chimiluminescence
Reference number
Foreword
ISO (the International Organization for Standardization) is a worldwide
federation of national Standards bodies (ISO member bodies). The work
of preparing International Standards is normally carried out through ISO
technical committees. Esch member body interested in a subject for
which a technical committee has been established has the right to be
represented on that committee. International organizations, governmental
and non-governmental, in liaison with ISO, also take part in the work. ISO
collaborates closely with the International Electrotechnical Commission
(IEC) on all matters of electrotechnical standardization.
Draft International Standards adopted by the technical committees are
circulated to the member bodies for voting. Publication as an International
Standard requires approval by at least 75 % of the member bodies casting
a vote.
International Standard ISO 10313 was prepared by Technical Committee
lSO/TC 146, Air quality, Sub-Committee SC 3, Ambient atmospheres.
Annexes A and B of this International Standard are for information only.
0 ISO 1993
All rights reserved. No part of this publication may be reproduced or utilized in any form or
by any means, electronie or mechanical, including photocopying and microfilm, without per-
mission in writing from the publisher.
International Organkation for Standardkation
Gase Postale 56 l CH-l 211 Geneve 20 l Switzerland
Printed in Switzerland
ii
INTERNATIONAL STANDARD ISO 10313:1993(E)
Ambient air - Determination of the mass
- Chemiluminescence method
concentration of ozone
2 Definition
1 Scope
For the purposes of this International Standard, the
1 .l General
following definition applies.
This International Standard specifies a chemi-
2.1 transfer Standard: An apparatus (transportable)
luminescence method for the determination of the
with associated operational procedures that is capable
mass concentration of ozone in ambient air.
of accurately measuring or reproducing ozone con-
centration Standards which are quantitatively related
The method is applicable to the determination of the
to the authoritative primary Standard.
mass concentration of ozone between 2 pg/m3
[O,OOl ppm(V/V)] and 10 mg/m3 [5 ppm(V/V)] at the
reference conditions of 25 “C and 101,3 kPa. 3 Principle
Ultraviolet (UV) photometry is specified as the primary
The air Sample is drawn continuously, at a constant
calibration method because of its proven accuracy and
flow rate, through a particle filter before it enters the
specificity to ozone. The use of transfer Standards is
chemiluminescence analyser. lt then flows into a re-
allowed if they have been previously calibrated against
action chamber where it is mixed with an excess flow
the primary calibration method.
of ethylene. Ozone and ethylene react instan-
taneously to produce light in the visible region with a
maximum at a wavelength of about 400 nm. The
1.2 Limitations
emitted light intensity is proportional to the concen-
tration of ozone in the air Sample and is measured by
The chemiluminescent reaction of ozone with
a photomultiplier tube. The resulting voltage is ampli-
ethylene is not subject to interference from any of the
fied, displayed, and calibrated in terms of the ambient
common air pollutants. However, particulate matter,
ozone concentration.
if not removed, will accumulate in the sampling line
and may Cause a measurable destruction of ozone. If
4 Reagents and materials
particulate matter is allowed to enter the reaction
chamber of the analyser, it will not only scatter the
emitted light but will also accumulate on the Optical
4.1 Sampling line
window, thereby causing further attenuation of the
emitted light. Also, any nitrogen(ll) Oxide in the sam-
The sampling line shall be made of material that is
pled air will to some extent react with the ambient
inert to ozone, such as glass or fluorocarbon polymer,
ozone; therefore, the time during which the ambient and it shall be as short as possible to keep the time
air remains in the sampling line must be sufficiently
the air Sample remains there to a minimum. Any am-
short to keep this effect to a minimum.
bient nitrogen(ll) Oxide present in the air Sample will
react with some of the ozone during the time it re-
NOTE 1 It has been reported by some researchers that,
mains in the sampling line. This decay of ozone is a
at about 80 % relative humidity and 22 “C, the responses for
complicated function of the mass concentration ratio,
some commercially available chemiluminescence analysers
p(03))/p(NO), and the differente in mass concen-
were about 10 % higher than that for dry air. However,
trations, ~(0~) - p(N0). Calculations have shown that,
comparisons of ambient ozone measurements using com-
if the residente time is less than 0,5 s, the decay in
mercially available chemiluminescence and UV-photometric
initial ozone will be less than 1 % for most ambient
analysers showed no significant differentes. This suggests
ozone and nitrogen(ll) Oxide concentrations encoun-
that, in practice, any errors associated with calibrations us-
tered. Hence, it is recommended that the sampling
ing dry air are compensated by other effects.
4.4 Zero air, required in the analyser calibration
line length and pumping Speed be Chosen such that
the time the air remains within the sampling line is procedure.
less than 05 s. However, in situations of routine
lt shall be free of ozone, nitrogen oxides and any other
monitoring, a time of up to 5 s is allowed.
interfering substance that tan Cause an undesired
Any sampling line or manifold preceding the filter shall positive or negative response in either the ultraviolet
be clean. Proper precautions shall be taken to prevent Photometer or the chemiluminescence analyser.
condensation inside the sampling line, for example,
The response of the ozone chemiluminescence ana-
by heating the line.
lyser is affected by the Oxygen content in the gas
Sample. Therefore, if synthetic air is used, the Oxygen
4.2 Particle filter
content shall be within + 2 % of the normal atmos-
pheric concentration of 20,9 %.
The filter and its support shall be made of material
inert to ozone, such as fluorocarbon polymer, and it
NOTE 4 Details on a scrubbing System for making zero
shall remove all particles likely to alter the perform-
air from ambient air may be found in [l] and [2] in
ante of the analyser. lt shall be changed on a regular
annex B.
basis, depending on the concentrations of ambient
particles at the sampling site. This is necessaty be-
Cause excessive accumulation of particles on the filter
5 Apparatus
tan Cause loss of ozone from the air Sample and an
excessive pressure drop across the filter.
5.1 Chemiluminescence analyser, consisting of
Sample and ethylene flow inlet Systems, a constant
NOTES
temperature reaction chamber coupled to a photo-
multiplier detector and accompanying Signal process-
Frequently, a fitter pore size of 5 Pm is used.
ing electronics. A flowmeter, if it is not an integral part
3 Generally, new filters need some time to be conditioned
of the analyser, shall be available for verifying that the
by the ambient atmosphere. As a res&, measured mass
flow meets the specifications of the instrument.
concentrations of ozone have been observed to decrease
temporarily by 5 % to 10 % for periods of 5 min to 15 min
A schematic diagram of a typical System is shown in
immediately following filter changes.
figure 1.
4.3 Ethylene, of minimum purity 995 %.
5.2 Apparatus for calibration, an ozone calibration
System shall be used. (See the simplified schematic
WARNING - Ethylene has 8 lower explosive limit
diagram in figure2.) .
of 27,5 l/m3. Any excess shall be V8nt8d outdoors
or, if necessary, chemically removed, especially at
NOTE 5 An equivalent System would be one that uses
sites where hydrocarbons are being m8aSur8d.
only the air line with the ozone generator to bring zero and
ObS8rv8 Standard safety precautions when using ozonized air to the manifold, hence eliminating the need for
the four-ports two-way valve.
this flammable gas.
Flowmeter
:j
Reaction chamber
,
Sample - 1
/ r
inlet
Particulate
1 Thermo-electric cooler
filter
Figure 1 - Schematic diagram of a chemiluminescence Ozon8 analyser

Flow
,
Flowmeter 1
Controller Four-ports
Zero two-way valve
air
\
Vent
Output manifold
\
am
Flow Ozone
G,
Flowmeter r
generator
To inlet of analyser
under calibration
Ultraviolet Photometer
-----------------------
r
Detector
i
mercury vapour ,
lamp
Signal processing
Flowmeter
electronics
\
Flow
Controller
--- --------------------------------------- ------------------------------------ J
Schematic diagram of a typical ultraviolet photometric calibration System
Figure 2 -
5.2.1 Ultraviolet Photometer, for primary cali- the simplified schematic diagram of a Photometer
bration only consisting of a low pressure mercuty System in figure 2.
discharge lamp, a Single or dual absorption cell, and
detection and Signal processing electronics. lt shall be
5.2.2 Ozon8 generator, which generates stable
meticulously maintained. To prevent ozone generation
ozone concentrations that, in turn, are measured by
within the absorption cell, a high-silica glass window
the calibrated Photometer (5.2.1). The ozone genera-
(or equivalent) shall be inserted between the mercury
tor shall be capable of producing steady ozone con-
lamp and the absorption cell to remove the
centrations in the range of measurement, at the
185 nm Hg line but transmit the 253,7 nm Hg meas-
required flow rate, and throughout the period of cali-
urement line. The detector shall be capable of meas-
bration. If a variable ozone generator is not available,
uring the transmittance through the absorption cell at
the calibration System shall include a means of suit-
a wavelength of 253,7 nm, with less than 0,5 % of
ably diluting the ozone with additional zero air (see
the radiation detected being from other wavelengths
4.4). In such a case, a mixing chamber shall be in-
(vacuum photodiodes with a caesium telluride
stalled before the output manifold.
sensitization meet this requirement). The length of
the light path through the absorption cell shall be
WARNING - Ozone is a toxic gas with a threshold
known to an accuracy better than 0,5 %, and the cell
limit value in air of 0,l ml/ms, and any excess
and associated plumbing shall be designed to mini-
should be vented i
...

INTERNATIONAL ISO
STANDARD 10313
First edition
1993-04-15
Ambient air - Determination of the mass
concentration of ozone -
Chemiluminescence method
Air ambian t - Dhtermination de Ia concentration en mass d ’ozone -
Methode par chimiluminescence
Reference number
Foreword
ISO (the International Organization for Standardization) is a worldwide
federation of national Standards bodies (ISO member bodies). The work
of preparing International Standards is normally carried out through ISO
technical committees. Esch member body interested in a subject for
which a technical committee has been established has the right to be
represented on that committee. International organizations, governmental
and non-governmental, in liaison with ISO, also take part in the work. ISO
collaborates closely with the International Electrotechnical Commission
(IEC) on all matters of electrotechnical standardization.
Draft International Standards adopted by the technical committees are
circulated to the member bodies for voting. Publication as an International
Standard requires approval by at least 75 % of the member bodies casting
a vote.
International Standard ISO 10313 was prepared by Technical Committee
lSO/TC 146, Air quality, Sub-Committee SC 3, Ambient atmospheres.
Annexes A and B of this International Standard are for information only.
0 ISO 1993
All rights reserved. No part of this publication may be reproduced or utilized in any form or
by any means, electronie or mechanical, including photocopying and microfilm, without per-
mission in writing from the publisher.
International Organkation for Standardkation
Gase Postale 56 l CH-l 211 Geneve 20 l Switzerland
Printed in Switzerland
ii
INTERNATIONAL STANDARD ISO 10313:1993(E)
Ambient air - Determination of the mass
- Chemiluminescence method
concentration of ozone
2 Definition
1 Scope
For the purposes of this International Standard, the
1 .l General
following definition applies.
This International Standard specifies a chemi-
2.1 transfer Standard: An apparatus (transportable)
luminescence method for the determination of the
with associated operational procedures that is capable
mass concentration of ozone in ambient air.
of accurately measuring or reproducing ozone con-
centration Standards which are quantitatively related
The method is applicable to the determination of the
to the authoritative primary Standard.
mass concentration of ozone between 2 pg/m3
[O,OOl ppm(V/V)] and 10 mg/m3 [5 ppm(V/V)] at the
reference conditions of 25 “C and 101,3 kPa. 3 Principle
Ultraviolet (UV) photometry is specified as the primary
The air Sample is drawn continuously, at a constant
calibration method because of its proven accuracy and
flow rate, through a particle filter before it enters the
specificity to ozone. The use of transfer Standards is
chemiluminescence analyser. lt then flows into a re-
allowed if they have been previously calibrated against
action chamber where it is mixed with an excess flow
the primary calibration method.
of ethylene. Ozone and ethylene react instan-
taneously to produce light in the visible region with a
maximum at a wavelength of about 400 nm. The
1.2 Limitations
emitted light intensity is proportional to the concen-
tration of ozone in the air Sample and is measured by
The chemiluminescent reaction of ozone with
a photomultiplier tube. The resulting voltage is ampli-
ethylene is not subject to interference from any of the
fied, displayed, and calibrated in terms of the ambient
common air pollutants. However, particulate matter,
ozone concentration.
if not removed, will accumulate in the sampling line
and may Cause a measurable destruction of ozone. If
4 Reagents and materials
particulate matter is allowed to enter the reaction
chamber of the analyser, it will not only scatter the
emitted light but will also accumulate on the Optical
4.1 Sampling line
window, thereby causing further attenuation of the
emitted light. Also, any nitrogen(ll) Oxide in the sam-
The sampling line shall be made of material that is
pled air will to some extent react with the ambient
inert to ozone, such as glass or fluorocarbon polymer,
ozone; therefore, the time during which the ambient and it shall be as short as possible to keep the time
air remains in the sampling line must be sufficiently
the air Sample remains there to a minimum. Any am-
short to keep this effect to a minimum.
bient nitrogen(ll) Oxide present in the air Sample will
react with some of the ozone during the time it re-
NOTE 1 It has been reported by some researchers that,
mains in the sampling line. This decay of ozone is a
at about 80 % relative humidity and 22 “C, the responses for
complicated function of the mass concentration ratio,
some commercially available chemiluminescence analysers
p(03))/p(NO), and the differente in mass concen-
were about 10 % higher than that for dry air. However,
trations, ~(0~) - p(N0). Calculations have shown that,
comparisons of ambient ozone measurements using com-
if the residente time is less than 0,5 s, the decay in
mercially available chemiluminescence and UV-photometric
initial ozone will be less than 1 % for most ambient
analysers showed no significant differentes. This suggests
ozone and nitrogen(ll) Oxide concentrations encoun-
that, in practice, any errors associated with calibrations us-
tered. Hence, it is recommended that the sampling
ing dry air are compensated by other effects.
4.4 Zero air, required in the analyser calibration
line length and pumping Speed be Chosen such that
the time the air remains within the sampling line is procedure.
less than 05 s. However, in situations of routine
lt shall be free of ozone, nitrogen oxides and any other
monitoring, a time of up to 5 s is allowed.
interfering substance that tan Cause an undesired
Any sampling line or manifold preceding the filter shall positive or negative response in either the ultraviolet
be clean. Proper precautions shall be taken to prevent Photometer or the chemiluminescence analyser.
condensation inside the sampling line, for example,
The response of the ozone chemiluminescence ana-
by heating the line.
lyser is affected by the Oxygen content in the gas
Sample. Therefore, if synthetic air is used, the Oxygen
4.2 Particle filter
content shall be within + 2 % of the normal atmos-
pheric concentration of 20,9 %.
The filter and its support shall be made of material
inert to ozone, such as fluorocarbon polymer, and it
NOTE 4 Details on a scrubbing System for making zero
shall remove all particles likely to alter the perform-
air from ambient air may be found in [l] and [2] in
ante of the analyser. lt shall be changed on a regular
annex B.
basis, depending on the concentrations of ambient
particles at the sampling site. This is necessaty be-
Cause excessive accumulation of particles on the filter
5 Apparatus
tan Cause loss of ozone from the air Sample and an
excessive pressure drop across the filter.
5.1 Chemiluminescence analyser, consisting of
Sample and ethylene flow inlet Systems, a constant
NOTES
temperature reaction chamber coupled to a photo-
multiplier detector and accompanying Signal process-
Frequently, a fitter pore size of 5 Pm is used.
ing electronics. A flowmeter, if it is not an integral part
3 Generally, new filters need some time to be conditioned
of the analyser, shall be available for verifying that the
by the ambient atmosphere. As a res&, measured mass
flow meets the specifications of the instrument.
concentrations of ozone have been observed to decrease
temporarily by 5 % to 10 % for periods of 5 min to 15 min
A schematic diagram of a typical System is shown in
immediately following filter changes.
figure 1.
4.3 Ethylene, of minimum purity 995 %.
5.2 Apparatus for calibration, an ozone calibration
System shall be used. (See the simplified schematic
WARNING - Ethylene has 8 lower explosive limit
diagram in figure2.) .
of 27,5 l/m3. Any excess shall be V8nt8d outdoors
or, if necessary, chemically removed, especially at
NOTE 5 An equivalent System would be one that uses
sites where hydrocarbons are being m8aSur8d.
only the air line with the ozone generator to bring zero and
ObS8rv8 Standard safety precautions when using ozonized air to the manifold, hence eliminating the need for
the four-ports two-way valve.
this flammable gas.
Flowmeter
:j
Reaction chamber
,
Sample - 1
/ r
inlet
Particulate
1 Thermo-electric cooler
filter
Figure 1 - Schematic diagram of a chemiluminescence Ozon8 analyser

Flow
,
Flowmeter 1
Controller Four-ports
Zero two-way valve
air
\
Vent
Output manifold
\
am
Flow Ozone
G,
Flowmeter r
generator
To inlet of analyser
under calibration
Ultraviolet Photometer
-----------------------
r
Detector
i
mercury vapour ,
lamp
Signal processing
Flowmeter
electronics
\
Flow
Controller
--- --------------------------------------- ------------------------------------ J
Schematic diagram of a typical ultraviolet photometric calibration System
Figure 2 -
5.2.1 Ultraviolet Photometer, for primary cali- the simplified schematic diagram of a Photometer
bration only consisting of a low pressure mercuty System in figure 2.
discharge lamp, a Single or dual absorption cell, and
detection and Signal processing electronics. lt shall be
5.2.2 Ozon8 generator, which generates stable
meticulously maintained. To prevent ozone generation
ozone concentrations that, in turn, are measured by
within the absorption cell, a high-silica glass window
the calibrated Photometer (5.2.1). The ozone genera-
(or equivalent) shall be inserted between the mercury
tor shall be capable of producing steady ozone con-
lamp and the absorption cell to remove the
centrations in the range of measurement, at the
185 nm Hg line but transmit the 253,7 nm Hg meas-
required flow rate, and throughout the period of cali-
urement line. The detector shall be capable of meas-
bration. If a variable ozone generator is not available,
uring the transmittance through the absorption cell at
the calibration System shall include a means of suit-
a wavelength of 253,7 nm, with less than 0,5 % of
ably diluting the ozone with additional zero air (see
the radiation detected being from other wavelengths
4.4). In such a case, a mixing chamber shall be in-
(vacuum photodiodes with a caesium telluride
stalled before the output manifold.
sensitization meet this requirement). The length of
the light path through the absorption cell shall be
WARNING - Ozone is a toxic gas with a threshold
known to an accuracy better than 0,5 %, and the cell
limit value in air of 0,l ml/ms, and any excess
and associated plumbing shall be designed to mini-
should be vented into an activated charcoal
mize surface loss of ozone. Provision shall be made
scrubber or outdoors (weil away from any sam-
for measuring the temperature and pressure of the
pling intake).
gas in the absorption cell (see 5.2.8 and 5.2.9). See
5.2.3 Airflow controllers, capable of maintaining
steady airflows throughout the period of calibration.

5.2.4 Airflow meters, of any type that i
...