PROCEEDINGS
FIFTH US-JAPAN CONFERENCE
ON
PHOTOCHEMICAL AIR POLLUTION
February 4-6, 1980
Environment Agency
Tokyo, JAPAN
US DELEGATION
Dr. A.P. Altshuller, Chairman
Environmental Sciences Research
Laboratory
USEPA
Dr. B. Dimitriades
Environmental Sciences Research
Laboratory
USEPA
JAPANESE DELEGATION
Mr. Tsuneo Fujita, Chairman
Environment Agency
Dr. Naoomi Yamaki
Saitama University
Dr. Michio Okuda
National Institute for
Environmental Studies
Dr. Toshiichi Okita
Hokkaido University
Dr. Mitsuru Udagawa
The Tokyo Metropolitan
Research Institute for
Environmental Pollution
COMPILED BY
AIR QUALITY BUREAU
ENVIRONMENT AGENCY
3-1-1, Kasumigaseki, Chiyoda-ku, Tokyo, JAPAN
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PROCEEDINGS
FIFTH US-JAPAN CONFERENCE
ON
PHOTOCHEMICAL AIR POLLUTION
February 4-6, 1980
Environment Agency
Tokyo, JAPAN
US DELEGATION
Dr. A.P. Altshuller, Chairman
Environmental Sciences Research
Laboratory
USEPA
Dr. B. Dimitriades
Environmental Sciences Research
Laboratory
USEPA
JAPANESE DELEGATION
Mr. Tsuneo Fujita, Chairman
Environment Agency
Dr. Naoomi Yamaki
Saitama University
Dr. Michio Okuda
National Institute for
Environmental Studies
Dr. Toshiichi Okita
Hokkaido University
Dr. Mitsuru Udagawa
The Tokyo Metropolitan
Research Institute for
Environmental Pollution
COMPILED BY
AIR QUALITY BUREAU
ENVIRONMENT AGENCY
3-1-1, Kasumigaseki, Chiyoda-ku, Tokyo, JAPAN
-------
Printed in August 1980
by the
JAPAN ENVIRONMENT AGENCY
3-1-1, Kasumigaseki, Chiyoda-ku
Tokyo, JAPAN
PROCEEDINGS—PAGE i
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PREFACE
This conference is a part of the activities fostered
under the US-Japan Environmental Agreement negotiated between
the two countries in August, 1975. Purpose of the Environ-
mental Agreement and associated activities is to develop
environmental awareness and to promote cooperation between
the US and Japan in effort to reduce air pollution. Coopera-
tive activities pertaining to photochemical air pollution
were commenced in June, 1973, when the First US-Japan Confer-
ence on Photochemical Air Pollution was held in Tokyo, Japan.
The Second Conference was held in Tokyo also, in November,
1975; the Third Conference took place in Research Triangle
Park, N.C., in September 1976; the Fourth Conference took
place in Honolulu, in February - March 1978.
PROCEEDINGS—PAGE ii
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TABLE OF CONTENTS
Introduction ........................ vi
Agenda of Meeting ..................... Viii
Joint Communique ...................... x
Technical Papers
1. Developments in NOx Air Pollution Control
( Fujita ) .................... !
2. Recent Advancements in the Modeling of
Photochemical Smog Formation ( Altshuller ) . . . . 43
3. Photooxidation of the Propylene-Nitrogen
Oxides-Air System Studied by Long-Path Fourier
Transform Infrared Spectrometry ( Okuda ) .... 5^
4. Water vapor effect on the Photochemical Ozone
Formation in the Propylene-Nitrogen Oxides-Air
System ( Okuda ) ................. 85
5. Intercomparison of Various Methods to Measure
Nitric Acid and Other Nitrates ( Dimitriades ) . .
6. Recent Developments in Measurement Methods in
Japan ( Yamaki ) ................. 125
7. Research on Sulfate, Nitrate and Nitric Acid
in Kan to area ( Okita ) ............. 149
8. Use of Aerometric Data to Evaluate the EKMA
Model ( Dimitriades ) .............. 217
9. Preliminary Study on EKMA Model in Japan
( Imai ) ..................... 225
PROCEEDINGS—PAGE iv
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INTRODUCTION
Dr. D.- Miura, director general of Air Quality Bureau, welcomed
the delegates and outlined briefly the major developments of
researches in both countries over recent years, placing
primary emphasis to the ozone formation theory, sulfate and
nitrate problems including their measurement methods, and EKMA
Model which constitute the subjects of the Fifth Conference.
PROCEEDINGS—PAGE vi
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Annex I
FIFTH US-JAPAN CONFERENCE
ON
PHOTOCHEMICAL AIR POLLUTION
ENVIRONMENT AGENCY
TOKYO, JAPAN
February 4-6, 1980
AGENDA
Monday, February 4, 1980
Acting Chairman : Mr. T. Fujita
10:00 — 10:30 a.m. Opening Remarks
Dr. D. Miura
Introduction of Participants
Election of Session Chairman
Approval of Conference Program
10:30 — 10:45 a.m. Refreshments
Session Chairman : Dr. N. Yamaki
10:45 — 12:00 N
Developments in NOx Air
Pollution Control
T. Fujita
Japan Environment
Agency
12:00 — 1:30 p.m. Lunch
1:30 — 3:00 p.m. Recent Research Developments A.P. Altshuller
on Atmospheric Reaction
Mechanisms
3:00 — 3:15 p.m. Refreshments
3:15 — 4:45 p.m. Smog Chamber Studies in
Japan
5:30 — 7:30 p.m. Reception
U.S. EPA
M. Okuda
Japan National
Institute for
Envi ronmenta1
Studies
PROCEEDINGS—PAGE viii
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Tuesday, February 5, 1980 Session Chairman : Dr. A.P. Altshuller
9:00 — 10:30 a.m. Intercomparisons of
Various Methods to
Measure Nitric Acid and
Other Nitrates
10:30 — 10:45 a.m. Refreshments
10:45 — 12:00 N Developments of
Measurement Methods in
Japan
12:00 — 1:30 p.m. Lunch
1:30 — 3:00 p.m. Photochemical Sulfate,
Nitrate and Nitric Acid
Research in Kanto Area
3:00 — 3:15 p.m. Refreshments
3:15 — 5:00 p.m. Use of Aerometric Data
to Evaluate the EKMA
Model
Application Study on EKMA
Model in Japan
B. Dimitriades
U.S. EPA
N. Yamaki
Saitama University
T. Okita
Hokkaido University
B. Dimitriades
U.S. EPA
S. Imai
Japan Environment
Agency
Wednesday, February 6, 1980
Session Chairman : Dr. N. Yamaki
9:00 — 10:30 a.m. General Discussion
Plans for Future Activities
10:30 — 10:45 a.m. Refreshments
10:45 ~ 12:00 N
Preparation of Joint Communique
Conclusion of Meeting
PROCEEDINGS—PAGE i
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JOINT COMMUNIQUE
The Fifth US-Japan Conference on Photochemical Air Pollution was held in
Tokyo, Japan, on February 4-6, 1980. The Japanese delegation consisted of
Mr. T. Fujita ( Head of delegation ), Dr. M. Okuda, Dr. N. Yamaki,
Dr. T. Okita, and Dr. M. Udagawa, while the US delegation consisted of
Dr. A. P. Altshuller ( Head of delegation ) and Dr. B. Dimitriades.
Discussions centered around the following subjects:
— NOx pollution control in Japan,
— recent developments in analytical methodology for air pollutants,
— atmospheric reaction mechanisms,
— ambient air analysis of S042~, N03~, and HN03, and
— EKMA Model for predicting ozone air quality,
The two delegations agreed that
(a) significant improvements had been achieved in the recent years in
their understanding of the limitations and merits of the various
research and monitoring procedures for measurement of ambient air
pollutants such as NMHC, N02, S042", N03~, HN03, aerosols, etc,
(b) there was a need for further studies of occurrence and cause of
acid precipitation, and
(c) a continuing effort should be made to promote further studies on
the chemical mechanisms of the photochemical air pollution related
atmospheric process.
The validity of the EKMA Model received considerable attention of both
delegations. The two delegations agreed to make further co-operative
efforts to evaluate the EKMA Model.
Furthermore, the two delegations agreed- to continue exchanging experts or
scientists as well as scientific data in the areas discussed in the
Conference.
Both sides agreed that the Sixth US-Japan Conference on Photochemical Air
Pollution would be held in the US.
Tokyo, February 6, 1980
-i
T
^ y
-
A.P. Altshuller, Head T. Fujita, Head
US Delegation Japan Delegation
PROCEEDINGS—PAGE X
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DEVELOPMENTS IN NOX AIR POLLUTION CONTROL
presented by T. Fujita
Environment Agency
Japan
PROCEEDINGS—PAGE 1
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Preface
In Japan, various measures against nitrogen oxides have been made
in order to prevent adverse health effects. Nitrogen dioxide, however,
not only has adverse health effects, but, plays a role as one of the
precursors of photochemical oxidznts.
Measures against nitrogen oxides in Japan are, in this sense,
associated with photochemical oxidants.
Amendment of ambient air quality standard for nitrogen dioxide and,
being aware of these situations, recent developments of measures against
nitrogen oxides are presented in the following.
PROCEEDINGS—PAGE 3
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I. Amendment of the Ambient Air Quality Standard for Nitrogen Dioxide
(July 11, 1978)
1. Introduction
Since the Ambient Air Quality Standard (AAQS) was promulgated in May 1973,
there has been remarkable advancement in the study of the effects of N0_ on
living organisms. Therefore, the Environment Agency had consulted the Central
Council for Control of Environmental Pollution to reevaluate the criteria for
the effects of N0_ on human health based on the latest scientific knowledge
and findings from Japan and overseas.
The Central Council for Control of Environmental Pollution established
an expert committee within itself, and made a careful study for about one
year. It submitted its report on health criteria and guides to the Environ-
ment Agency in May 1978. The Council collected data regarding the latest
scientific findings on the effects of nitrogen dioxide on living organisms,
which included laboratory animal tests, human tests on volunteers and epide-
miological studies, and evaluated them from a purely academic point of view.
Based on an overall evaluation of the results and taking the health of the
community population groups as a prime consideration, the Council proposed
that the following levels of nitrogen dioxide in the ambient air are adequate
as guides:
Short-term exposure (one hour average) 0.1 - 0.2 ppm
Long-term exposure (annual average) 0.02 - 0.03 ppm
These guides should indicate a level low enough that adverse effects upon
human health can be prevented in high probability. The level of human health
upon which the above guides are based in the state in which no ill health
does exist, or at which normal human health is maintained and the human body
functions are within the range of individual normal amplitude of homeostasis.
PROCEEDINGS—PAGE 4
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2. Amendment of the Ambient Air Quality Standard for NO-
Based upon the report submitted from the Central Council for Control of
Environmental Pollution and taking the opinions of many experts into
consideration, the Environment Agency revised the ambient air quality standard
for NO- pursuant to Article 9, Paragraph 3 of the Basic Law for Environmental
Pollution Control. Environment Agency issued a notification of the new
standard on July 11, 1978. The following is Notification No.38 of the
Environment Agency.
Ambient Air Quality Standard for Nitrogen Dioxide
(July 11, 1978)
The following are promulgated on the standard desirable for the protection
of human health (hereinafter referred to as the "ambient air quality standard")
concerning the environmental conditions for nitrogen dioxide pursuant with
Article 9, Paragraph 1 of the Basic Law for Environmental Pollution Control,
as well as on the lead time for its achievement, etc.:
1. Ambient Air Quality Standard
1. The ambient air quality standard for nitrogen dioxide shall be
within or below the range between 0.04 ppm and 0.06 ppm in terms
of a daily average of hourly values.
2. The standard in item 1 shall be based on the data measured by the
absorptiometry method using Saltzman reagent at places where the
state of the ambient air pollution by nitrogen dioxide can be
properly grasped.
3. The standard in item 1 shall not be applied to exclusive industrial
districts and roads, nor to areas and places which are not usually
inhabited by the general public.
2. Lead Time for Achievement, Etc.
1. In an area where the daily average of hourly values exceeds
0.06 ppm, efforts should be made to achieve the level of 0.06 ppm
within the period of not more than 7 years in principle.
PROCEEDINGS—PAGE 5
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2. In an area where the daily average of hourly values is within the
range between 0.04 ppm and 0.06 ppm, efforts should be made so
that, within the range, the ambient concentration level is maintained
around the present level or not remarkably exceeding it.
3. Not only emission control measures against individual sources, but
also other various countermeasures should be implemented in an
integrated, effective and appropriate manner in order to maintain
and achieve the ambient air quality standards.
Regarding the measurement method, the same Salzman method was employed.
However, the Saltzman coefficient (conversion coefficient of NO^ to nitrous
acid ion) has been revised from 0.72 to 0.84 for improved accuracy. Notifica-
tion of this revision was announced to prefectural governors and mayors.
The new environment standard, like the old, is based on a daily average
of hourly values. 98 percentile of the daily average value on an annual
basis is closely related to annual average value. Therefore, a daily average
within the range of 0.04 ppm - 0.06 ppm approximately corresponds to the
annual average value of 0.02 - 0.03 ppm which is the guides for long-term exposur*
If this standard is maintained, the guides for short-term exposure will probably
also be sustained.
The new environment standard is based on the guides recommended in the
report of the Central Council for Control of Environmental Pollution. The
Environmnet Agency considers the criteria and guides in the report to be the
best and latest scientific and technical findings on the effects of NO- on
human health available at present, and that the guides show the desirable
level at which human health can be maintained (Basic Law for Environmental
Pollution Control, Article 9, Paragraph 1).
Honouring opinions of Expert Committee who recommended guides for N0_ with
a range for the prevention of human health and noting that the level of
pollution caused by N02 differs in each area, ambient air quality standards
for N09 was established as those with a range. Furthermore, the Environment
Agency considered it appropriate with a view to developing steady measures
against NOx pollution.
PROCEEDINGS—PAGE 6
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Regarding the ambient air quality standard established between 0.04 ppm
to 0.06 ppm, a new idea has been introduced to set administrative targets in
each areas, according to the level of pollution caused by NCL. Therefore,
it was decided in principle that: (a) in an area where the daily average of
hourly values exceeds 0.06 ppm, efforts should be made to attain the level of
0.06 ppm within a period of not more than 7 years; and (b) in an area where
the daily average of hourly values is within the range of 0.04 ppm and 0.06 ppm,
efforts should be made that, within the range, the ambient concentration level
is maintained around the present level, or not remarkably exceeding it.
Based on these principles, (a) six areas have been designated as areas
where the daily average of hourly values exceed 0.06 ppm, and (b) eighteen
areas have been designated as areas where the daily average of hourly values
are within a range of 0.04 ppm to 0.06 ppm (August 7, 1979).
PROCEEDINGS—PAGE 7
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II. Measures Taken Against NOx Pollution
Regarding NOx pollution countermeasures, we implemented a Fourth
Regulation on NOx from stationary sources in August, 1979. This includes new
regulatory measures upon wider scope of target facilities. In addition to this,
comprehensive studies are being carried out in Tokyo and five other areas
because it is expected to introduce in highly polluted areas like major cities
a total mass emission regulation for NOx when it is regarded necessary after
taking into consideration the expected effects of automotive exhaust gas
control measures.
Regarding automotive exhaust emissions, we have enforced a stringent
exhaust gas emission standard at 0.25 g/Km on passenger cars, which is less
than one tenth of the emission levels up to 1972 when there was no such
emission standard. We initiated strengthened regulations on trucks and buses
in 1979, to be followed by further strengthened standards on gasoline-powered
light trucks and buses from 1981. We are currently endeavouring to accelerate
our technological assessment for disel-powered cars or gasoline-powered heavy
trucks so as to conclude necessary regulations as early as possible.
II-l Trends in Emission Control of NOx for Stationary Sources
The following regulations concerning emission control of NOx for
stationary sources have been enacted: The first phase emission controls for
large size facilities were enacted in August, 1973; the second phase emission
controls which consisted of the expansion of target facilities were enacted
in December 1975; and the third phase emission controls which consisted of
the reinforcement of the standard for the existing large size facilities, the
expansion of target facilities, and the reinforcement of the standard for
newly 144,000 soot and smoke emitting facilities defined by the Air Pollution
Control Law, about 13,000 facilities (about 9% of the total soot and smoke
emitting facilities) that are the main source of NOx have been progressively
designated as target facilities for emission control of NOx.
PROCEEDINGS—PAGE 8
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However, among the soot and smoke emitting facilities that have not been
designated as targets for the controls, there are some facilities whose
contribution to environmental pollution cannot be ignored. Basically, the
efforts for the prevention of air pollution should be shared impartially by
the emitters of soot and smoke. For these reasons, the Environment Agency had
decided to enact the fourth phase emission controls which consisted of
expansion and reinforcement of the emission regulations for the soot and smoke
emitting facilities not covered by the previous controls. On August 2, 1979
a portion of the Implementing Regulations for the Air Pollution Control Law
was amended and promulgated.
The standard for the emission of NOx amended at this time is unified
nationally based on Article 3 of the Air Pollution Control Law. It can be
considered the national minimum standard which should be maintained at soot
and smoke emitting facilities throughout the country. In formulating the
fourth phase emission controls at this time, the standard value was set at
the level where low NOx combustion techniques can be applied, as in the cases
of the first to the third controls.
As the result of the enactment of these controls, approximately 105,000
facilities (more than 70% of the total soot and smoke emitting facilities)
have become target facilities for NOx controls.
The comprehensive list of the standard value of emission is indicated in
the following Table.
II-2 Trends in the Emission Controls for Motor Vehicle Exhaust Gas
Concerning NOx
(1) Passenger Cars (LPG or gasoline fueled)
NOx control on the LPG or gasoline fueled passenger cars started in 1978.
Before the implementation of this control, the Central Council for
Environmental Pollution Control submitted its interim report in Oct. 1972.
In this report, the Council concluded that the target of NOx emission
standard for LPG or gasoline fueled passenger cars should be set at the
equivalent level to the Clear Air Act of the U.S.A.
PROCEEDINGS—PAGE 9
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In accordance with this recommendation, the NOx standard had been
strengthened gradually in 1975 and 1976. And in April 1978, the NOx
standard of 0.25 g/Km (average value) was implemented for domestic new
model cars. The date of enforcement of this standard for imported
passenger cars in April 1981.
As the result of this newest standard, NOx emitted from LPG or gasoline
fueled passenger cars is to be decreased by more than 90% when compared
with the period prior to the enactment of NOx controls.
(2) Vehicles other than LPG or gasoline fueled passenger cars.
The NOx controls were implemented in 1978 for gasoline fueled vehicles
other than passenger cars, and in 1979 for diesel powered vehicles.
And the standards were reinforced in 1975 for medium and light weight
vehicles, and in 1977 for heavy weight and diesel powered vehicles.
Furthermore, on December 26, 1977, the Central Council for Environmental
Pollution Control presented a report concerning the establishment of a long-
term targets of NOx emission for motor vehicles other than LPG or gasoline
fueled passenger cars.
The report recommended that NOx control should be strengthened in two
stages; Phase I to be enforced by the end of 1979 and Phase II by the end of
1984 at the latest. Based on this report, the NOx controls for the first
phase were implemented in 30 January 1979 for gasoline fueled vehicles and
in April 1979 for diesel-powered vehicels.
In order to study the feasibility of the implementation the second phase
targets, the "Investigation Committee for Motor Vehicle Pollution Control
Technology" was established at the Environment Agency in March 1978.
The Committee is entitled to appraise the state of technological develop-
ment of NOx reduction of auto-makers. The first report of this Committee was
announced in May, 1979. And the report concluded that light and medium duty
vehicles would be able to achieve the Phase II standard in the near future.
Based on this report, it was decided that the second phase control is to be
PROCEEDINGS—PAGE 10
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implemented for light and medium weight gasoline fueled vehicles from 1981.
As for the remaining types of vehicles such as heavy weight lorries or
diesel-powered vehicles, the Committee had decided to continue its evaluation
of the technological development of auto-makers.
PROCEEDINGS—PAGE 11
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w
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Classification
Chart
Item No. 1
Number
1
Type of Facility
Gas Fired Boilers
50 -
10 - 50
4-10
1-4.
0.5 - 1
- 0.5
Coal Fired Boilers
(ceiling burner; below
5,000kcal/kg)
10 -
4-10
1-4
0.5 - 1
- 0.5
Coal Fired Boilers
(Furnace divided radiation type)
(Furnace heat generation
capacity - over 140,OOOkcal/H)
10 -
4-10
1-4
0.5 - 1
0.5
Standard Value of Emission
Date Of
Instal-
On lation
% of the
Facility
5
6
6
73. 75. 77. 70.
-73 8.10- 12.10- 6.18- 8.10-
8>9 75. 77. 79.
12.9 6.17 8.9
130 130 100 60 60
130 130 100 100 100
130 130 130 100 100
150 150 130 ! 130 130
150 150 150 150 150
(150) (150) (150) 150 150
650 480 480 400 400
650 480 480 400 400
650 650 480 400 ' 400
650 650 650 400 400
(650) (650) (650) 400 400
550 480 480 400 400
550 480 480 400 400
550 550 480 400 400
550 550 550 400 400
(550) (550) (550) 400 400
Date of Application
of the Standard
73. 75. 77. 79.
-73. 8.10- 12.10- 6.18- 8.10-
8-9 75. 77. 79.'
12.9 6.17 8.9
15] [1] [1] HI [1]
(5] (11 [1] [1) [1]
[5] U) [1] HI ID
[5] [5] [1] [1] [1]
[8] [8] [8] [1] [1]
[12] [12] [12] [1] |1]
[6] (11 (1) [1] [1]
[6] 11] [1] [1] [1]
[6] [61 [1J (1) (1)
[6] [6] [(,] [1] [1]
[12] [12] [12] [1] [1]
[8)750 {11 [1] [1] [1]
[8)750 [1] [1] [1] [1]
[8)750 [8)750 [L] (11 [].]
[8)750 [8J750 E8J750 [1] [1]
[12] [12] [12J [1] [1]
Remarks
*Numbers encircled in
the "Date of Application
of the Standard"
column indicate the
following dates.
UlDate of installation
of the Facility
[ZJJul. 1, 1975
[3JDec. 10, 1975
[4]Jul. 1, 1976
[5]Dec. 1, 1977
[6]Jun. 18, 1977
[7]Sept.lO, 1977
[8]May 1, 1980
[9]0ct. 1, 1980
[10] Apr. 1, 1981
[UJAug.lO, 1982
[12]Aug.lO, 1984
^Numbers in the "Type of
Facility" column are
amounts of flue K
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8
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CO
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Classification '
Chart
Item No. 1
Number
1
Type of Facility
Coal Fired Boilers (excluding
coal fired boilers mentioned
above)
10 -
4-10
1 - 4"
0.5 - 1
- 0.5
Solid Material Fired Boilers
(excluding coal fired boilers)
10 -
4-10
1-4
0.5 - 1
0.5
Crude oil tar fired Boilers
equipped with flue gas desulfuri-
zatlon facilities
(Nm3/H of flue gas)
50 - 100
10 - 50
4-10
1-4
0.5 - 1
- 0.5
Standard Value of Emission
Date of
Instal-
On lotion
~ of the
" Facility
6
6
4
73. 75. 77. 79.
-73 8.10- 12.10- 6.18- 8.10-
8'9 75. 77. 79.
12.9 6.17 8.9
480 480 480 400 400
(480) 480 4BO 400 400
(480) (480) 4SO 400 400
480 480 480 400 400
(480) (480) (480) 400 400
480 480 480 400 400
(480) 480 480 400 400
(480) (480) 480 400 • 400
480 480 "BO 400 400
(480) (480) (480) 400 400
210 180 150 no no
210 180 130 150 ISO
280 180 150 130 150
2fiO 280 150 150 150
280 280 280 -'77.9.8 180
280
(280) (280) (280) " '"b's 180
'77.9.10
109
Date of Application
oŁ the Standard
73. 75. 77. 79.
-73. 8.10- 12.10- 6.18- 8.10-
8l9 75. 77. 79.'
12.9 6.17 8.9
[8)750 [1] [1] [1] [1]
[11)750 ID ID ID ID
[11)750 [11)750 [i] [1] [1]
[3] [8] [8] [1) [1]
[12] [12][12] [1] [1]
[8)600 [1] [1] ID ID
[11)600 [1] [1] [1] [1]
[11)600 [11)600 [1] [1] [1]
[3) [8) [8] [1] [1]
[12) [12][12] [1) [1]
[8]280 11] ID ID (11
[»)280 [1] |lj [1) ID
[5] [1] [1] [1] ID
15] [5] [1] [I) (D
[9] [9] [9) -•"." (D
191
•77.9.10-
111
[12] [12][12] [1]
" [12!
'77,9.10-
! 1 1
I* 1
Remarks
'Numbers encircled in
the "Date of Applica-
tion of the Standard"
column indicate the
following dates.
[IjDate of installation
of the Facility
[2]Jul. 1, 1975
[3)Dec. 10, 1975
[4]Jul. 1, 1976
[5]Dec. 1, 1977
[6]Jun. 18, 1977
[ZJSept.lO, 1977
[8]Hay 1, 1980
[9)0ct. 1, 1980
[10]Apr. 1, 1981
(ll)Aug.lO, 1982
I12]AUŁ.10, 1984
Excluding package type
botlcrs(opcratlnR by
high-load) with [.Luc
gas below 500 ,OOONm3 /H ,
and installed before
Sept. 10, 1977.
O
W
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8
8
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en
w
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Classification
Chart
Item Ho. 1
Number
1
Type of Facility
Crude Oil Tar Fired Boilers
(excluding those equipped with
flue gas desulfurization
facilities mentioned above)
50 -
10 - 50"
4 - 10
1-4
0.5 - 1
- 0.5
Liquid Fired Boilers equipped
with flue gas desulfurization
facilitiesdimited Nm'/H of flue
gas excluding crude oil tar)
50 - 100
10 - 50
4-10
1-4
0.5 - 1
- 0.5
Standard Value of Emission
Data of
Instal-
On lotion
.. of the
Facility
4
4
73. 75. 77. 79.
-73 8.10- 12,10- 6.18- 8.10-
8'9 75. 77. 79.
12.9 5.17 8;9
180 J80 150 130 130
190 180 150 150 150
(250) 180 130 150 150
(250) (250) 150 150 150
250 250 250 -'";9.9 i8o
"11. 9.10-
(250) (250) (250) .^00^ iso
(2001
•77.9.10-
160
210 180 150 130 130
210 180 150 150 150
210 180 150 150 150
250 250 150 150 150
280 280 280 " 7j'jŁ" 180
•77.9 10
(280) (280) (280) .^ 180
I2BO)
V7.9.10
100
Date of Application
of the Standard
73. 75. 77. 79.
-73. 8.10- 12.10- 6.18- 8.10-
8'9 75. 77. 79:
12.9 6.17 8.9
[8J280 [1] [1J [1] [1]
[81280 [1] Jl] [1] 11]
11)280 [11 [1] [1] [1]
11)280 [111280 [1] [lj [1]
[9] [91 191 -'%,"•" [1]
•77.0.10-
[12] [12] [12] _.7y.9.9 (11
112]
•77,9.10
Ml
[8]230 [1] [1] [1] [1]
[8)230 [1] [1] [11 [1]
IS] [1] [1] [1] [1]
[81 [8] [l] [^ [1]
(9) (9) [9i;;g (11
[12] [12] [12] -'7719.9 [1]
•77,9.10
M 1
Remarks
Excluding package type
boilerstopcrntions by
high-load) with flue
Gas below 5000Nm3/H,
and installed before
Sept. 10, 1977
*Numbers encircled in
the "Date of Applica-
tion of the Standard"
column indicate the
following dates.
(l]Date of installation
of the Facility
[2]Jul. 1, 1975
(3]Dec. 10, 1975
[4]Jul. 1, 1976
[SjBcc. 1, 1977
[6]Jun. 18, 1977
[7]Sept.lO, 1977
[SJHay 1, 1980
[9]0ct. 1, 1980
(lOjApr. 1, 1981
[11] Aug. 10, 1982
[12)Aug.lO, 1984
Excluding package type
boilcrsfoporatlons by
high-load) with f ] ,,L,
KOS below 5000Nm!/ll,
and installed before
Sept. 10, 1977
-------
Classification '
Chart
Item Mo. 1
Number
1
2
3
Type of Facility
Liquid Fired Boilers
(Excluding all liquid fired
boilers mentioned above)
50 -
10 - 50
4 - 10"
1-4
0.5 - 1
- 0.5
Gas Generators and Heating
1'urnaces
Gas Generators for the
manufacture of hydrogen gas
(ceiling burner combustion type)
Pellet Baking Furnace
1
1
Pellet Baking Furnace
(gas fired type)
1
1
Standard Value of Emission
Date of
Instal-
On lation
% of the
Facility
it
7
7
15
15
73. 75. 77. 79.
-73 8.10- 12.10- 6.18- 8.10-
8'9 75. 77. 79.
12.9 6.17 8.9
180 180 150 130 130
190 180 150 150 150
190 180 150 150 150
230 230 150 150 150
250 250 250 ISO 180
'77.0.10
180
(250) (250) (250) "'Y™? 180
'77. 0.10
ICO
(170) (170) (170) (170) (150)
(360) (360) (360) (360) (150)
(300) (300) (300) 220 220
(300) (300) (300) (300) (220)
(540) (540) (540) 220 220
(540) (540) (540) (54'0) (220
Date of Application
of the Standard
73. 75. 77. 79.
-73. 8.10- 12. 30- 6.18- 8.10-
8'9 75. 77. 7?:
12.9 6.17 8.9
(8J230 [1J [1] [1] [1]
[81230 (1) [1] 11] [1]
(5J [1] [1] [1] [1]
[8] [81 [1] [IJ [1]
19) [91 [91 "'"o;99 [1]
•77.9.10
111
[12] [12] [12] -•','; 9,-S" [1]
•77.9.10-
111
[11] [11] [111 [11] [1]
[11] [11] [11] [11] [1]
[111 [111 [11] [1] [1]
[11] [11] [11] [11] [1]
[11] [11] [11] [1) [1]
[11] [11] [11] [11] [1]
Remarks
Excluding package type
boilers(operatins by
high-load) with fj.uc
gas below 500,OOONni3/H,
and installed before
Sept. 10, 1977.
''Numbers encircled in
llio "Date of Application
of the Standard" column
indicate the
following dates.
[l]Datc of installation
of the Facility
(2]Jul. 1, 1975
[3]Dcc. 10, 1975
(4]Jul. 1, 1976
[5]Dcc. 1, 1977
(6]Jun. 18, 1977
(7]Sept.lO, 1977
[SJMay 1, 1980
[9)0ct. 1, 1980
[lOUpr. 1, 1981
[llJAug.10, 19S2
[UiAufi.lO, 198-',
-------
(Ti
Classification
Chart
Teem Mo. 1
Number
3
3
3
Type of Facility
Sintering Furnaces
(Excluding Pellet Baking
Furnaces)
10
1 - 10"
1
Sintering Furnaces, used Tor
manufacture Of f urromangaiiesc
10
1-10
1
Calcination Furnaces
1 -
1
Calcination Furnaces used Cor
manufacture of alumina
1
1
Roasting Furnaces
Roasting Furnaces used for
manufacture of
ferromangancse
Standard Value of Emission
Date of
Instal-
On latlon
„ of the
A Facility
15
15
10
10
14
14
73. 75, 77. 79.
-73 8.10- 12.10- 6.18- 8.10-
8'9 75. 77. 79.
12.9 6.17 8,9
260 260 260 220 220
270 270 270 220 220
(300) (300) (300) (300) (220)
260 260 260 220 220
270 270 270 220 220
(800) (800) (800) (800) (220)
(200) (200) (200) (200) (200)
(200) (200) (200) (200) (200)
(350) (350) (350) 200 ) 200
(350) (350) (350) (350) (200)
(250) (250) (250) (250) (220)
(400) (400) (400) (400) (220)
Date of Application
of the Standard
73. 75. 77. 79.
-73. 8.10- 12.10- 6.18- 8.10-
8l9 75. 77. 79.'
12.9 6.17 8.9
[81 (8] [8] [1] [1]
(8) (8) [8] [1] [1]
[11] [11] [111 [11] [1]
[8] [8] [8] [1] [1]
[8] [8] [8] [1] [1]
[11] [ID [11] [HI [1]
[11] [11] [11] [11] [1]
[11] [11] [11] (11) [1]
111) [11] (11) HI til
[11] 111] [11] [11] [I]
[11] [11] [U] [11] [1]
[11] [11] [11] [11] [1]
Remarks
*Numbers encircled in
the "Date of Application
of the Standard" column
indicate the
following dates.
[l]Date of installation
of the Facility
[2]Jul. 1, 1975
[3]Dec. 10, 1975
[4]Jul. 1, 1976
[SjDec. 1, 1977
[6]Jun. 18, 1977
[7]Sept.lO, 1977
[8]May 1, 1980
[9]0ct. 1, 1980
[lOjApr. 1, 1981
[11] Aug. 10, 1982
[12]Aug.lO, 1984
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Classification
Chart
Item No. 1
Number
it
5
6
Type of Facility
Blast Furnaces
Metal Smelting Furnaces
Metal Heating Furnaces
(Radiant tube type)
10
4-10
1-4
0.5 - 1
- 0.5
Metal llcalinu Furnaces
(for welded steel pipe)
10 -
1-10
0.5 - 1
- 0.5
Standard Value of Emission
Date of
Instal-
On la t ion
, of the
'' Facility
15
12
LI
11
73. 75. 77. 79.
-73 8.10- 12.10- G.18- 8.10-
8'9 75. 77. 79.
12.9 6.17 8.9
(120) (120) (J20) (120) (100)
(200) (200) (200) (200) (180)
200 200 100 100 100
200 200 150 150 150
200 200 150 150 150
200 200 200 150 150
(200) (200) (200) 180 180
100 100 100
180 180
150 150
180 180
Date of Application
of the Standard
73. 75. 77. 79.
-73. 8.10- 12.10- 6.18- 8.10-
8'9 75. 77. 79:
12.9 6.17 8.9
[11] [11] [11] [U] [1]
[11] [11] [11] [11] [1]
[81220 11] [1] [1] [1]
[81220 [1] [1] [1) [1]
[5] [1] [1] [1] [1]
18] 18} [8} [I] [1]
111] [U] [U] [1] [1]
UJ [U [U
[1] [U
[11 [U
[1] ID
Remarks
Excluding application
for Cupola
^Numbers cncieclcd in
the "D.itc of Application
of the Standard" column
indicate the following
dates.
[IJDate oC installation
oC Che Facility
[2].htl. 1, 1975
[•Jlllec. 10, 1975
UlJul. 1, 1976
[5]Ucc. 1, 1977
[6]Jun. 18, 1977
[7)Scpt.lO, 1977
[8]May 1, 1980
[9]0ct. 1, 1980
[10]Apr. 1, 1981
[ll]Aup,.10, 1982
w
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Classification
Chart
ILetn No. 1
Number
6
7
Type of Facility
Metal Heating Furnaces
(Excluding metal heating furnaces
mentioned above)
10 -
4-10
1-4"
0.5 - 1
- 0.5
Petroleum Heating Furnaces
(Equipped with flue gas
desulfurization facilities)
10 -
4-10
1-4
0.5 - 1
0.5
Petroleum Heating Furnaces
(Ethylena resolving furnaces)
10
4-10
1-4
0.5 - 1
- 0.5
Standard Value of Emission
Date of
Instal-
On lacion
•y Of tllC
Facility
11
6
6
73. 75. 77. 79.
-73 fl.10- 12.10- 6.18- 8.10-
8'9 75. 77. 79.
12.9 6.17 8.9
160 160 100 100 100
170 1.70 J5o no no
(170) (170) 130 130 130
170 170 170 J50 150
(200) (200) (200) 180 180
370 170 100 100 100
170 1.70 100 100 100
180 .170 150 130 130
190 190 190 150 150
(200) (200) (200) 180 180
170 170 100 100 100
170 170 lOt) 100 100
(180) (tso) ijo uii no
180 180 180 150 150
(200) (200) (200) 180 ISO
Date oŁ -Application
of the Standard
73. 75. 77. 79.
-73. 8.10- 12. JO- 6.18- 8.10-
8>9 75. 77. 79."
12.9 6.17 8.9
[8)220 [8)200 [1] [11 [1]
[8J220 [8)200 (1) [1) (1)
[11)200 [11)200 [1] [1] [1)
(8) [8] [8] (1) [1J
[11] 111] UD (1) [1)
[8)210 [1] [1] [1) [1]
[8)210 [1] [1] [1] [1]
[5) [1] [1) U) (1)
[81 [8] [8] (1) [1]
[111 111] [U] [11 [1]
[8J (8) [1] [1] [1]
18) IB] HI ID tU
[11) [HJ ID [1] ID
18) [8] [81 U) HI
[111 [U] 111] [1] [1]
Remarks
*Numbcrs encircled in
the "Date of Application
of the Standard" column
indicate the
following dates.
[l)Date of installation
of the Facility
[2)Jul. 1, 1975
[3)Dec. 10, 1975
[4]Jul. 1, 1976
[5]Dec. 1, 1977
[6]Jun. 18, 1977
[7]Sept.lO, 1977
[8]May 1, 1980
[9]0ct. 1, 1980
[10] Apr. 1, 1981
(ll)AuE.10, 1982
[IZJAug.lO, 1984
-------
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Classification '
Chart
Item No. 1
Number
7
7
7
Type of Facility
Petroleum Heating Furnaces
(among ethylene resolving
furnaces, those having burners
equipped at the bottom of
furnace)
10
A - 10
1 - A
0.5 - 1
- 0.5
Petroleum Heating Furnaces
(Ethylene independent super-
heating furnaces and methanol
reforming furnaces)
10 -
4-10
1-4
0.5 - 1
0.5
Petroleum Heating Furnaces
(among ethylene independent
super-heating furnaces or
methanol reforming furnaces,
those having air prcheatcrs)
10
It - 10
1-4
0.5 - 1
- 0.5
Standard Value of Emission
Date of
Instal-
On lation
of the
^ Facility
6
6
6
73. 75. 77. 79.
-73 8.10- 12.10- 6.18- 8.10-
8'9 75. 77. 79.
12.9 6.17 8.9
170 170 100 100 100
170 170 100 100 100
(280) (280) 150 130 130
180 180 180 150 150
(200) (200) (200) 180 180
170 170 100 100 100
(180) (180)- 100 100 100
180 180 150 130 130
180 180 180 150 150
(200) (200) (200) 180 180
170 170 .100 100 100
(430) (430) 100 100 100
180 1.80 150 130 130
180 180 180 150 150
(200) (200) (200) 180 180
Date of Application
of the Standard
73. 75. 77. 79.
-73. 8.10- 12.10- 6.18- 8.10-
8'° 75. 77. 79:
12.9 6.17 8.9
[8] [8] [1] [1J [1]
[8] [8] [1] [1] [1]
[111 HI] U! HI [1]
[8] [8] [8] [1J (1)
[11] HI] [11] [1] [1]
[8] [8] [1] [1] [1]
[11] [11] [1] [1] [1]
[8] [8] [1] [1] [1]
[S] [8] [8] [1] [1]
[U] [11] [11] [1] [1]
[8] [3] [1] [1] [1]
[11] [11] [11 [U ID
[8] [8] [1] [1] [1]
(8) [8] [8] [1] [1]
[11] (11) [11] UJ [1]
Remarks
^Numbers encircled in
the "Date of Application
of the Standard" column
indicate the following
dates.
(l]Datc of installation
of the Facility
[2]Jul. 1, 1975
[3)I)cc. 10, 1975
[4]Jul. 1, 1976
[5)Dec. 1, 1977
[6]Jun. 18, 1977
[7]Sept.lO, 1977
(SjMav 1, 1980
(9]0ct. 1, 1980
[lOjApr. 1, 1981
[HjAug.lO, 1982
(12M"g.lO, 1984
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Classification
Chart
Item No. 1
Number
7
7
8
8-2
9
9
Type of Facility
Petroleum Heating Furnaces
(ammonia reforming furnaces)
10 -
4-10
1 - A.
0.5 - 1
- 0.5
Petroleum Heating Furnaces
(Excluding Petroleum heating
furnaces mentioned above)
10 -
4-10
1-4
0.5 - 1
- 0.5
Catalyst Regeneration Towers
Catalyst Regeneration Towers
equipped with Petroleum gas
treating facilities
Lime Baking Furnaces
(g.is fired rotary kilns)
Cement Baking Furnaces (wet type)
10
- 10
Standard Value of Emission
Date of
Instal-
On lation
of the
* Facility
6
6
6'
8
15
10
73. 75. 77. 79.
-73 8.10- 12.10- 6.18- 8.10-
8'9 75. 77. 79.
12,9 5.17 8.9
170 170 100 100 100
170 170 100 100 100
180 180 150 130 130
180 180 180 150 150
(200) (200) (200) 180 180
170 170 100 100 100
170 170 100 100 100
180 170 150 130 • 130
180 180 ISO 150 150
(200) (200) (200) 180 180
(300) (300) (300) (300) (250)
(300) (300) (300) (300) (250)
(300) (300) (300) (300) (250)
250 250 250
350 350
Date of Application
of the Standard
73. 75. 77. 79.
-73. 8.10- 12.10- 6.18- 8.10-
8'9 75. 77. 79;
12.9 6.17 8.9
[8] [8] [1] [1] [1]
[8] [8] [1] [1] [1]
[8] [8] [1] [1] [1]
[8] [8] [8] (1) [1]
[11] [ID [11] ID [1]
[8]210 [1] [1] [1] [1]
[8)210 [1] [1] [1] [1]
[5] [1J [1] [1] [1]
[8] [8] [8] [1] [1]
[11] [11] [11] [1] [1]
[11] [11] [11] [11] [1]
[11] [11] [11] [11] [1]
[11] [1.1] [11] [11] [1]
[1] ID [1]
[1] ID
Remarks
*Numbers encircled in the
"Date of Application of
the Standard" column
indicate the following
dates.
[l]Date of installation
of the Facility
UUul. 1, 1975
[3]Dcc. 10, 1975
[4]Jul. 1, 1976
[5]Dec. 1, 1977
[6]Jun. 18, 1977
[7)Sept.lO, 1977
[8]May 1, 1980
[9]0ct. 1, 1980
[10]Apr. 1, 1981
[ll]Aug.lO, 1982
[12)Aug.lO, 1984
-------
Classification
Chart
Item No. 1
Number
9
9
9
9
9
9
10
10
10
11
13
Type of Facility
Cement Baking Furnaces
(Excluding wet types)
10 -
- 10
Baking Furnaces used for manu-
facturing refractories and fire
bricks
Melting Furnaces used tor manu-
facturing plate glasses and
glass fibers
Melting Furnaces for manufactur-
ing frits, optical glasses and
glass tubes for electrical use
Molting Furnaces for other types
of glass (excluding melting
furnaces mentioned above)
Melting Baking Furnaces (Exludins
baking furnaces mentioned above)
Reaction Furnaces and Direct
Fire Furnaces
Reaction Furnaces used for
potassium sulfatc
Reaction Furnaces for Sulfuric
Acids (Using NOx as Catalyst)
Drying Furnaces
Waste Incinerators
(continvious type only)
4
4
Waste Incinnrntors
(Excluding continuous Lvprs)
Standard Value of Emission
Date ot
Instal-
On latJon
,, of the
facility
10
18
15
16
15
i
15
6
(j
15
16
12
''
73. 75. 77. 79.
-73 8.10- 12.10- 6.18- 8.10-
8-9 75. 77. 79.
12.9 6.17 8.9
430 480 250 250 250
480 480 480 350 350
(450) (450) (450) (450) (400)
(400) (400) (400) (400) (360)
(900) (900) (900) (TOO) (800)
(500) (500) (500) (500) (450)
(200) (200) (200) (200) (180)
(200) (200) (200) (200) (180)
(250) (250) (250) (250) (180)
(700) (700) (700) (700) (180)
(250) (250) (250) (350) (230)
(1)00) (WO) (300) 250 210
OOO) (300) OOO) (300) (250)
Date of Application
of the Standard
73. 75. 77, 79.
-73. 8.10- 12.10- 6,18- 8.10-
8r9 75. 77. 79.'
12.9 6.17 8,9
UO] [10] 11] [1] [1]
[10] [10] [10] [1] [1)
[11] [11] [11] [11] 11}
[11] [11] [11] [11] [1]
(11) [11] [11] [11] [1]
[11] [11] [11] [11] [1]
(1-U MJJ [11] [111 [1]
[111 !U] [11] [11] [1]
111] ill] 111] [11] [1]
[U] [11] (11) [11] [1]
[11] |H] ID] HI] [1]
in] i .1 \ } [MI [ i i in
m i mi mi [in in
Remarks
*Numbers encircled in
the "Dace of Application
of the Standard" column
indicate the following
dates.
[IJDatc of installation
of the Facility
[2]Jul. 1, 1975
[3JOcc. 10, 1975
(4]Jul. 1, 1976 .
[SjDcc. 1, 1977
[6]Jun. 18, 1977
[7]Scpt.lO, 1977
[BJMay 1, 1980
[9]0ct. 1, 1980
[10]Apr. 1, 1981
[lllAug.10, 1982
[12]Aug.lO, 1984
*0n: 6
230 230
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Classification •
Chart
Item Ho. 1
Humber
13
13
14
14
14
Type of Facility
Incinerators with cyclone
Combustion Type
(continuous type only)
It
- 4.
Distinctive Waste Incinarator
(continuous type only)*
4
4
Smelting Facilities for Copper,
Zinc and Lead
Roasting Furnace
Sintering Furnace
Blast Furnace
Among Blast Furnaces, those for
smelting zone, sludge processing
furnaces(only those which use
coal or coke as a fuel or
reducing agent)
Among Blast Furnaces, those for
smelting zinc, vertical
distillating furnaces
Standard Value of Emission
Date or
Instal-
On In t ion
% of the
Facility
12
12
14
15
15
15
15
73. 75. 77. 79.
-73 8.10- 12.10- 6.18- 8.10-
B'9 75. 77. 79.
12.9 6.. 17 8.9
(900) (900) (900) (450) (450)
(900) (900) (900) (900) (450)
(300) (300) (300) 250 250
(900) (900) (900) (900) (700)
(250) (230) (250) (250) (220)
(300) (300) (100) (300) (220)
(120) (120) (120) (120) (100)
(450) (450) (450) (.',50) (450)
(230) (230) (230) (230) (100)
Date of Application
of the Standard
73. 75. 77. 79.
-73. 8.10- 12.10- 6.18- 8.10-
8'9 75. 77. 79.'
12.9 6.17 8.9
[11] [11] [11] [1] [1]
[11] [11] [11] [11] [1]
[11] [11] [11] [1] [1]
[11] [11] [11] [11] [1]
[11] [U] [11] [11] [1]
(111 [11] [11] [111 [1]
[11] [11] [11] [11] [1]
[11] [11] [11] [11] [1]
[11] Ul] Hi] [11] [1]
Remarks
''Here, distinctive wastes
arc those disposed during
the processes which
produce or use nitro
compounds, aratno compounds,
cyano compounds, or their
derivatives; or procedures
which treat waste water
with ammonia.
* Number s encircled in the
"Date of Application of
the Standard" column
indicate the
following dates.
[IJDatc oŁ installation
of the Facility
(2]Jul. 1, 1975
[3]Dcc. 10, 1975
[4]Jul. 1, 1976
[5]Dec. 1, 1977
[6]Jun. 18, 1977
[7]Sept.lO, 1977
[8]May 1, 1980
[9]0ct. 1, 1980
[lOUpr. 1, 1981
[lllAug.10, 1982
[12]Aug.lO, 1984
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Classification
Chart
Item No. 1
Number
14
14
14
14
14
18
21
23
Type of Facility
Dissolving Furnace
(Excluding chose undermentioned)
Among Dissolving Furnaces, chose
for smelting copper refining
(only those using ammonia as a
reducing agent)
Among Dissolving Furnaces, chose
for smelcing zinc, Rectifying
Zinc and Cadmium (only chose
firing LPG and COG)
Among Dissolving Furnaces, chose
for smelting zinc, Zinc Sludge
(rotary type)
Drying Furnaces
Reaction Furnaces for
Manufacturing Accivatcd Carbon
Manufacturing Facilities for
Phosphorus, etc.
Baking Furnaces
Dissolving Furnaces
Manufacturing Facilities for
Sodium Tripoli Phosphate
Baking Furnaces
Drying Furnaces
Standard Value of Emission
Date of
Instal-
On latinn
j; of the
Facility
12
12
12
12
16
6
15
15
15
16
73. 75. 77. 79.
-73 8.10- 12.10- 6.18- 8.10-
8-9 75. 77. 79.
12.9 6.17 B.9
(200) (200) (200) (200) (180)
(330) (330) (330) (330) (330)
(330) (330) (330) (330) (330)
(330) (330) (330) (330) (180)
(200) (200) COO) (200) (180)
(200) (200) (200) (200) (180)
(200) (200) (200) (200) (180)
(650) (f.50) (650) (650) (600)
(ZOO) (200) (200) (200) (ISO)
(200) (200) (200) (200) (180)
Date oŁ Application
of the Standard
73. 75. 77. 79.
-73. 3.10- 12.10- 6.18- 8.10-
8'9 75. 77. 79.'
12.9 6.17 8.9
[11] [11] [11] [11] HI
[11] [11] [11] [11] [1]
[11] [11] [11] [11] [1]
[11] [11] [11] [11] [1]
[111 [U] [11] [11] [1]
[11] [11] [11] [11] [1]
[11] [U] [11] [11] [1]
[11] [U] [U] [11] [1]
(11) (11] [11] [11] [1]
[11] [11] [111 [11] [1]
Remarks
*Numbcrs encircled in the
"Date of Application of
the Standard" column
indicate the
following dates.
[l]Date of installation
of the Facility
[2]Jul. 1, 1975
[3]Dec, 10, 1975
[4]Jul. 1, 1976
[5]Dec. 1, 1977
[6JJun. 18, 1977
[7]Sept.lO, 1977
[8] Hay 1, 1980
[9]0ct. 1, 1980
[lOJApr. 1, 1981
[IDAug.lO, 1982
[12]Aug.lO, 1984
NJ
Ul
-------
§
o
M
w
D
H
z
Q
w
I
I
w
Classification
Chart
Item No. 1
Number
24
25
26
26
27
28
Type of facility
Dissolving Furnaces used for
Secondary smelting of Lead
Dissolving Furnaces used for
Manufacturing Lead Storage
Batteries
Manufacturing Facilities for
Lead Pigment
Dissolving Furnaces
Dissolving Furnaces used for
Manufacturing Lead Oxides
Reverberatory Furnaces
Reaction Furnaces
Reaction Furnaces for
Manufacturing Lead Oxides or
Lead Nitrate
Nitric Acid Manufacturing
Facilities
Coke Furnaces
(Otto type)
10
- 10
Coke Furnaces
(Excluding Otto type)
10
- 10
Electric Furnaces are
excluded
Standard Value of Emission
Dace of
Instal-
On la t ion
of the
'• Facility
12
12
12
IV
Os
15
6
A
Os
*
Os
7
7
73. 75. 77. 79.
-73 8,10- 12.10- 6.18- 8.10-
"•9 75. 77. 79.
12.9 6.17 8.9
(200) (200) (200) (200) (180)
(200) (200) (200) (200) (180)
(200) (200) (200) (200) (180)
(200) (200) (200) (200) (180)
(650) (650) (650) (650) (600)
(200) (200) (200) (200) (ISO)
(200) (200) (200) (200). (180)
200 200 200 200 200
200 170 170
170 170
350 350 200 170 170
350 350 J30 170 170
Date of Application
of the Standard
73. 75. 77. 79.
-73. 8.10- 12.10- 6.18- 8.10-
8'9 75. 77. 73:
12.9 6.17 8.9
[11] [11] [11] [11] [1]
[11] [11] [11] [11] [11
[11] [11] [11] [11] [1]
[11] [11] [11] [11] [1]
[1.1] [11] [11] [11] [1]
[11] [U] [11] [U] [1]
[11] [11] [11] [11] [1]
14] HI ID HI U]
[1] [1] [1]
[1] [1]
13] [8] [1] [1] [1]
[8] [8] [3] [1] [I]
Remarks
'"Numbers encircled in
the "Date of Application
of the Standard" column
indicate the
following dates.
[l]Date of installation
of the Facility
[2]Jul. 1, 1975
[3]Dcc. 10, 1975
[4]Jul. 1, 1976
[SjDec. 1, 1977
[6]Jun. IS, 1977
[7]Sept.lO, 1977
[8]May 1, 1980
[9]0ct. 1, 1980
[10] Apr. 1, 1981
[HjAug.lO, 1982
[12] Aug. 10, 1984
*0s means that the
concentration of NOx in
flue gas shall not be
converted by residual
oxgen concentration.
-------
Table 1
Long Term Targets for Permissible Levels of Motor Vehicle Exhaust Gas
Types of Vehicles
, Rate of
Targeted Permissible Levels -no^r.f,t.
. against
(Average) Present
1st Phase
Gasoline Fueled regular &
small size vehicles
Gasoline or LPG fueled regular
and small size vehicles
(excluding vehicles for
passenger use with a
capacity of less than
10 persons.)
Direct Injection Type
Indirect Injection Type
Gross
2,500
Gross
kg and
Gross
1,700
weight
kg
weight
under
weight
kg
Light motor vehicles (excluding vehicles for
use and vehicles with 2 cycle engines)
over
over 1,700
2,500 kg
under
passenger
540
340
1,100
1.2
1.0
1.2
ppm
ppm
ppm
g/km
g/km
g/km
2nd
Phase 1st
470
290
750
0
0
0
.9
.6
.9
ppm
ppm
ppm
g/km
g/km
g/km
Phase
17
11
29
33
44
33
Decrease
the
Rate(%)
2nd Phase
18
24
52
50
67
50
Method of
Measurement
D6-mo.de
6-mode
10-mode
H
W
D
H
2
O
CO
I
I
*a
s
w
to
Ul
(Notes) 1. The targeted value of the 1st phase should be achieved in 1979.
2. It is considered essential to implement the regulations according to the 2nd phase targeted value
several years after the implementation of 1st phase controls, but within the next five years at most,
(Reference) "Concerning the Setting of Long Term Policy for Permissible Levels of Motor Vehicle Exhaust Gas
(Report)", December 26, 1977, the Central Council for Environmental Pollution Control
-------
Passenger Vehicles
100%
71%
39%
27%
20%
Before April 1973 (not controlled)
April 1973 (controls of 1973)
April 1975 (controls of 1975)
(Equivalent Inertia Weight over 1000kg)
April 1976
1 c\}Ji-J-±. j.s i \J
(Equivalent Inertia Weight under 1000kg)
April 1978 (controls of 1973)
Light Weight Gasoline Fueled Vehicles (gross weight under 1.7 tons)
Before April 1973 (not controlled)
100%
71%
59%
32%
19%
April 1973 (controls of 1973)
April 1975 (controls of 1975)
(Controls of 1979)
January 1981 (controls of 1981)
Light Freight Vehicles Medium-weight Gasoline Fueled Vehicles
(Gross weight over 1.7 tons under 2.5 tons)
Before April 1973 (not controlled)
100%
71%
59%
April 1973 (controls of 1973)
April 1975 (controls of 1975)
39%
29%
j(controls of 1979)
2nd phase (light freight vehicles)
Dec. 1981, (controls of 1981)
(medium weight gasoline fueled vehicles)
Figure 1
The Transition in the Effects of Emission Controls
for Motor Vehicle Exhaust Gas
(Average Amount of NOx Emission)
PROCEEDINGS—PAGE 26
-------
Heavy Weight Gasoline Fueled Vehicles (gross weight over 2.5 tons)
100%
Before April 1973 (not controlled)
70%
50%
^ April 1973 (controls of 1973)
August 1977 (controls of 1977)
42%
(controls of 1979)
29%
The 2nd phase
Diesel-Powered Vehicles (Direct Injection Type)
100%
Before September 1974 (not controlled)
80%
September 1974 (controls of 1974)
68%
August 1977 (controls of 1977)
56%
(controls of 1979)
49%
The 2nd phase
Diesel-Powered Vehicles (Indirect Injection Type)
100% | Before September 1974 (not controlled)
80%
Sept. 1974 (controls of 1974)
68%
August 1977 (controls of 1977)
60%
(controls of 1979)
52%
The 2nd phase
Figure 1 ( continude ) The Transition in the Effects of Emission
Controls for Motor Vehicle Exhaust Gas
( Average Amount of NOx Emission )
PROCEEDINGS—PAGE 27
-------
ANNEXES
1. The Concentration of Ox, NMHC and NOx in Kanto Area in FY 1978
2. Number of Oxidznts Warning Days
3. Number of Harning Days by Year and Month
4. Number of Warning Days by Concentration Grades in Tokyo Bay Area
5. Level of Oxidznts Concentration on Marninq Days in Tokyo Bay Area
PROCEEDINGS—PAGE 29
-------
1. The Concentrations of Oxidants(0 ), Non-methane hydrocarbons (NMHC) and
jC
Nitrogen oxides (NO ) in Kanto Area in Fiscal 1978
jC
O I monthly (yearly) average of inaxinnum one-hour value from
x 5 a.m. to 8 p.m.
NMHC I monthly (yearly) average of one-hour value from 6 to 9 a.m.
NO I monthly (yearly) average of one-hour value from 6 to 9 a.m.
SW-n.
j
i |
\fc\-
xK^
\
\
fc
NHHC
NO*
0*
HWC,
NO*
Da
i
3
\ f^HHC
NO,
' Of
4" i Ntftfc
//#/
I ftr
F HMHC
y
7
Ł
HO*
0,
t^nnc
HO,
Or
NHH-C
NO*
Of
Mac
fi/G*
111?
.
ppm]
(PP*.
ppm)
(ppm)
(ppmci
(ppm
(ppm
(ppmc
(ppm
(ppm
(ppm
(ppm
(ppmc)
ppm)
ppm)
„*
tfml
ppm)
(ppmc)
Ppm)
ppm;
(ppmc)
ppir.;
4
0.053
0.47
0.031
0.042
0.65
0.048
0.045
0.49
0.05
0.053
0.62
0.028
0059
0.72
0.01S
0.040
0,42
0.034
0028
0.73
0.067
0.039
0.56
0.047
!>
0.047
0.48
0.017
0.037
1.12
0.037
0.052
0.47
0.023
O.OG8
0.55
0.013
0.045
0.49
0.032
0.036
0.89
0.053
0.011
0.56
0.039
(,
0.037
a co
0.017
0.057
0.81
0.034
0.040
0.76
0.029
0.041
0.34
0.024
0.053
0.72
0.012
0.031
0.41
0.023
0.023
0.95
0.050
7
0.046
0.64
0.014
0.075
0.71
0.035
0.045
0.33
0.028
0.034
0.31
0.022
0.041
0.90
0.009
0.035
0.52
0.029
0.024
L15
aw
0.036 0.034
0.60 0.60
0.0390. 036
Ł
0.051
O.G9
0.017
0.062
0.72
0.035
0.045
0.40
a027
0032
0.5G
0.023
0.059
1.10
0.013
0,043
ass
0.032
0.050
1.26
0.050
0.049
0.56
0.034
*\
0.034
0.5G
0.011
0.034
0.62
0.043
0.029
0.38
0.034
0.026
O.G5
0.029
0.013
0.87
0.022
0.028
O.G1
0.041
0.027
1.08
0.057
10
0.028
a 57
0.017
0.026
0.63
0.066
0.028
0.32
0.049
0.024
0.51
0.039
0.042
0.77
0.031
0.025
0.73
0.059
0.022
1.06
0.075
0.0300.020
0.60
0.037
0.56
11
0.043
0.57
0.028
0.030
L62
0.081
0.018
055
0.077
0.028
039
0.054
0.032
0.70
0.042
a 020
0.69
0.074
0.021
0.82
0.091
0.020
0.67
0.0530.074
12-
0.029
0.55
0.057
0.035
0.98
0.134
0.027
0.77
0.096
0.021
0.69
0.090
0.038
0.77
0.062
0.018
0.70
0.112
0.018
1.00
0.182
0.021
0.83
0.140
ml
1
0.026
0.55
0.030
0.037
0.95
0.114
0.027
0.82
0.089
0.021
0.55
0.081
0.032
0.75
0.043
0.023
O.G3
0.116
0.021
0.97
0.163
0.024
0.81
0.157
1
0.040
0.62
0.04C
0.037
0.59
0.069
1
0.040
0.56
0.039
0.042
0.48
0.058
0.0290.037
0.53
0.072
0.020
0.37
0051
a 034
0.73
0.039
0.029
0.43
0.076
0.024
0.99
0.131
0.027
0.60
0.089
Ml
0.061
0024
0.30
0.041
0.048
0.80
0.031
0.029
0.30
3.060
0.030
0.73
0.100
0.030
0.49
0.075
flfj
ffl?
0.04C
0.57
0.027
0.043
0.78
0.063
0.035
0.54
0.056
0.031
3.50
0.042
0.04G
0.80
0.028
0.031
0.55
0.056
0.027
0.98
0.089
3.032
0.64
3.068
PROCEEDINGS—PAGE 31
-------
II
, >*
0*
0,
NHHc
NO?
0,
A/tff/C
;VCx
A/ AW
A/Ox
ftr
&
0*
NO,
NHHC
A/0/
. A/A/W
i
—
/rl't
ppm)
(jjpmo)
ppm)
ppm)
(ppmc)
(ppm)
(ppm)
(pprac)
(ppm
(ppm
(ppm
(ppm
(ppme)
ppm)
(ppm)
(ppinc)
(ppm)
(ppm)
(PP»)
PP«)
(ppnic)
ppm)
ppnic)
ppm)
PPm)
pmt)
ppm)
4-
0.040
0.27
0.0-18
0.032
0.36
0.039
0.042
0.23
0.066
0.023
0.055
0.024
0.84
0.071
0.043
0.74
0 066
0.045
0.30
0.039
0.054
a 053
3.063
0.38
0.025
0045
a 44
0.053
Y
a ose
0.37
0.045
0.036
0.32
0.037
0.034
0.37
0.066
0.028
0.050
0.030
0.056
0.037
0.94
0.048
0.049
0.30
0.033
0.042
0.039
0.071
132
0.018
0.047
O.G6
0.041
\>
0.040
0.31
0.043
0.024
0.47
0.034
0.043
0.68
a 054
0.018
0.050
0.022
078
0.048
0.035
0.87
0.041
0.040
0.32
0.029
0.030
0.036
3.052
0.38
0.019
0.052
a so
1038
I f
V
0.035
0.27
a 047
0.024
0.60
0.030
0.038
0.83
).041
0.018
0.048
0.025
0.81
0.048
a 045
0.80
0.046
3.044
127
1025
a 023
0.032
1070
0.48
3.019
0.052
9.49
1035
7 i
0.067
0.36
0.055
0.057
0.72
0.031
0.047
198
0.041
0.029
0.042
0.041
0.85
0.037
0.058
0.68
0.033
0.059
0.40
0.033
tt 050
0.035
1081
0.30
0.017
0.051
0.45
0.032
\ (I'M
^ /o // a i z 5
0.029
0.41
0.056
0.037
0.66
0.040
0.025
0.78
0.046
0.020
0.063
0.024
0.78
0.045
0.023
3.043
1047
138
1044
1026
0.042
0.066
0.19
0.02G
0.045
143
0.029
0.032
0.59
0.098
0.037
0.60
0.048
0.029
0.69
0.076
0.020
0.71
0.098
0.016
0.87
0.065
0.021
9.061
1047
146
0.055
1032
0.050
1055
0.38
0.033
1044
148
0.040
0.015
0.49
0.088
0.033
0.71
0.066
0.023
0.66
0.110
0.012
0.67
0.102
0.012
0.90
0.085
0.016
0.099
1040
0.64
0.080
a 022
1.02
0.071
.043
0.50
.035
0.043
151
.064
1037
0.62
0.141
U.042
0.63
0.089
0.035
0.84
0.155
0.013
0.92
0.146
0.010
1.07
0.109
0.011
1.02
1140
0.037
178
1096
0.014
133
0.100
1024
0.58
0.048
0.030
3.60
1073
0.021
0.53
0.124
0029
0.43
0.079
0.033
0.78
0.192
0.013
0.122
0.015
0.98
0.110
0.011
093
0.124
0.046
074
1101
0.023
1.35
0.088
0.020
0.83
0.055
0.027
0.52
0.082
0.013
0.46
0.101
0.024
0.33
0.065
0027
0.64
0.152
0.022
0.63
0.092
0.025
0.85
0.078
0.019
0.75
0.092
0.033
0.49
0.069
0.022
1.14
0.075
0.021
075
0.048
0.024
0.52
0.089
0.023
145
0.078
0.031
0.28
0.050
0.030
0.27
1115
0.031
0.45
3.073
0.025
0.58
0.062
0.029
0.53
1073
0.050
0.43
1065
0.036
0.79
0.060
0.036
0.56
0.035
0.047
0.45
3.069
f}'
1034
0.43
0.078
0.034
0.51
0.051
0.034
0.66
1093
0.020
(0.69)
0.079
0.023
0.85
i
0.067
0.029
0.80
0.072
3.045
147
1056
0.031
1.13
0.057
0.052
0.48
0.032
1042
151
.054
PROCEEDINGS—PAGE 32
-------
Distribution of monitoring stations where O , NMHC and NO
are measured
station
1
2
3
4
5
6
7
8
9
nvf
\ ^jf-1
\ (
o
\
TORIDE
URANA
NODA
NARASHINO
ICHIHARA
SKENJUKU
OTA
EDOGAIiZA
YOKOHAMA NO 1
stati
10
11
12
13
14
15
16
17
18
YOKOHAMA NO 2
YOKOHAMA, NO 3
KAWASAKI NO 1
KAWASAKI NO 2
KAWASAKI NO 3
YOKOSUGA
FUJISAWA
ODAWARA
ATSUGI
PROCEEDINGS—PAGE 33
-------
2. Number of oxidants warning days:
1970 - 1979
PROCEE
PROCEEDINGS—PAGE 34
^""-^-^Year
PrefecturS^^^
Miyagi
Fukushima
Ibaragi
Tochigi
Gunma
Saitama
Chiba
Tokyo
Kanagawa
Yamnashi
Fukui
Ibyama
Ishikawa
Shizuoka
Aichi
Mie
Shiga
Kyoto
Osaka
Hyogo
Nara
Wakayaina
Okayama
Hiroshima
Yamaguchi
Tokushima
Kagawa
Ehime
Total
-
'70
7
' 7
'71
23
19
33
11
1
4
7
98
'72
16
15
21
33
31
5
4
7
18
19
1
1
3
2
176
'73
3
21
10
1
45
28
45
30
8
8
6
4
17
26
23
6
1
14
9
1
22
328
'74
14
10
4
29
26
26
26
15
2
7
4
I"7
27
19
3
1
16
18
5
2
4
13
288
'75
3
17
6
11
44
33
41
27
6
6
4
11
23
11
9
5
4
1
2
1
1
266
'76
1
9
7
1
15
21
17
17
3
3
3
5
6
25
3
3
1
1
2
3
4
150
'77
18
11
26
7
21
12
1
2
1
1
9
25
4
3
5
6
5
3
7
167
'78
1
12
5
3
36
14
22
18
1
1
1
1
5
16
2
3
8
9
3
1
6
1
169
'79 '
3
2
8
11
12
19
2
1
3
5
1
12
1
1
1
2
84
-------
3. Number of warning days by year and month
1975 - 1979
1
o
"ii!
13
a <8
M
ro y
(O1 o t-i
Jtj
^
(Cj 0)
§ §
>i O
fa CD
^flj
Ł &
H 1
CN
"8 Si
>i *
ffl 4-1
(U
1 ^
0 ~
03
II
H (3 CD
•8 $ 1
LT1
"\>fonth
Year ^""v-^.
1 9 75
1976
1977
1978
1979
5-year average
1975
1976
1977
1978
1979
5-year average
1975
1976
1977
1978
1979
5-year average
1975
1976
1977
1978
1979
5-year average
1975
1976
1977
1978
1979
5-year average
4
2
6
5
4
3
2
3
2
1
2
—
2
1
1
-
5
19
21
16
28
13
19
11
10
8
14
6
10
1
—
3
5
1
5
1
3
1
4
2
1
2
6
47
22
24
22
11
25
24
6
5
8
9
10
1
-
17
6
11
4
1
8
3
6
7
4
4
7
72
29
65
58
30
51
29
15
29
25
21
24
4
1
1
19
8
12
10
1
10
3
1
5
17
1
5
8
68
47
36
48
22
44
43
23
14
38
10
26
5
2
1
7
9
10
5
8
8
2
3
3
1
2
9
52
12
12
7
8
18
32
6
2
3
4
9
1
-
6
4
4
2
3
4
3
1
4
1
2
10
6
13
8
2
6
4
7
5
1
3
-
2
3
2
1
1
-
Total
266
150
166
169
84
167
145
70
65
90
50
84
6
6
3
0
o
3
54
37
41
26
14
34
12
8
23
27
4
15
PROCEEDINGS—PAGE 35
-------
(day
20
15 '
03
Q
X -
O ' v
1975
1 9 7 6
1977
1 9 7 8
1979
10
o
s_
/ A / V1
/ c/ \/ _ \\ G
' 7 8 M a x .
r~7 5 M a x
-Ł?-
_n Q-
12 13 14 15
lb 17 18 19 20 22 23 24
Concentration Grades (pphm).
4. Number of Warning Days by Concentration Grades in Tokyo Bay Area
1975- 1979 (June- August)
25 26 27 28 29 30
31
ro
U
a
0,
I
w
0
Q
W
W
CJ
§
-------
5. LEVEL OF OXDANT CONCENTRATION ON WARNING DAYS IN TOKYO BAY AREA.
1975 - 1979 (JUNE - AUGUST)
INDEX
12 - 15 pphm
(Q) 16 - 19 pphm
() 20 - 23 pphm
More than 24 pphm
PROCEEDINGS—PAGE 37
-------
Level of Oxdant Concentration on Warning Days in
1975
Tokyo Bay Area
(June- August)
Day
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
Sai-
tana
®
o
©
©
.©
©
©
o
J U N
Chi-
ba
•
O
O
O
E
To-
kyo
®
®
O
o
©
o
o
Kanar
gawa
•
O
o
©
o
Sai-
tana
0
o
•
©
©
©
©
©
©
©
©
o
©
J U L
CM-
ba
©
O
©
O
©
o
o
Y
To-
kyo
O
i
o
•
©
o
o
Kana-
gawa
O
©
•
A
Sai-
tama
©
©
©
©
•
©
O
©
©
^-^
©
©
©
U G U
Chi-
ba
©
0
0
o
©
o
0
©
©
o
o
S T
To-
kyo
©
O
©
®
©
O
©
©
©
o
©
Kana-
gawa
;
0!
1
©
Ol
o
o
©
©
o
PROCEEDINGS—PAGE 38
-------
Level of Oxdant Concentration on Warning Days in Tokyo Bay Area
(June- August)
Day
1
2
3 !
4
5 1
6 '
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
JUNE
Sai-
taraa
o
Chi-
ba
©
0
To-
kyo
Cana-
gaira
O
i
i
•
©
O
JULY
Sai-
tana
©
"©
O
o
o
Chi-
ba
©
O
O
o
ro- K
s.yo
.ana-
gaT?a
I
©
O
o
®
O
O
AUGUST
Sai-
taraa
©
©
O
(•)
©
©
CM- 1
ba 1
©
(•)
O
O
ro- K
iyo
O
©
o
<§)
©
o
ana-
gawa
O
o
-------
Level of Oxdant Concentration on Warning Days in Tokyo Bay Area
g 7 7 (June- August)
Day
1
2
3
4
5
6
7
8
9
10
11
12
13
14
i 15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
Sai-
tama
'
o
J U N
Chi-
ba
E
To-
kyo
O
O
i
Kana-
gawa
O
O
Sai-
tana
O
0
0
(•)
(o)
©
o
©
o
o
o
J U L
Chi-
ba
O
o
'©
Y
To-
kyo
O
O
O
o
1
©
®
o
o
o
0
0
Kana-
garca
O
o
o
©
A
Sai-
tama
O
©
©
©
©
!
-
©
I' G U
CM-
ba
O
O
S T
To-
kyo
©
O
(•)
O
Kana7;
gara'
©
-------
Level of Oxdant Concentration on Warning Days in Tokyo Bay Area
(June- August)
7 8
Day
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
Sai-
tana
©
O
©
©
] U N
Chi-
ba
O
O
©
E
To-
kyo
O
Kanar
gawa
Sai-
taiaa
©
®
•
®
O
®
®
©
O
©
O
©
O
J U L
Chi-
ba
O
O
Y
To-
kyo
O
©
O
'
O
O
O
Kana-
gaira
O
©
O
O
A
Sai-
tama
©
©
©
©
©
!
©
o
©
©
o
U G U
Chi-
ba
©
O
©
o
o
o
0
S T
To-
kyo
O
©
o
0
©
©
0
o
©
0
o
Kana-
gawa
O:
®
©
©
O
o
©
©
o
PROCEEDINGS—PAGE 41
-------
Level of Oxdant Concentration on Warning Days in
1979
Tokyo Bay Area
(June- August)
1
Day
1
2
3
4
5
6
7
8
9
10
n
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
JUNE
Sai-
tama
Chi-
ba
o
o
O
o
To-
kyo
O
Kana-
gaira
0
o
©
©
JULY
Sai-
tana
O
o
o
Chi-
ba
©
0
©
o
o
To-
kyo
O
©
i
©
©
©
Kana-
gawa
0
(§)
o
o
o
©
o
©
AUGUST i
Sai-
tama
O
O
|
i
Chi-
ba
To-
kyo
©
O
i
o
o
KanaJ
gaira
i
i
*
'i
0!
i
©
oi
i
!
i
r
i
OI
'•'.
'*-.
T
•?
y
;i
•i
<
t
"1
-!
PROCEEDINGS—PAGE 42
-------
RECENT ADVANCEMENTS IN THE MODELING OF
PHOTOCHEMICAL SMOG FORMATION
presented by A. P. Altshuller
Environmental Protection Agency
United States
PROCEEDINGS—PAGE 43
-------
Recent Advancements in the Modeling of
Photochemical Smog Formation
A. P. Altshuller
February 4, 1980
During the past two years, significant progress has been made towards
an understanding of atmospheric transformation processes and our ability
to model these processes. This progress has been due, in part, to
several recent laboratory studies that have yielded new mechanistic in-
formation on key reaction processes. The information furnished in these
studies has been used to develop and refine chemical kinetic computer
models of smog formation. Most notable among these recent developments
are the followingt
(1) Until very recently it has been impossible to include aromatic
hydrocarbons in photochemical smog mechanisms. Very little was known
about the products of aromatic oxidation reactions, making it impossible to
construct a mechanism to describe the atmospheric chemistry of this
important class of hydrocarbons. In the past year, however, biacetyl
was identified as a major product of a smog chamber study of irradiated
O-xylene/NQ /air mixtures, conducted at the University of Riverside.
X 2
Based on rhls result, a mechanism was constructed for the toluene/NO
x
system, that involves oxygen addition to the initially-formed toluene-
OH adduce, followed by cleavage of the ring to yield unsaturated
dialdehydes, glyoxal and methylglyoxal. Although this mechanism is
still in the preliminary states of development and testing, it has
been usad successfully to model a number of toluene/NO experiments
conducted in the indoor smog chamber facility at the University of
Riverside and the outdoor chamber facility of the University of North
Carolina.
(2) One of the shortcomings of kinetic mechanisms in the past has been
that the mechanisms exhibited little temperature-dependency. And yet,
smog chamber data and ambient data suggest a correlation between peak
0, levels and temperature. Other conditions being equal, more 0_ is
generated on a hot day than on a cold day. Recently it was determined
that peroxyacetylnitrate (PAN), a product of photochemical smog systems and
PROCEEDINGS—PAGE 45
-------
a strong eye irritant, can thermally decompose to a free radical and
4 5
N0_. ' The rate of decomposition is extremely temperature-dependent.
Because of this temperature dependency, significant levels of PAN can
build up early in the day when temperatures are relatively cool. In
the late afternoon, when temperatures are elevated, the decomposition
of FAN can proceed at a rapid rate, liberating N0_ molecules that can
lead to enhanced ozone production. This finding has been shown to
explain a significant portion of the temperature effect that has been
observed in smog chamber studies.
Recently, data were also obtained on the relative rates of reaction
of peroxybenzoyl radicals with NO and NO- and the thermal rate of
* t
dissociation of peroxybenzoyl nitrate (PBzN) . This information has
been incorporated into the toluene mechanism under development.
(3) Several years ago peroxynitric acid (HO,N07) was identified as an
7 8
intermediate of photochemical smog systems. ' This species, and
the related organic, peroxynitrates (RO-NO-), could act as radical
sinks and affect the rate of smog formation. Recent experimental
evidence, however, has shown that the decomposition of peroxynitric
acid, ' and the organic peroxynitrates as well, proceeds so
rapidly at room temperature that these species are not a significant
sink for NO- and free radic.
pospheric modeling studies.
sink for NO- and free radicals and can be neglected in lower tro-
12 13
(4) Recently new data ' were reported for the reaction of hydroperoxy
radicals with NO;
H02 + NO -»• HO + N02
The new race constant for this reaction is a factor of six greater
than the rate constant that previously had been used in modeling
studies. The new rate constant significantly increases the rate
of photochemical smog formation and has substantially altered the
predictions of photochemical models.
PROCEEDINGS—PAGE 46
-------
(5) Recent evidence has been obtained to suggest that the reaction of olefins
with 0_ produces considerably fewer free radical species than had been
14
assumed in the past. Prior to the emergence of this new information,
photochemical mechanisms assumed that each olefin-O, reaction lead to
the formation of two free radical species. Present photochemical
mechanisms, ' which have been revised to be consistent with the new
experimental evidence, assume less than a 40% yield of free radicals
for the propylene-0- reaction. This reduced radical yield has had a
considerable impact on predictions of photochemical models.
These and other recent advancements in smog chemistry, and their effect
on the predictions of photochemical models are described in the EPA
report "Modeling of Simulated Photochemical Smog with Kinetic Mechanisms,
Volume 1" (Reference 3). This report will be available for distribution
in late February, 1980.
PROCEEDINGS—PAGE 47
-------
References
1. K.R. Darnall, R. Atkinson and J.N. Pitts, Jr., J. Phys. Chem, 83,
1943 (1979).
2. R. Atkinson, W.P.L. Carter, K.R. Darnall, A.M. Winer and J.N. Pitts, Jr
Int. J. Chem. Kinet., submitted for publication (1979).
3. G.Z. Whitten, J.P. Killus and H. Hogo, "Modeling of Simulated Photo-
chemical Smog with Kinetic Mechanisms, Volume 1," U.S. Environmental
Protection Agency Report EPA-600/3-80-028a (February 1980).
4. D.G. Hendry and R.A. Kenley, J. Amer. Chem. Soc., 99, 3198 (1977).
5. R.A. Cox and M.J. Roffey, Environ. Sci. Technol., 11, 900 (1977).
6. D.G. Hendry, R.A. Kenley, J.E. Davenport and B.Y. Lan, Quarterly Progre
Report, EPA Grant No. 806093, Project Officer Marcia C. Dodge (January
30, 1979).
7. S.W. Levine, W.M. Uselman, W.H. Chan, J.G. Calvert and J.H. Shaw, Chem.
Phys. Letters, _48_, 528 (1977).
8. H. Niki, ?.D. Maker, C.H. Savage, and L.P. Breitenbach, Chem. Phys.
Letters, 45., 564 (1977).
9. R.A. Graham., A.M. Winer and J.N. Pitts, Jr., Chem. Phys. Letters, 51,
215 (1977).
10. R.A. Cox, S..G. Derwent and A.J.L. Button, Nature, 270, 328 (1977).
11. E.G. Edrsey, J.W. Sparxce, and P.L. Hanst, J. Air Poll. Control Assoc.,
^9, 741 (1979).
12. C.J. Howard and K.M. Evenson, Geophys. Res. Lett., _4, 437 (1977).
13. C.J. Howard, J. Chem. Phys., Tl, 2352 (1979).
14. J.T. Herron and R.E. Huie, J. Amer. Chem. Soc., 99, 5430 (1977).
15. M.C. Dodge and R.R. Arnts, Int. J^. Chem. Kinet., 11, 399 (1979).
PROCEEDINGS—PAGE 48
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PHOTOOXIDATION OF THE PROPYLENE-NITROGEN OXIDES-AIR SYSTEM
STUDIED BY LONG-PATH FOURIER TRANSFORM INFRARED SPECTROMETRY
presented by M. Okuda
The National Institute for Environmental Studies
PROCEEDINGS—PAGE 49
-------
Photooxidation of the Propylene-Nitrogen Oxides-Air System
Studied by Long-Path Fourier Transform Infrared Spectrometry
Hajime Akimoto*, Hiroshi Bandow, Fumio Sakamaki,
Gen Inoue, Mikio Hoshino and Michio Okuda
.The National Institute for Environmental Studies
P.O. Tsukubagakuen, Ibaraki 305 Japan
PROCEEDINGS—PAGE 51
-------
The photooxidation of C3Hg in the presence of NOX has
been studied in dry (H,,O < 1 ppm) and humid air (R.H. = 40%
at 30°C) using an evacuable photochemical smog chamber.
Quantitative analysis of products was made in situ by a
Igng - path Fourier transform infrared spectrometer. The
concentrations for C3Hg, NO, NO2, O3, HCHO, CH-jCHO, HCOOH,
CO, CO2, PAN, PGDN (1,2— propanediol dinitrate), HNO3 and
N2°5 were determined as a function of irradiation time.
t
Addition of H2O vapor was found to increase the yield of
HCOOH markedly. The importance of the NO, radical reaction
in the reaction system is discussed. Stoichiometric factors
of NO oxidation and aldehyde formation as well as carbon
balance and nitrogen balance are also discussed.
PROCEEDINGS—PAGE 52
-------
Introduction
The photooxidation of the propylene — nitrogen oxides -
air system is an important model reaction of photochemical
air pollution, and computer simulation of the smog reaction
has been attempted most frequently for this reaction system
(1-5). As reliable kinetic data on elementary reactions
which are of key significance to the smog reactions have
recently been accumulated, the importance of obtaining
i
reliable and detailed smog chamber data for the reaction
system has increased as well, since the computer modeling
can be validated only by comparing with such experimental
data sets.
Although the phtooxidation of propylene in a smog
chamber has been studied well (6-10), reports on the
quantitative analysis of the reaction products other than
oxidant (ozone), PAN, and NO« are very few. Altshuller et
al. (7) attempted a total analysis of reaction products, and
reported the yields of oxidant, HCHO, CH3CHO, PAN, CH3ONO2
and CO. Formation of HNO3 and HCOOH are reported by Spicer
and Miller (8), and Spicer et al. (9), respectively. This
paper reports the yield of reaction products and their
formation profiles for the propylene - nitrogen oxides - air
system studied in an evacuable and bakable photochemical
smog chamber. Quantitative analysis of the products was
PROCEEDINGS—PAGE 53
-------
made in situ using an long - path Fourier transform infrared
spectrometer (LP - FTIR). The yields of HCOOH, CO2, PGDN
(1,2-propanediol dinitrate or propylene glycol 1,2-dinitrate)
HNO-j and N^O,. were determined in addition to those of the
products reported by Altshuller et al. (7). The formation
mechanism of the products, the material balance as well as
the effect of water vapor on the yield of HCOOH will be
discussed.
Experimental
Details of the evacuable and bakable photochemical smog
chamber and the experimental procedure have been described
elsewhere (10,11). Products were identified and analyzed
quantitatively by the LP - FTIR (Block Engineering Co. - JASCO
International Inc.). The multi - reflection mirrors are of
the eight - mirror system type described by Hanst (12). The
base path length.is 1.7 m and the total path number used was
130, 'resulting in a total path length of 221.5 m. The spectr
were obtained about every 20 minutes by scanning 512 times
with a resolution of 1 cm" . The, time required for 512
scannings was about 17 minutes, and thus the spectra obtained
were the average for that period. The absorption coefficient
of NO, N02, CO, CO2, HCHO, CH3CHO, HCOOH, and PGDN were
PROCEEDINGS—PAGE 54
-------
determined in this laboratory using a quartz, 40 m long -
path cell (12 cm i.d., 100 cm in length, and 11 i in volume),
which can be used with the same spectrometer by switching
the- optical path from the multi - reflection mirrors of the
smog chamber. All absorption coefficients were obtained
in the 0.1-10 ppm concentration range in the presence of
1 atm air. The pressure of each gas was measured by an
MKS Baratron capacitance manometer in a constant volume,
and then each gas was flushed into the cell with purified
air. The absorption coefficient was determined from the
slope of the plot of absorbance vs. concentration. The
absorption coefficients thus determined are summarized in
Table I together with those for PAN, HN03 and N-O- taken
from the literatures (13-15): and employed in this work. Since
absorptivity changes with absorbance for CO and CO_,
calibration curves shown in Fig.l are used to obtain their
concentrations. Estimated errors in concentration
determined in this study are also shown in Table I.
Propylene and PAN were also analyzed by automatic
sampling gas chromatographs with FID and BCD detectors,
respectively. Propylene was separated by means of a 2 m by
3 mm stainless steel column packed with OV - 1 2% on 80-100
mesh Shimalite at 100°C. PAN was separated by means of a
30 cm by 3 mm Teflon column .packed with PEG 400 5% on 80 -
100 mesh Chromosorb AW at room temperature. The sampling
PROCEEDINGS—PAGE 55
-------
3 3
volumes of C_Hg and PAN were about 5 cm and 1 cm ,
respectively. Methyl nitrate was detected by the column
for PAN, but the yield was less than a few percent of PAN
and quantitative analysis was not made. The concentrations
of O_, NO and NO were monitored continuously by commercial
•3 X
chemiluminescent analyzers. Calibration of the analyzers
has been described previously (11,16).
The purified dry air used for:the experiment•contained
less than 1 ppm of H_O and CO2. A humidifier added water
vapor when necessary. All experiments were performed at
30°C. The light intensity employed corresponded to a k,
value of 0.27 + 0.02 min"1.
Results
Identification of Products Figure 2 shows the typical
FTIR absorption spectrum of products in ratio mode (i.e.
divided by the absorption spectrum of without "contaminants"
when the C^H, (3.05 ppm) -NO (1.48 ppm) -dry air mixture was
irradiated for 257 min. The reactants and products identifia
CH-jCHO, CO, C02, CH2CO, HCOOH, PAN, PGDN, N^, and HNO.J.
The identification of N_O5 is based on the IR absorption at
PROCEEDINGS—PAGE 56
-------
1245 cm . The kinetic behavior of this peak, which will be
discussed later, supports the identification. The
identification of PGDN was made by comparison of IR spectrum
and'GC chromatogram with a synthesized authentic sample.
A note describing the identification has been reported
elsewhere (17).
Formation of CH-CO arid HCOOH in the C-,H, - NO,. - air
2 J D x
system, was reported by Pitts et al. (18)r and Spicer
i
et al (9) , respectively. Formation of HNO., identified by
a coulometric method was reported by Spicer and Miller (8).
Observation of IR absorption peaks of HNO3 in this work
and Spicer et al. (9) further confirmed the formation of
the compound for this reaction system.
In Fig.2, an unidentified IR absorption peak is appearent
in the 1090-1150 cm region, overlapping that of HCOOH.
This absorption is tentatively assigned to ozonide such as
reported by Niki et al. (19) in the dark reaction of 03,
cis-2-C4HR and HCHO. In addition to the reaction products
observed by IR absorption, trace amounts of methyl nitrate
were detected by an ECD-GC, agreeing with the result of
Altshuller et al. (7).
Product Yields Four runs were carried out either in the
presence or absence of H_O vapor and varing the initial NO,
PROCEEDINGS—PAGE 57
-------
NO, composition of NO , while keeping the initial
Ł• X
concentrations of C3Hg and NOX constant at approximately
3.0 and 1.5 ppm, respectively. Initial concentrations for
*
the runs are presented in Table H together with the maximum
yields of O3, HCHOr CH3CHO, PAN, PGDN, N2O5 and HN03.
Since the HNO3 absorption peak at 1326 cm was interfered
by H_O absorption, the"concentration was not determined
for the humidified systems. The S/N ratio for the absorption
peak of HNO3 at 896 cm was poorer and this peak was not
used to determine the concentration in this study.
Figures 3(a) and (b) show the variation of the
concentrations of reactants and products as a function of
irradiation time for the C-HJ - NO - dry air mixture (Run 1).
3 o
Similar plots for the C,H,. - NO - humidified air mixture (Run
o b
2) are shown in Figs.4(a) and (b). In Figs.3(b) and 4(b),
•
the concentrations of NO and O- are those monitored by the
chemiluminescent analyzers. The concentration of NO monitored
by the IR absorption in the dry air systems agreed within
5% with that monitored by the chemiluminescent analyzer.
In the humidified system, N02 concentration was not
determined directly in this study since the IR absorption
band of NO2 at 1603 cm" is masked by the overwhelming
absorption of H^O. The NO,, concentration estimated from
N0x- (NO + PAN .+ PGDN) is shown by a dashed line in Fig.4(b) .
PROCEEDINGS—PAGE 58
-------
Figures 5 and 6 shows the variation of the concentrations
of reactants and products for Runs 3 and 4.
Discussion
Effect of Water Vapor on Formic Acid Formation It has
been generally recognized that addition of water vapor to
the photochemical,system of hydrocarbon - NOX - air
accelerates the overall photooxidation process due mainly
to the thermal reaction to form HNO» from NO, NO,, and H.,0,
4« Ł.2.
and the subsequent photolysis of HN02 (2-5). However, the
effect of water vapor on the product distribution has not
been clarified yet. Comparison of Figs.3(a) and 4(a)
clearly indicates that the addition of water vapor enhances
the yield of HCOOH very markedly. The same result was
obtained for the C_Hg - NO- system (Runs 3 and 4). The time
profile of the formation of HCOOH suggests that this
compound is mainly formed in the reaction of O-, and C-H,..
-> Jo
Formic acid is known to be one of the final products of
ozone - olefin reactions (20-24). Although the formation
mechanism has not been well established yet, isomerization
of Criegee intermediate diradioal, -CH-OO-, has been
suggested (23-25) to give HCOOH as follows:
.O
'CH-OO >• CH0CT I " *• HCOOH (1)
PROCEEDINGS—PAGE 59
-------
Another possibility of the formation of HCOOH in ozone-
olefin reactions was suggested to be hydrolysis of some
peroxidic reaction products (21) . Oxidation of ketene is
als9 proposed to be a formation path to HCOOH (26).
In our recent study of the dark reactions of the 0~-
C2H4 and C3Hg system, it was found that the addition of
water vapor does increase the yield of HCOOH (27). Therefore,
the water vapor effect observed in the present study on the
formic acid formation in the photooxidation of the C-H.. -
-3 O
NO - air system can be ascribed to that for the C..H,. - 0,
x J b 3
reaction. Water vapor effect in ozone reactions has been
reported by Cox and Penkett (28), who observed an inhibition
of the oxidation of SO« by H0O in the cis - 2 - C.H_— O,— S00
^ ~- *• -** o j Ł.
reaction. Calvert et al. (29) proposed a competitive reaction
CH3CHOO- + SO2 ^ CH3CHO + SO., (2)
CH3CHOO- + H20 > CH3COOH + H20 (3)
to interpret the water vapor effect, and speculated on a
complex between the Criegee intermediate and a H_O molecule.
The marked increase in formic acid formation observed in
this study might, at least in part, be explained by an
analogous homogeneous or heterpgeneous reaction
•CH200- + H20 > [CH200-H20] > HCOOH + H2O . (4)
Since the complex between the H02 radical and H2O was
PROCEEDINGS—PAGE 60
-------
shown to be present (30, 31), and the calculated dipole
moment of CH2O2 (3.03D) (25) is greater than that of HO2
(2.34D) (32), complex formation between CH_0, and HLO which
Ł•Ł*!,
favors the formation of HCOOH, may be plausible.
On the other hand, as shown in Figs.2(a) and 3(a),
formation of HCOOH was found to continue even after C,H,
J b
was entirely dissipated. This fact suggests that HCOOH is
also formed from relatively stable products such as
peroxidic products' or ketene as suggested by Vrbaski and
Cvetanovic (21), and Walter et al. (26). The presence of
H2O may enhance hydrolysis, decomposition or oxidation to
form HCOOH from these compounds. Actually, enhanced
decomposition of ozonide in the presence of H_0 vapor was
recently found in our laboratory (27) . The reaction of
HCHO with OH radicals may also give continuing formation
of HCOOH, but the yield of HCOOH in the photooxidatiori of
HCHO is reported to be very small by Hanst and Gay (33).
Importance of NO, Reaction The identification of N^O^
and_PGDN in the photooxidation of the C_H, - NO - air system
*j O X
PROCEEDINGS—PAGE 61
-------
strongly suggests the importance of the NO3 reaction in
photochemical smog chemistry. As shown in Figs.2(b) and
3 (b) , N-Oj. started to appear when O, accumulated to
appreciable concentration while N02 concentration was also
high. After reaching its maximum concentration, N-O,-
disappeared as NO2 was consumed. This kinetic behavior is
consistent with that of N2O5 expected from known reactions,
NO
N2°5
H2°
wall
N2°5
2HNO.
products.
(5)
(6)
(7)
(8)
The NO3 radical is known to react with C3Hg with a
rate constant of (5.3 + 0.3) x 10~ cm molecule" sec"
(34). While the reaction path of NO3 and C3Hg has not been
reported yet, the formation mechanism of PGDN is thought to
be as. follows:
NO.
/"ITT /TJ
jCH-CH2 ,
ONO,
CH..CH - CH
°4
I 2
ONO,
CH,CH - CH0 , CH-CH -CH
3| | 2 3
ONO2 OO-
OO- ONO,
NO
NO,
PROCEEDINGS—PAGE 62
-------
NO
CH,CH - CH0 *•
3, , 2
ONO^
I
CH,CH
3j
u
r PIT — PH
i_j«_n un, ,
3| I 2
O-
CH_ - CH-CH - CH0
2 3 2
OON02 OON02
0 wn ^n -
3, ,2
Scheme I.
A study of the reaction of N20g and C3Hg which gives the
identification of the intermediate nitroxyperoxypropyl
nitrate (CH3CH(ON02)CH2OON02 or CH3CH(OON02)CH2ONO2), and
elucidates the above reaction scheme will be reported
elsewhere.
Using the equilibrium constant of reaction (6),
K = k f/'k-e = 0.8 x 10 molecule cm (33) , the maximum
—o o
concentration of the NO., radical can be calculated to be
9 -3
3.9 x 10 molecule cm from the observed concentration of
N20g "and NO_ for the run shown in Fig.2. Since the maximum
concentration of the OH radical for the same run has been
estimated to be 6.6 x 10 molecule cm (35), the relative
importance of C-jHg decay due to NO., radicals as compared to
that due to OH radical can be given as.
k1Q[OH]
5.3 x 10~15x 3.9 x 109
2.5 x 10"11 x 6.6 xlO6
= 0.13
(9)
PROCEEDINGS—PAGE 63
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OH + C.,H, >• Products (10) .
j b
The values for kfi and k.. Q used were those given by Japer
and Niki (33) and Atkinson and Pitts (36), respectively.
Equation (9) shows that for a particular phase of C3Hg
photooxidation where O^ and NO_ coexist in the appreciable
concentrations, the relative importance of NO., reaction with
C0H,- amounts to up to 13% of the OH reaction. Thus, although
J o
the average importance of N03 as compared to OH would be much
smaller than this figure, the NO3 reaction with olefins is aa
important-process which not only accounts for the appreciable
hydrocarbon consumption but also gives new types of nitrogen
containing secondary pollutants, and should be included in
future computer modeling work.
Maximum Yield of 03 In our previous study (10) of the
photooxidation of the C3Hg - N0x - dry air system at lower,
reactant concentrations ([C^H^]Q, 0.1-0.5 ppm and [NOx]Q,
0.009 r- 0.29 ppm), the maximum concentration of O3 ultimately
reached, [O,] , was found to be estimated as
J XRclX
-k, H- /k 2+ 4k V [NO ]._
I°3^ax - <12'4 ± ^ x — 2k <"
when tC3H6l0/[NOx]0 > 3. Here, KI and k2 are the rate
constant of NO2 photodissociation and the O3 - NO reaction,
respectively. Our previous' data(10) suggest that [O-
PROCEEDINGS—PAGE 64
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should be approximately 80% of the value estimated from
Eq. (11) at the ratio of [C3H6]Q/ [NOxl Q = 2 which is
employed in the present work. Using the values of k, =
—1 —i _i
0.27 min and k, = 27.5 ppm min , [O_] for Runs 1
^ J IU3.X
and 3 can be estimated to be 1.16 + 0.14 and 1.19 + 0.14
ppm, respectively, which agree quite well with the experimental
value of 1.20 and 1.30 ppm. Thus, it is to be expected
that the maximum yield of 03 in the photooxidation of the
C3Hg-NOx-dry air system can generally be predicted by Eq.
(11) when the values of k, and [NOXJQ are given.
In the humidified air system, [O-,] is found to be
J ITlcljC
slightly lower compared to the dry air system as shown in
Table H. A. higher wall decay rate of 03 in humidified air
(10) would be partly responsible for the lower [O.,]
«3 XT13.2C
values.
Stoichiometry of the Conversion of NO to NO_ Figure 7
shows the plot of the amount of NO decreased vs. the amount
of C3'Hg dissipated in the early stages of photooxidation.
From the slope of the plot, the number of NO molecules
oxidized to NO~ per C..H,. molecule, consumed was found to be
1.7 + 0.1 for the runs both in the absence and presence
of water vapor. This result agrees fairly well with the
stoichiometric factor value of 1.8-2.3 in our previous
PROCEEDINGS—PAGE 65
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study (38) of the C-H-- NO - H_O - air system and also with
JO Z
the factor of -\>2 obtained by Niki et al. (37) for C_Hx--
3 D
HONO - NOX - H2O - air system. In an earlier smog chamber
study of Altshuller et al. (7), factor values varing from
1 to 3 were reported for most of the runs with different
initial concentrations and for different stages of
photooxidation.
The fairly constant stoichiometric factor of about
2 under different experimental conditions is consistent
with the basic scheme of the proposed OH radical chain
«
mechanism (37-39).
Although the
formation of HCHO and CHjCHO in the photooxidation of the
C3H6*-NOx-air system is well known (6,7,37), the
stoiahiometry of these compounds in smog chamber experiments
has not been well established. Figure 8 shows the plot of
the yields of HCHO and CHjCHO vs the amount of C3Hg dissipate
for all four runs studied in this "work. From the initial
slope of the combined plot, the" stoichiometric factors of
(AHCHO) /-{AC3H6) = 1.0 + 0.1 and (ACH3CHO) / (AC-jHg) = 0.75 +
PROCEEDINGS—PAGE 66
-------
0.1 can be obtained. On .the other hand, the ratio of
the averaged maximum yields of aldehydes to the initial
concentration of C-jHg can be obtained as [HCHO]max/
[C3H6.]Q « 0.60' ± 0.02 and [CH3CHO]in|U/[C3H6]0 «
0.42+0.02.
Altshuller et al. (7) reported a 1.0 to 1 ratio of
CH..CHO to HCHO yields .and a ratio of [CHQCHO] /
j o nicLX
lC3Hg]0 = 0.45-0.60 in their smog chamber study of
static flow conditions. The results are in fair
agreement with the present work. Niki et al. (37)
reported that (AHCHO) / (AC-,H,) = (ACH^CHO) / (AC_H,) = 1 in
J D J OO
the OH radical initiated photooxidation of the C3Hg - HONO -
NO - air mixture. The -initial stoichiometric factor of
X.
unity for HCHO observed in the present study agrees well
with the result of Niki et al. (37) but the factor for
CH^CHO in the present study is smaller than the value
reported by them. Since the photolysis of CH3CHO followed
by subsequent reactions generated HCHO (15), a higher ratio
of HCHO to CH3CHO would in part reflect the higher rate of
photodecomposition of CH3CHO in .the present study. This
should be reasonable since the Xe arc lamps employed in
this study are richer in the short wavelength component
(<340 nm), which is efficiently absorbed by the CH3CHO
PROCEEDINGS—PAGE 67
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Literature Cited
(1) Niki, H.f Daby, E.E., Weinstock, B.f Adv. Chem. Ser.
113. 16 (1972) .
(2) Hecht, T.A., Seinfeld, J.H., Environ. Sci. Technol.,
Ł, 47 (1972) .
(3) Demerjian, D.L., Kerr, J.A., Calvert, J.G., Adv.
Environ. Sci. Technol., 4_, 1 (1974).
(4) Falls, A.H., Seinfeld, J.H., Environ. Sci. Technol., 12,
1398 (1978).
(5) Carter, W.P., Lloyd, A.C., Sprung, J.L., Pitts, J.N. Jr.,
Int. J. Chem. Kinet. 11, 45 (1979).
(6) Altshuller, A.P., Bufalini, J.J., Photochem. Photobiol.,
4_, 97 (1965), and references therein.
(7) Altshuller, A.P., Kopczynski, S.L., Lonneman, W.A.,
Becker, T.L., Slater, R., Environ. Sci. Technol., 1^
899 (1967).
(8) Spicer, C.W., Miller, D.F., J. Air Pollut. Control-
Assoc., 26_, 45 (1976) .
(9) Spicer, C.W., Ward, G.F., Gay, B.W.,Jr., Anal. Lett.,
All, 85 (1978).
(10) Akimoto, H., Sakamaki, F., Hoshino, M., Inoue, G.,
Okuda, M., Environ. Sci. Technol., 13, 53 (1979).
(11) Akimoto, H.f Hoshino, M., Inoue, G., Sakamaki, F.,
PROCEEDINGS—PAGE 68
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Washida, N., Okuda, M., Environ. Sci. Technol., 13f
471 (1979).
(12) Hanst, P.L., Adv. Environ. Sci. Technol., 2, 91 (1971).
(13) Hanst, P.L., Wilson, W.E., Patterson, R.K., Gay, B.W., Jr.,
Chaney, S.W., Burton, C.S., A Spectroscopic Study of
California Smog, Environmental Protection Agency, EPA
Publication No. 650/4-75-006, Research Triangle Park,
N.C., 1975.
(14) Stephens, E.R., Anal. Chem. 36, 928 (1964).
(15) Goldman, A., Kyle, T.G., Bonomo, F.S., Appl. Opt. 10,
65 (1971).
(16) Akimoto, H., Inoue, G., Sakamaki, F., Hoshino, M.,
Okuda, M., J. Japan Soc. Air Pollut., 13, 266 (1978).
(17) Akimoto, H., Hoshino, M., Inoue, G., Sakamaki, F.,
Bandow, H., Okuda, M., J. Environ. Sci. Health, A13,
677 (1978).
(18) Pitts, J.N. Jr., Lloyd, A.C., Sprung, J.L., "Chemical
Reactions in Urban Atmospheres and their Application to
Air Pollution Control Strategies", Proceedings of the
International Symposium on Environmental Measurements,
Geneva, October 1973.
(19) Niki, H., Maker, P.O., Savage, C.M., Breitenbach, L.P.,
Chem. Phys. Lett., 46, 327 (1977).
(20) Scott, W.E., Stephens, E.R., Hanst, P.L., Doerr, R.C.,
PROCEEDINGS—PAGE 69
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Proc. Am. Petrol. Inst., Sect. 3, 37, 171 (1957).
(21) Vrbaski, T., Cvetanovic, R.J., Can. J. Chem., 38, 1063
(1960).
(22) Atkinson, R., Finlayson, B. J. , Pitts, J.N., Jr., J. Am.
Chem. Soc. 9_5, 7592 (1973) .
(23) Kuhue, H., Vaccani, S., Ha, T.K., Bauder, A., Gunthard,
Hs. H., Chem. Phys. Lett., 38, 449 (1976).
(24) Martinez, R.I.,, Huie, R.E. , Herron, J.T., Chem. Phys.
Lett., 51, 457 (1977).
(25) Wadt, W.R., Goddard, W.A., m., J. Am. Chem. Soc., 97,
3004 (1975).
(26) Walter, T.A., Bufalini, J.J., Gay, B.W. , Jr., Environ.
Sci. Technol., 11, 382 (1977).
(27) Bandow, H., Akimoto, H., Okuda, M., unpublished data.
(28) Cox, R.A., Penkett, S.A., J. Chem. Soc. Faraday Trans.
I, Ł8, 1735(1972).
(29) Calvert, J.G., Su. F., Bottenheim, J.W., Stransz, O.P.,
Atmos. Environ., 12, 197 (1978).
(30) Hamilton, E.J., Jr., Lxi, R.-R. , Int. J. Chem. Kinet. ,
9_, 875 (1977).
(31) Hamilton, E.J., Jr., Naleway, C.A., J. Phys. Chem., 80,
2037 (1976).
(32) Carsky, p., Machacek,M.. Zahradnik, R., Collect. Czech.
Chem. Commun., 38, 3067 (1973).
PROCEEDINGS—PAGE 70
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(33) Hanst, P.L., Gay, Jr., B.W., Environ. Sci. Technol.,
11, 1105 (1977).
(34) Japer, S.M., Niki, H., J. Phys. Chem., 79_, 1629 (1975).
(35) Akimoto, H., Sakamaki, F., Inoue, G., Okuda, M.,
"Estimation of OH Radical Concentration in Propylene-
Nitrogen Oxides-Dry Air System", submitted to Environ.
Sci.' Technol.
(36) Atkinson, R., Pitts, J.N., Jr., J. Chem. Phys., 63,
3591 (1975).
(37) Niki, H. , Maker, P.D., Savage, C.M. , Breitenbach,' L.P.,
J. Phys. Chem., Ł2^ 135 (1978).
(38) Washida, N., Inoue., G., Akimoto, H. , Okuda, M. , Bull.
Chem. Soc. Jpn., 51, 2215 (1978).
(39) Giychell, A., Simonaitis, R., Heicklen, J., Air Pollut.
Control Assoc.j 24_, 357 (1974).
(40) Pitts, J.N., Jr., Calvert, J.G., "Photochemistry", Wiley
Interscience, p.368. 'New York, 1966.
PROCEEDINGS—PAGE 71
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Table I Infrared Absorptivities Employed and Estimated Errors in
Concentration Determined in This Study
Compound
HO
NO-
2
CO
C02
HCHO
CH3CHO
HCOOH
HN03
N205
PAN
PGDN
Measurement
Wavenumber
(cm-1)
1876 (Q)
1603
2177(R(8))
2362
2780
2706
1105
1326
1245
1160
1280
/a\
Absorptivity^ •'
(xlO"4ppm"1m~1)
0.821 ± 0.012
11.7 t 0.6
see Fig.la(d)
see Fig.lb(d)
1.86 t 0.06
0.468 + 0.006
9.21 Ł 0.31
10.5
17
13.9
26.6.+ 2.5
References
this work
this work
this work
this work
this work
this work
this work
(f)
Hanst(13)
Stephens (14)
this work
Notes (b)
peak to valley
peak to valley
(e)
peak to valley
peak to Q-R valley
(g)
(g)
Estimated Error^
in Concentration
(+ppm)
0.03
0.002
0.007
0.01
0.06
0.1
0.01
0.01
0.005
0.01
0.01
(a) Spectral Resolution 1 cm" , Base 10, 30°C. Given uncertainties are 2o of scattered
error only. Errors caused by adsorption on walls are not included.
(b) Peak to base line unless otherwise noted.
-------
(c) Errors estimated from base line noise and absorbance reading only (AC=AA/ctŁ).
Errors caused by uncertainty in base line due to overlap of absorption.and uncertainty
in absorptivity are not included. Errors associated with the concentration of NO
determined by chemiluminescent analyzer is estimated to be + 0.001 ppm.
(d) Absorptivity changes with absorbance.
(e) Peak to sloped base line connecting between a valley at 2720 cm" and an envelope at
-1 -4 -1 -1 -1
2670 cm . Absorptivity for peak to base line is 1.11 + 0.01 x 10 ppm m at 2706 cm ,
(f) Integrated absorption intensity for 1275-1350 cm given by Goldman et -al. (14) was
allocated to observed spectrum at 1 cm resolution.
(g) Values given in the literature were used without correction for difference in resolution
since these bands are broad.
-------
w
tt
D
H
S3
O
w
w
Table IE Initial Concentrations of Reactants and Maximum Yields of Products in the
Photooxidation of C3Hg-NOx-Air System.
1
2
3
4
C3H6
3.05
3.04
3.06
3.01
Initial
N0x
1.500
1.403
1.583
1.516
Concentration
NO N02
1.477 0.023
1.358 0.045
0.016 1.567
0.012 1.504
(ppm)
H20(a)
< 1
1.7 x'104
< 1
1.7xl04
°3
1.20
1.04
1.30
1.15
HCHO
1.75
1.82
1.92
1.82
Maximum
CH3CHO
1.30
1.32
1.18
1.32
Yield
PAN
0.75
0.64
0.76
0.59
(ppm)
PGDN
t '
0.10
0.11
0.10
0.09
N2°5
' 0 .03
0.05
0.06
0.04
HN03
0.23
n.d.(b>
0.19
n.d.
(a) R.H * 40% at 30°C.
(b) Not determined due to H20 interference.
-------
M
W
O
H
g
a
CO
I
I
Q
M
0.60
cr
1/1
o
D-
§ 0.40
o
00.20
ro
0.15
0.10 cr
o
cr
P
D
O
0)
0.05
0
1.0
2.0
3.0
4.0
5.0 (x102)
Fig. 1
Concentration x Path Length (ppm-m)
O
O
Ui
-------
O
8
w
O
H
en
I
i
nd
3"
B0.
M
z
LJ
U
40..
CD
01
a
LSI
m
CH20
CH3CHO
0_
3200 31
C0
CH20, CH2CHO,
PAN, HCOOH
PGDN
PAN
HN03
H20 A
2^00 2^0
te ld00I
-------
300
AGO
Fig. 3
100 200 300
Irradiation Time (min)
400
PROCEEDINGS—PAGE 77
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0
100
200
300
Fig. 4
PROCEEDINGS—PAGE 78
100 200 300
Irradiation Time (min)
400
-------
300
AGO
Fig. 5
100 200 300
Irradiation Time (min)
400
PROCEEDINGS—PAGE 79
-------
200
300
400
Fig. 6
PROCEEDINGS—PAGE 80
100 200
Irradiation Time (min)
300
400
-------
1.5
e
a.
a
1.0
D
2:
0.5
0
o
Fig. 7
0.25
0.5
AC3H6 (ppm)
0.75
PROCEEDINGS—PAGE 81
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Fig. 8
PROCEEDINGS—PAGE 82
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Fig. 9
AC3H6
PROCEEDINGS—PAGE 83
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1.5
Q.
Q.
0.5
0
oo;
0.5
Fig. 10
1.0
1.5
PROCEEDINGS—PAGE 84
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WATER VAPOR EFFECT ON THE PHOTOCHEMICAL OZONE FORMATION
IN THE PROPYLENE-NITROGEN OXIDES-AIR SYSTEM
presented by M. Okuda
The National Institute for Environmental Studies
PROCEEDINGS—PAGE 85
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Water vapor effect on the "Photochemical Ozone Formation
in the Propylene-Nitrogen Oxides-Air System
F. Sakamaki, H. Akimoto*and M. Okuda
The National Institute for Environmental Studies,
P.O. Tsukuba-gakuen, Ibaraki 305, Japan
PROCEEDINGS—PAGE 87
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Effect of water vapor on the photochemical ozone
formation in a propylerie-'nitrogen oxides-air system
has been studied using an evacuable and bakable smog
chamber.
Presence of water vapor enhances the photooxidation
rate appreciably. The-effects of impurity and nitrous
acid formation were 'discussed as well as the possibility
of the enhancement of the reaction rate of a certain
water-complexed free radical. The proportionality
between [O_J and IQ.,1 „ was established as in the
O ItlclX O F
case of dry system, where [O-.l_,, is the maximum ozone
•j ZucuC
concentration reached ultimately and [0,] _ is the
*3 JpS
generalized parameter related to the photostationary
state concentration of ozone in the absence of C_Hg.
The [O- ] tmcorrected for the enhanced wall decay of
•3 max
ozone in the presence of water vapor, decreased 25% at
R.H. = 50 ± 10 % as compared to that in the dry system. -
PROCEEDINGS—PAGE 88
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Although the presence of water vapor in the
atmosphere might affect the photooxidation kinetics in
the polluted or unpolluted troposphere, its effect on
atmospheric reactions has not been studied well except
for on aerosol formation.
It has been reported (1-3) that the presence of
water vapor in the photooxidation of hydrocarbon-NO —
jŁ
air system accelerates the oxidation rate of NO, and
the effect has been ascribed (3-5) to the additional
formation of OH radicals in tha photolysis of nitrous
acid formed in the reaction of NO, N02 and H2O. However,
quantitative validation of the explanation has not
been made due to the lack of reliable and systematic
experimental data. . Water vapor effect on the maximum
ozone concentration formed in the hydrocarbon-NO -air
*t
system is less certain and even a qualitative trend
has not been established yet. Thus, Dimitriades (1)
noted that maximum ozone concentration in the C,H.-NO
•W T» X
system increased slightly as humidity increased from
1.5 to 11.7 % (34°C) while Wilson and Levy (2) reported
that it decreased appreciably with the increase of
humidity in the l-C^Hg-NO system. In-the photochemical
study using a dynamic flow cascade reactor, Nieboer
and Duyzer (6) reported .that the integrated dose of
PROCEEDINGS—PAGE 89
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O.j in the C-jHg-NO^ system decreased slightly with the
increase of relative "humidity.
In our previous paper (7) , tha maximum concentration
of O3 reached ultimately, l°33raax» i*1 the photooxidation
of the C,Hg-NO -dry air system has been analyzed as
a function of reaction parameters such as light intensity
and initial concentrations of C-Hg and NO . Particularly,
in the C3Hg excess region proportionality between tO_]
and a generalized parameter, [0.,] . was presented and.
•j ps
the proportionality coefficient was proposed to be
defined as an ultimate ozone formation potential of a
specific hydrocarbon. Here, [O_] is the photo stationary
P
concentration of O3 expected under the conditions of
the same light intensity and sama initial NOV concentration
Ji
but in .the absence of C-H,.. In order to extend the
o o
above discussion of the ozone formation. potential to
the analysis of the ambient atmosphere, humidity effect
on the photochemical ozone formation has to be studied
in detail, since the presence of water vapor may
invalidate the generalized relationship presented
before .(7) .
This paper reports tne photochemical ozone formation
in the C3Hg-NO -humid air system studied by the evacuable
and bakable photochemical smog chamber. The generalized
PROCEEDINGS—PAGE 90
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relationship between [0,] and [0-] was confirmed
*5 Ulcl. jC J P
in the humidified system, too. The water vapor effects
on the NO oxidation rates. C-,HC dissipation rates and
JO
EO,] ._„ will be discussed.
J HlclX
Experimental
Reactions were carried out in the evacuable and
bakable photochemical smog chamber described previously
(7,8). A humidifier added heated water vapor to the
purified dry air (H20 < 1 ppm, NO^ < 2 ppb, THC<100 ppbc)
through a capillary. Prior to each run, the humidified
pure air was introduced into the chamber at about 770
Torr. The premeasured amounts of C_Hg and NO were
then injected into the chamber through a 1/8" o.d.
glass - lined stainless steel tube using the purified
air as carrier gas. Before irradiation was started,
the sample mixture was stirred by a fan for about 45
lain in order to attain rather uniform initial condition
of NO, N02 and HONO. All experiments were performed
at 30 ± 1 °C. The light intensity (k.^ was 0.22 ±0^02
min for the runs of humidity variation and 0.24± 0.02
w"l
min for the runs of [C3Hg]Q or 1NOX10 variation.
The concentrations of O-., NO and NO were
•J 3C
PROCEEDINGS—PAGE 91
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monitored continuously .by commercial cherailuminescent
analyzers. All data were corrected for the pressure
drop due to sampling from the chamber (^7% for a 10
hour run) . Calibration of the analyzers has been
described previously (8,9). The concentration of
C-Hg was monitored by a gas chromatograph with a 2 m
column of 2% OV-1/Shimalite at 100'C.
Ru'sttrts' 'arid: Discussion
Background Reactivity Figure 1 shows the background
ozone formation when humidified (R.H. = 50%) air with
about 0.08 ppm of N02 was irradiated in the prebaked
and ozone-treated smog chamber. Thus, NO, NO, and 03
reached a photostationary state within two minutes and
the additional O_ exceeding the photostationary level
was not formed during the first 10 hour irradiation.
Slow decay of 03 and slight increase in NO for the
first few hours would be due to the wall decay of O3/
whose rates has been determined (8) to be 0.16^0.22
hour" for the initial 0^ concentration of 0.05^0.17
ppra in the presence of water vapor. The results shown
in Pig.l is in contrast with the data presented in
Pig.6 of our previous paper (8), where photochemical
PROCEEDINGS—PAGE 92
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ozone formation exceeding the photostationary level
was observed for the N02-humidified air system. It
can be concluded from the "data shown in Fig.l, that
the photooxidation of NO does not occur in the
hydrocarbon-free system even when H2O is added to
the NO -air mixture. Therefore, the formation of O_
X «5
in the N02 - humid air system in our previous study
(8) can be ascribed to soms reactive impurity introduced
into the air with the haated water vapor.
Water Vapor Effect on the Photooxidation Rate Figure 2
shows the effect of water vapor on the maximum rate
(min"*1) of NO oxidation, (~d [NO]/[N03dt) , and on tha
max
_•}
average rate (rain ) of C3Hg dissipation due to OH
OH
radical, (-d[C,H,]/[C,H,.]dt) r, during the period
jo jo av
when the maximum decay of NO is observed. Under tha
experimental condition of [G3Hg]0= 0.20 ppm, [NO]Q Cf
0.06 ppm, [NO2]0^ 0.02 ppm, and 1^=0.22 min"1, the
decay of NO generally shows an induction except for
a few runs with high humidity. The maximum decay rate
of NO shown in Fig.2 was obtained from the maximum
slope of the linear part of the plot of In[NO] vs.
irradiation time for each run. The CH dissipation
PROCEEDINGS—PAGE 93
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rate due to OH has been defined in our previous study
(10) as the difference between the total decay rate
of C.,Hg and the decay rate due to O,. The latter was
calculated from the O^ -concentration profile and the
—17 3 —7
O.-C^Hg reaction rate constant, 1.30x10 era molecule
obtained by Japar et al.(ll). .The average C3Hg
dissipation rate was obtained from the average slope
of the plot of Equation (2) of our previous paper (10)
during the period of the maximum NO decay. During the
period, the contribution of O., to the C_Hg dissipation
was less than 10%. Detailed photooxidation profiles
from which the data in Pig. 2 were reduced are available
elsewhere (12).
As shown in Pig, 2, the decay rates of C_Hg and NO
increase with the increase of humidity. This fact is
qualitatively in agreement with the data given by
Dimitriades (1), and Wilson and Levy (2). -Diraitriades
(1) reported that N02 formation rate increased from 1.9
to 4.8 ppb min when relative humidity increased from
1.5 to 35 % (at 34°C) for the run of C2H4(1.65 ppmC)-
NO(0.50 ppra) mixture. Wilson and Levy (2) showed that
the time for NO,, and O_ to reach their maximum decreased
f» • *j
from 65 to 35 min and 100 to 55 min, respectively, when
the relative humidity was changed from 0 to 65 % (at 28°C)
for the run of 1-C4H_(4 ppm)~NO(l ppm) mixture.
PROCEEDINGS—PAGE 94
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In the present study, the CgHg dissipation rate dus to
OH radical and the maximum NO decay rate changed from
2.7 to 4.7 x 10"3 min"1 and 1.5 to 2.7 x 10~2 rain""1,
respectively, when the relative humidity increased
from 0 to 60 %. Thus, the increase of the decay rates
of CUHg and NO was both about 80%. Under our
experimental conditions, the decay of C^Hg due to OH
is still in the induction period during the period of
maximum NO decay. If we take the maximum dissipation
rate of C..H,., the increase of the rate is about 20%
J b
for the same increase of humidity.
The average concentration of OH during the period
of NO decay can be estimated from the average decay
rate of CH shown in Pig. 2,
.d[C,H.] OH
[OH1
a
where k0 is the rate constant of the OH-C,H,. reaction.
2 Jo
Using -the k, value of 2.51 x 10 cm molecule" sec
(13), the [OH]aV is estimated to be 0.73 x 10~7 ppm
{1.8 x 106 molecule cm**3) and 1.28 x 10~7 ppra (3.1 x
10 molecule cm" ) for the runs with the humidity 0
and 60 %, respectively. Thus, the increment of the
[OH] „ with the introduction of H00 at about 2.5 x 10
Ci V *••
PROCEEDINGS—PAGE 95
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ppm (R.H. = 60%), is 0.56 x 10~7 ppia. Assuming that
the formation rate of OH is .equal to the dissipation
rate, the increment of the OH formation rate can be
deduced to be 0.39 ppb min""1. Here, we take into
consideration the OH dissipation reactions,
k2
OH + C3Hg • - * products (1)
1 k
OH -»- N02 - -3— > HON02 (2)
•^ Id *•
*4
OH + NO - -7—3- HONO (3)
M
4
and the rate constants, k2=3.6 x 10- (13), k., = 1.5 x
104 (14) and k4 = 1.0 x 104 ppra"1 min*"1 (15), and the
average concentrations during the period, [C^K-] ^0.165,
l = 0.06, and [NO] = 0.02 ppm, are used to obtain the
value .
The effect of water vapor on the photooxidation
rate has been ascribed (3-5) to the additional OH radical
produced by the photolysis of the HONO formed in Reacton
(4).
k5
NO +-NO--+ H0O y " > 2HONO (4)
Ł. f. K_ 5
HONO + hV -- > OH -i- NO (5)
Then, the approximate concentration of the additional
HONO for the humid run may be estimated from Reactions
(4) and (5) as;
. 2k. [NO] {NO ] IH70]
[HONO] = - - - - - = - (H)
PROCEEDINGS—PAGE 96
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since the main homogeneous Loss process of HONO is
thought to be the photolysis. Using the rate constants.
of k5s=2.2 x 10 ppm~2 'min determined by Chan et al.
(17) and kg=i 0.2 3^ based on the data of Stockwell and
Calvert (18), IHONO] during the period of the apparent
first order decay of NO can be calculated as t4 x 10~3
ppb for the typical run of R.H. 60%. This leads us to
the conclusion that the additional OH production rate
by the photolysis of HONO is only less than 2 x 10~4
ppb min , which is more than three orders of magnitude •
smaller than-the observed increment, .0.39 ppb min .
Thus, the rate constant kg must be more than 1000 times
as great as the value obtained by Chang et al.(17) in
order to ascribe the water vapor effect to the formation
of HONO during the course of the photooxidation.
Although the HONO formation rate in our smog chamber
has not been determined, and the surface material is
different (PPA-M coat, quartz and Pyrex glass in the
present study and stainless steel in their study (17))r
such a large enhancement of the rate seems to be
implausible since the surface area-to-volume ratio
of the reaction chamber is smaller in this study (3.7
—1 —1
m against 5.4 m in their study).
On the other hand, if we assume that the
PROCEEDINGS—PAGE 97
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equilibrium between HONO, NO, NO2 and H2O has been
attained during the cource of sample introduction into
the chamber, the initial concentration of HONO is 7.5
ppb using the values of k = 1.4 x 10 ppm tain
" -
(17*, .[NO30»0.060 ppm, [NO2JQ«0.024 ppm and [H2O]
of
*"1
A
2.5 x 10 ppm. Then, the initial formation rate of OH
due to the photolysis of the HONO is 0.33 ppb min*
(k3= 0.044 min~* ) , which is close to the increment of
the OH formation rate. However, Carter etal.(19) reported i
their computer modeling study that the initial charge of HONO cou|
give good fit, and some unknown additional OH source
was neccessary to simulate their smog chamber run
and ascribed it to the "dirty" chamber, effect. The
additional production rate of OH required was (0.6-3) x
8 *~3 —I — 1
10 molecule cm s (0.15-0.73 ppb min a) , and the
lower value was required for low NO or low humidity
2C
runs. In the present study, however, the background
reactivity expressed as the NO oxidation rate ranged
—3 —1
from zero (Fig.l) to 4.4 x 10 min (Fig. 6 of our
previous paper (8)). Thus, the enhancement of NO
oxidation rate due to water vapor as shown in Fig. 2
exceeds the enhanced background reactivity accompanied
by water vapor, or the dirty chamber effect.
The third possibility is the effect of water vapor
PROCEEDINGS—PAGE 98
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on the radical reactions involved in the photooxidation.
Complex formation between free radical and H^Q has been
observed or suggested for HO2 (20,21), CH3O2 (22) and
CH2O2 (16, 23). Particularly, Hamilton and Lu (19)
found that the apparent bimolecular rate constant of
the H02 - HO, reaction increased with the increase of
H2O pressure, and ascribed the effect on the enhanced
rate of the reaction, H02 + H02'H2O as compared to the
reaction between uncompleted HO2. Although speculative
at .this stage, water vapor effect on the photooxidation
rate might be in part due to the enhanced rate of the
reaction of water-complexed free radical. In order to
access .the water .vapor effect more essentially, however,
the formation of HONO before the start of irradiation
has to be determined experimentally.
Dependence of [O^^,, on [NO-Jo and fC3Hg]0. Figure 3
shows the dependence of the maximum concentration of
O0 formed ultimately, [0-]_ •, on the initial concentrate
J O JuoJt
of NO , [NO ]n, for the three different constant initial
Jb X V
C3Hg concentration, tC3Hg]Q, in the C3H6-NOx-huraid air
(R.H. = 50±10 %) system. More detailed numerical
values of initial concentrations and [O,]_av are reported
PROCEEDINGS—PAGE 99
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elsewhere (12).. The general trend of the dependence
is the same as in the .case of dry air system reported
*
before (7) . The new evidence observed in this study
is that [O,] reaches a maximum value at around
O iUaJv
[C3H6J0/ INOX]Q^0.7 and decreases slightly as the
ratio decreases further. Although an inverse
corelation between INOl/j &&& the maximum 03 concentration
within a fixed irradiation tims at the low ratio of
[C3H6]Q/ [NOxJQ have often been presented previously
(24-26), it mostly reflects slow formation of O3 under
the condition and is not neccessarily applied to the
ultimate '[O,] - • defined here. At the lowest [C,,H,.]A/
O JtlclX • O D U
[NO ln ratio of 0.4 studied in this work ([C,H,.]n =
x u o o U
0.1 ppm, [NOx]0=0.238 ppm, and ^=0.24 min""1) the
time for O3 to reach the maximum was about 20 hours.
For such a long irradiation time, the wall decay of
O, tends to lower [O,] . Nevertheless, the decrease
j o max •
of [0,]^,^. at higher [NO ln is only slight and may
•5 Tuo^C * A v
not be observed under our experimental conditions if
the correction for the wall decay of O3 is-taken into
account. In the dry air system studied previously
(7), the dependence of [0-3 ,„ on [NO ln at the lower
j max x u
[C,Hg]Q/ [NO ]Q ratio than unity could not be studied
due to the prohibitively long irradiation time to get
t03]max'
PROCEEDINGS—PAGE 100
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Figure 4 shows the variation of [0-] „„ on [C0H..]rt
J max J O u
for a. constant [NO ]n of 0.084 ppm. The dependence
x u
agreed well with that for the dry air system(7). Thus,
l°ol~ „ increases first with the increase of [C0Hc]n
j max J o u
and then leveled off at the C^Hg excess region.
Using the data presented in Figs.3 and 4, isopleths
of [03Jmax against [C-jHg^ and [NOX]0 for a fixed ^
value can be drown as shown in Fig.5. The contour
shape is very similar to the one obtained for the dry
air system except the absolute value of [O,] _ , which
j max
will be discussed later. In Fig.5, the full contour
line except for [O,] =0.20 ppm could not.be drawn
*> itlojC
due to the sparce data points at the lower ratio of
Water Vapor Effect on [0,3 „ and Ozone Formation Potential
.j ITict «C
In our previous study (7) of the photooxidation
of the C-,H,.-NO -dry air system, [O,1 „„ was found to
j o x j max
be proportional to [0-,] in the C^H,. excess region/
j ps
-------
••V .L' */ tr 4> Air V— rwn 1
JV- T .T. /w« ~ *«JS--| Jv*^ juv-i j «
[O ] « i_ ± -±-1 2_y_ (37)
•5 P" *5V
,7
(V)
Here, k.^ is the primary photodecomposition rate constant
"1) of NO2 and k?- is the bimolecular rate constant
of the N0-03 reaction {k?=27.5 ppm*"1 min" (27)).
Figure 6 shows the plot of [03]max vs. /
using all the data presented in Pig.3. A good linear
relationship between [O-,] ^ and /[NO ]n can be seen
•j TuoX X U
except for the data points in the initial concentration
ratio region, lC,H,]rt/ [NO ]- 1.
Several data points from Fig. 4 in the C^Hg-excess region
are also included in Fig. 7. Good proportionality
between [O-] and [O.J gives,
^ lilcLX O o '
where the given error is the" "twice" of the standard
PROCEEDINGS—PAGE 102
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deviation. The proportionality constant, which may
be referred to the ultimate .ozone formation potential,
is 9.2 in the C.,HC-NO .-humid air (R.H. » 50 ± 10 % at
j o x
30°C) system as compared to 12.4 obtained in the dry
system \T) . Thus, the ozone formation potential in
the humid system is about 25% lower than that in the
dry system under our experimental conditions.
The effect of humidity on [O_]__v can further be
•3 TOclX
confirmed in Fig.8. In this series of runs, relative
humidity was varied for the fixed initial concentrations
of C3H6 and NO^, .[C3HgJ0 » 0.20 ppm, [NOX3Q= 0.084 ppm.
(Same runs as shown in Fig.2). Figure 8 shows that
[0,] decreases with the increase of the humidity.
•j iHcLX
The decrease seems to be marked between 0 and 20 % of
relative humidity, and less apparent between 20 and
60 %. At the relative humidity of 50 ± 10 %, tt^J^^
is about 25% lower than that for R.H. = 0%, which is
in excellent agreement with the humidity effect on
the ozone formation potential discussed above and
obtained from different series of runs.
Our results of water vapor effect on [0,] are
O Iud.A
qualitatively in accord with, the data of V7ilson and •
Levy (2) and Nieboer and Duyzer (6), who reported the
decrease 'of maximum O3 concentration or O, dosage with
PROCEEDINGS—PAGE 103
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the increase of humidity. However, at least a part
of the water vapor effect observed both in our study
and other studies should be due to the enhanced wall
decay of CU in the humid air (8) . Although computer
simulation to eliminate such an artificial effect has
not been applied yet, such a treatment would yield much
less water vapor effect on Ł0,1 „„. It can be concluded
J max
that the presence of water vapor does affect the rate
of photooxidation appreciably, but the effect on [O,J
•3
or ultimate ozone formation potential may not be
significant.
PROCEEDINGS—PAGE 104
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literature Cited
(1) Dimitriades, B.f J. Mr Pollut. Control. Assoc.,
1967, 17, 460.
(2) Wilson, W.E., Jr*; Levy, A, J. Air Pollut. Control.
Assoc., 1970, 20/305.
(3) Damerjian, D.L.; Kerr, J.A.; Calvert, J.G., Adv.
Environ. Sci. Technol., 1974,' Ł, 1.
<4) Falls, A.H.; Seinfeld, J.H., Environ. Sci. Technol.,
1978, 12^, 1398.
(5) Niki, H.; Daby, E.E.; Weinstock, B., Adv. Chen.
Ser., 1972, 113, 16.
(6) Nieboer, J.; Duyzer, J.H., wExperimental and
Mathematical Simulation of Photochemical Air
Pollution," in Photochemical Smog Formation in the
Neatherlands (R. Guicherit Ed.), TNO'a Gravenhage,
1978, p.89.
(7) Akimoto, H.; Sakamaki, P.; Hoshino, M.; Inoue,.G.;
Okuda, M., Environ. Sci. Technol., 1979, 13, 53.
(8) Akimoto, H.; Hoshino, M.; Inoue, G.; Sakamaki, P.;
Washida, N.; Okuda, M., Environ. Sci. Technol.,
1979, 13, 471.
(9) Akimoto, H.; Inoue, G.; Sakamaki, P.; Hoshino, M.;
Okuda, M., J. Japan Soc. Air Pollut., 1978, 13, 266.
PROCEEDINGS—PAGE 105
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(10) Akimoto, H.; Sakamaki, F.j Inoue, G.; Okuda, M.j
"Estimation of OH Radical Concentration in Propylene-
Nitrogen Oxides-Dry Air System", Environ. Sci.
Technol., (in press).
(11) Japar, S.M.; Wu, C.H.; Niki, H.; J. Phys. Cham.,
1974, 21' 2318.
(12) "Smog Chamber Studies on Photochemical Reactions
of Hydrocarbon-Nitrogen Oxides System", Research
Report from the National Institute for
Environmental Studies, R-4-78, Aug. 1979.
(13) Atkinson, R.; Pitts, J.N. Jr., J. Chem. Phys.,
1975, Ł3, 3591.
(14) Overand, R.; Paraskevopoulos, G.; Black, C., J.
Chem. Phys., 1976, 6_4_, .4149*
(15) Anastasi, C.; Smith, I.W.M., J. Chem. Soc. Faraday
Trans E , 1976,' 72, 1459.
(16) Akimoto, H.; Bandow, H.; Sakamaki, P.; Inoua, G.;
Hoshino, M.; Okuda, M, "Photooxidation of the
Propylene-Nitrogen Oxides-Air System Studied by
Long-Path Fourier Transform Infrared Spactrometry",
Environ. Sci. Technol., (in press).
(17) Chan, W.H.; Nordstrom, R.J.; Calvert, J.G.;
Shaw, J.H., Environ. Sci. Technol., 1976, 10, 674.
PROCEEDINGS—PAGE 106
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(18) Stockwell, W.R.; Calvert, J.G., J. Photochem.,
1978,' Ł, 193.
(19) Carter, W.P.L.; Lloyd, A.C.; Sprung, J.L.; Pitts,
J.N. Jr., Int. J. Chem. Kinet., 1978, 11, 45.
H
(20) Hamilton, E.J., Jr; Lu, R. -R., Int. J. Cham.
Kinet., 1977, 9_, 875.
(21) Hamilton, E.J., Jr.; Naleway, C.A., J. Phys. Cheiru,
1976, 80., 2037.
(22) Kan, C.S.; Calvert, J.G., Chem. Phys. Lett., 1979,
63_, 111.
(23) Bandow, H.; Hatakeyama, S.; Okuda,'M.; Akimoto, H.,
unpublished data.
(24) Altshuller, A.P.; Xopczynski, S.L.; Lpnnaraan, W.A.;
Becker, J.L.; Slater, R., Environ. Sci. Technol.,
1967,' 1., 899.
(25) Glasson; W.A.; Tuesday, c.s., Environ. Sci. Technol.,
1970, Ł, 37.
(26) Dimitriades, B., Environ. Sci. Technol., 1972, 6^
253.
(27) Wu, C.H.; Niki, H.,.Environ. Sci. Technol.r 1975,
9, 46.
PROCEEDINGS—PAGE 107
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Figure Captions
Fig.l Background reactivity of humidified air with 0.084
ppm of NO . R.H. = 50% at 30°C, k, = 0.24 rain""1.
2k JL
Fig. 2 The effect of water vapor on the maximum decay
rates of CgHg <©) and NO (A). [C3Hg]Q = 0.20,
[NO] flAŁ 0.061, [N02]<* 0.024 ppm, 3^=0.22 ±0.02
min
Fig. 3 Dependence of ŁO«] ' on [NO ]n for the constant
A U
initial concentration of C.,Kg. R.H. ** 50 ± 10 %,
k^ 0.24 ± 0.02 min"1.
Fig. 4 Dependence of [O,l „ on [C,H.-]n for the constant
w ItlaX «3 O U
initial concentration of NOX. INOX!O~ °-084
R.H. = 50 ±10 %, klS= 0.24 ±0.02 min"1.
Fig. 5 Isopleths of [O-],,.,^ composed using the curves in
3 max
Fig. 3 and 4. R.H. = 50 ±10. % at 30°C, k-L=0.24±
0.02 min"1.
Fig.6 Plot of IQ.,1 vs. /[NO 1n . The absciassa is
•j Iu3. jŁ jŁ \J
in a square root scale. Symbols are the same as
in Fig.3.
Fig.7 Plot of 10,1 -vs. to.] Symbols (O,D,A)
J IHa^k -J c*^
are the same as in Fig. 3. The data in Fig. 4 are
denoted by V.
Fig.8 The effect of water vapor on [°3]max- Runs are in
common with those shown in Fig.2, [C3H6]Q= 0.20,
Q^ 0.061, tNO23Q^ 0.024 ppm, ^=0.22 + 0.02 min*"1,
PROCEEDINGS—PAGE 108
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5 10
Irradiation Time (hour)
15
-------
CH20] (torr)
5 10 15
- 2
10
20 30 40
R.H. (%) at
50
30*C
60
70
PROCEEDINGS—PAGE 110
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[NOX]0
PROCEEDINGS—PAGE 111
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Q25
0.1
0.2
0.3 0.4
(ppm)
0.5
PROCEEDINGS—PAGE 112
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PROCEEDINGS—PAGE 113
-------
0.4
03
Q.
CL
0.2
0.1
1
O
O
A A
1
o
Q01
0.05
[NOX]0
0.10
(pprn)
0.20
0.30
PROCEEDINGS—PAGE 114
'
-------
o
O
A
A
ai
o
l
1
0.01 0.02
t03]ps.
0.03
(ppm)
0.04
PROCEEDINGS—PAGE 115
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6
0.2-
Ł
ex
D.
X
a
JE
CO
o
0.1
0
10
20
30
40
50
60
R.H. at
30 DC
PROCEEDINGS—PAGE 116
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ozone exhaust -,
-high pressure
xenon arc lamp
Solar
• Simulator
stirring fan
multi-
ref lection
mirrors
FTIR
Spectrometer
critical flow orifice
sample outlet |
(^[-sample inlet
^Cylinders
Gas |
Analyzers^
Chromaicgraphs
Analyzers
PROCEEDINGS--PAGE 117
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INTERCOM?ARISON OF VARIOUS METHODS TO
MEASURE NITRIC ACID AND OTHER NITRATES
presented by B. Dimitriades
Environmental Protection Agency
United States
PROCEEDINGS—PAGE 119
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Intercomparison of Various Methods to
Measure Nitric Acid and Other Nitrates
B. Dimitriades
February 5, 1980
Evidence obtained in the US in the last 3 years indicated that nearly
all ambient particulate nitrate measurements are in error because of
positive and negative artifact formation. It is generally believed now
that positive artifacts are caused by retention of nitric acid and/or
conversion of N02 into nitrate on filter. Such artifacts occur on glass
fiber but not on Teflon filters. Negative artifacts are caused by on-
filter volatilization of volatile nitrates (i.e., NH.NO,) as well as by
T" 3
on-filter displacement of HN03 by H^SO.. Negative artifacts occur in
all filters and increase in magnitude with sampling time. Besides
particulate nitrate measurement, these latter volatilization and displacement
phenomena affect also nitric acid measurements whenever such measurements
are done by capturing nitric acid in a collection medium following a
pre-filter for particulate nitrate removal. Thus, volatilization or
acid-displacement of nitric acid through the pre-filter will cause
erroneously high nitric acid results. In addition to the artifact-
related errors, the measurement of nitrates is also affected, of cource,
by other factors such as interferences, instrument instability, etc.
In the face of these problems, it became of interest to USEPA to intercompare
the various existing methods for HN03 and nitrate measurements, and to
determine, if possible, whether the errors caused by the above factors
vary with analytical procedure and analyst and to what degree. A methods
intercomparison study was then designed in a workshop conducted in
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Southern Pines, NC, on Oct. 3-4, 1979 (workshop report attached), and
implemented in the Los Angeles basin in the summer of 1979. The participating
analysts brought with them and operated their own sampling and analysis
instrumentations. The intercompared methods were:
HN03:
1. Microcoulometric measurement of oxidants in air sample before and
after scrubbing HN03 out with a Nylon column (Battelle)
2. Chemi luminescence measurement of NOV before and after HN07 scrubbing
X «3
(Battelle)
3. High sensitivity chemi luminescence measurement of NOX before and
after HMO., scrubbing (Stedman, U. Mich.)
4. Collection of HNO- on Nylon, extraction, conversion into nitrobenzene-
measurement fay GC-EC (Monsanto, Un. Colo.)
5. Collection of HN03 on Nylon, reduction to MH4 , measurement by
indophenol method (Lazarus, NCAR)
6. Collection of HNO, on MaCl -impregnated cellulose filters, extraction,
measurement by hydrazine reduction-diazotization (Brookhaven-
Neuman)
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7. Direct FTS-LPIR (1km) measurement of IR (Harvey Mudd College, kok)
8. Collect HN03 in Nylon, extract, measure by ion chromatography
Particulate Nitrate:
9. Hi-Vol preceded by HN03 scrubber (Quartz filter)
10. Dichotomous sampler (Teflon filter)
11. Denuder Difference Experiment (DDE), i.e., parallel assemblies of
pre-filter and HN03 collector, with and without an acid denuder
preceding the pre-filter
While results from the intercomparison study are still being analyzed,
there are indications that the artifact errors are reduced when measurements
are made by the DDE nethod and the acid denuder and sample flow conditions
are designed for optimum sample residence time. Additional indications
are:
On glass fiber filters, positive particulate nitrate artifact
seems to dominate the negative artifact (volatilization)
On Teflon filters, negative artifact can be as much as 50% of
nitrate collected in 12-hour samples, and probably less for
shorter sampling times
PROCEEDINGS—PAGE 123
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Negative (volatilization) artifact varies widely from sample
to sample. This creates a problem in measurement of HNO^
because, the pre-filter releases an undetermined amount of
HN03.
Final report on the 1979 intercomparison study will be issued in the
fall of 1980.
PROCEEDINGS—PAGE 124
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RECENT DEVELOPMENTS IN MEASUREMENT METHODS IN JAPAN
presented by N. Yamaki
Department of Environmental Chemistry
Faculty of Engineering
Saitama University
PROCEEDINGS—PAGE 125
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RECENT DEVELOPMENTS IN MEASUREMENT METHODS IN JAPAN
Naoomi Yamaki
Department of Environmental
Chemistry, Faculty of Engi-
neering, Saitama University
PROCEEDINGS—PAGE 127
-------
This paper will discuss briefly recent developments in
the standard measurement methods for continuous air monitor-
ing, closely connected with photochemical air pollution, as
well as other some measurement methods relating to particulate
matters.
1. Oxides of Nitrogen
In Japan, an automated colorimetric analyzer based on the
Saitzman method has been used as a monitor for NOj and NO in
the ambient air. This analyzer, automated form of the manual
analysis method, differs from a continuous-type Saitzman
analyzer employed in the U.S. The one used in Japan is an
batch-type analyzer which indicates averaged values .-of .NO2 and
NO concentration over one hour intermittently (Figure 1) .
For the measurement of NO2 , the modified Saitzman reagent is
used, and for NO, after the measurement of N02, converted N02,
which is attained through oxidation of NO in the sample air
with a KMnO^-HzSOi, solution, is measured (series-type) .
The calibration for the automated analyzer has been carried
out under the static method using a Saitzman. coefficient of
0.72 until recently.
The automated Saitzman analyzer still faces the pending
problems of uncertainty with regard to N02 collection efficien-
cy, the Saitzman coefficient, and the oxidation efficiency of
NO ->• MO2 in the oxidizing solution. In the 1970's, the
development of a chemilunrinescent NOX analyzer for measure-
ments of N02 and NO concentration has made rapidly.
In addition, it is generally Considered that the establish-
ment of a means for supplying or preparing calibration gas is
essential for reliability of dynamic calibration of an automa-
ted analyzer. Progress has also been made in this area.
Under these circumstances, a detailed technical evaluation of
the two types of the NOX analyzers mentioned above was
conducted. The results are showed in Table 1, and some
important points are described below.
For the batch-type automated Saitzman analyzer, the
evaluation using advanced standard gas generation equipment
indicated that the Saitzman coefficient (including collection
efficiency) was about 20% higher than 0.72, and it was diffi-
cult to recognize any change caused by the variation of the
PROCEEDINGS—PAGE 128
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Saltzman coefficient at a normal range of N02 concentration.
For measurement of NO, it was recognized that the oxidation
efficiency of NO was low and that reduction process from N02
to NO in the absorbing solution for N02 measurement exerted
some influence. Moreover, it was concluded that the inter-
ference of ozone and sulfur dioxide which coexist in the
ambient air is negligible at the normal level in ambient air.
This negligible level of ozone interference does not apply in
the case of a continuous-type analyzer which performs counter-
current contact of the sample gas and absorbing solution.
Detection limits for hourly values of N02 and NO concentration
were estimated to be 0.01 ppm, and the measurement precision
were estimated to have a variation coefficient of 20% or an
error within 0.005 ppm.
Cheraiiuminescent analyzers experience problems with
regard to NOa+NO conversion efficiency of the reduction con-
verter, the stability thereof, the positive interference
caused by conversion of ammonia, PAN and nitrogeneous com-
pounds to NO, and the negative interference resulting from
the quenching effect of moisture in the air. Many efforts
have been made to solve these problems along with the progress
in technological development. However, since this type of
analyzer requires dynamic calibration, it does not seem
appropriate to promote immdiate use of the analyzer widely.
The detection limit of I-J02 and NO concentration and the pre-
cision of the chemilirninescent analyzer were estimated to be
almost equivalent in terms of hourly values to those of
Saltzman analyzer.
For the dynamic calibration of the automated analyzer,
it is essential, as mentioned earlier, to disseminate the
supply and preparing device of reliable standard gas for
calibration. Although remarkable progress has been observed
recently in this field (Figure 2), further improvement is
necessary for a calibration gas for an ambient air monitor
to its wide spread use.
Based on the results discussed above, the Committee of
Experts on Criteria for Nitrogen Dioxide of the Air Quality
Subcommittee of the Central Council for Control of Environ-
mental Pollution reported its evaluation of measurement methods
for N02 and NO as follows. The Saltzman method is the most
PROCEEDINGS—PAGE 129
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practical as far as the present circumstances are concerned,
and it is advisable to perform static calibration, at least
for the time being, on the batch-type automated analyzer.
Moreover, as mentioned earlier, it may be necessary to modify
the Saltznian coefficient on the basis of above. Similarly
for the measurement of NO, appropriate corrections concerning
oxidation efficiency, etc. are required. Continued efforts
must be made to improve the reliability and practical utility
of standard gas supply. Only when the necessary prequisites
for dynamic calibration are satisfied, should standard ana-
lytical methods for continuous monitoring including the chemi-
luminescent method be reviewed.
2. Hydrocarbon 2)'3)
In July 1976, the Committee of Experts on Environmental
Standards for Hydrocarbon of the Air Quality Subcommittee of
the Central Council for Control of Environmental Pollution
submitted its report concerning a guideline for hydrocarbon
concentration in the anibient air in order to prevent the
generation of photochemical oxidant. -The guideline, in con-
sidering nonmethane hydrocarbons, encouraged the utilization
of a direct-type method, a nonmethane hydrocarbon analyzer,
a composite form of gas chromatography and a flame ionization
detector. Some regions in Japan had been conducting continu-
ous measurement of the total hydrocarbon concentration using
a flame ionization detector prior to the announcement of the
report.
In general, nonmethane hydrocarbon analyzer can be classi-
fied into two categories: one is a differential method and the
other is a direct method. In the differential method, the
concentration of nonmethane hydrocarbons is obtained as a
difference of the concentration of the total hydrocarbons in
the sample air and that of methane. With the direct method,
methane is first eluted, then immediately after this a separa-
tion column is back-flushed in order to elute the remaining
nonmethanehydrocarbons. The concentration of'nonmethane hydro-
carbons is then measured directly using a flame ionization
detector.
The direct method is more advantageous than the differ-
ential method since it is not influenced by the error on the
PROCEEDINGS—PAGE 130
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measurement of methane, and the response per carbon-atom is
almost independent on type of hydrocarbon since it employs
nitrogen as a carrier gas. Furthermore, it was found that an
analyzer using the differential method cannot perform accurate
measurements unless the concentration of oxygen in the qali-
bration gas and the carrier gas is same as that in the sample
air. These are the results of the collaborative study,
conducted prior to the above-mentioned report of the expert
committee, concerning the performance of the direct and differ-
ential methods. The study also pointed out that some steps
must be taken to improve the accuracy of measurement on the
direct method, particularly its performance in a low concen-
tration region.
In 1978, a collaborative study including basic performance
tests and actual measurement tests was carried out using three
types of direct-method analyzers. Figure 3 shows an example
of a flow chart of one of the analyzers used in the tests.
The results of the actual measurement tests of ambient air are
described below.
Measurements (hourly values) obtained during the test are
as follows:
Dec. 3,1973 - Methane - 1.49-2.57 ppmC
Jan. 17, 1979 (average 1.73 ppmC)
(Full scale range: Nonmethane HC 0.14 -4.36 ppmC
0-5ppmC) (average 1.03 ppmC)
Jan. 24, 1379- Methane 1.40 - 2.38 ppmC
Feb. 15, 1979 (average 1.67 ppmC)
(Full scale range: Nonmethane HC 0.15-3.65 ppmC
0-10ppmC) (average 0.83 ppmC)
The "apparent error", which is the difference between a
"nominal reference value" (an average of hourly values taken
with the three analyzers) and a measured value of each device
for methane was an average of -3.8 pphmC~4.5 pphmC (the
standard deviation: 1.8 pphmC~4.8 pphmC) throughout the test
period. The "apparent error" of each analyzer showed a level
which was about 3% of the average concentration of methane in
the ambient air (approximately ISOpphmC). The "apparent error"
for nonmethane hydrocarbons was an average of -3.6pphmC~3.8
pphmC, but the standard deviation of the average value was
considerably large showing 8.7 pphmC - 12.OpphmC.
In addition, regarding the relation between the concentration
PROCEEDINGS—PAGE 131
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of nonmethane hydrocarbons and the "apparent error", there was
a tendency for the "apparent error" to grow larger with the
increase in concentration (Figure 4). This may be mainly due
to the fact that some of the analyzer were able to give only
low response to a high boiling components.
For analyzer using the direct method, nonmethane hydro-
carbons are backflushed from the separation column of the gas
chromatograph and is introduced into the flame ionization
detector. Finally, a peak area of the chromatogram is obtained
using an integrator. Therefore, important factors for design
include the selection of a separation column and integrating
time of the peak area. The above implies that further develop-
ment for the direct-method analyzer is required.
2) 4)
3. Photochemical Oxidant '
In Japan, automated colorimetric analyzer which uses a
10% neutral buffered KT solution and a static calibration
method using standard solution has been commonly used for
measuring photochemical oxidant until recently. This standard
method was revised in July 1977, and two major areas subjected
to the revision were: application of a dynamic calibration
instead of static calibration, and'change in concentration of
KI from 10% to 2%.
The dynamic calibration method was employed because the
measurement with conventional static calibration had shown
excessive values when ozone of known concentration was intro-
duced. 10% neutral buffered KI solution was replaced by 2%
neutral buffered KI solution in order to decrease the inter-
ference of NO;; and as the result, experiments conducted for
the analyzers which were widely used in Japan indicated that
the interference of NOa lowered from 25% of the response
against ozone to 5%.
With the application of dynamic calibration, a method to
determine ozone concentration became a subject of discussion.
When dynamic calibration was first adopted, a method using 1%
neutral buffered KI method (JIS B7957) was temporarily employ-
ed as a primary standard. However, in the future it may be
replaced with U.V. photometry, I.E. photometry, or gas phase
titration method. In addition, a U.V. ozone analyzer, chemi-
luminescent ozone analyzer, and gas phase titration device
PROCEEDINGS—PAGE 132
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will be used as a secondary standard when dynamic calibration
is actually applied.
In conjunction with the method to determine ozone concen-
tration, the consistency of U.V. photometry and gas phase
titration method with I.R. photometry was recently investigated,
and the results have been reported. They are shown in the
following least square linear regression fit. Given error are
twice of standard deviation. Equation (1) was obtained when
03 concentration was 0.5 ppm to 5 ppm, and (2) when 03 concen-
tration was 0.05 ppm to 0.8 ppm.
[ 03 ].. v = (0.974±0.001) [ 03 ]T _ + (0.058±0.004) (1)
* _ J. • r\ •
= (0.954±0.004) [ 03 1I.R.+ (0 . 020±0. 004) (2)
In Japan, the use of a chemiluminescent ozone analyzer,
based on the reaction of ethylene and ozone, is limited to
research purposes since it employs a combustible gas, ethylene.
4 . Nitric Acid Vapor
In Japan, NaCl-impregna.ted filters are often used to
measure nitric acid vapor in the. ambient air. However, only
a few reports have been made concerning the continuous analyzer
which can trace concentration changes over a short period.
The recent study0 in the above direction will be discussed
in the following.
The study lays emphasis on investigations concerning the
method of preparing air diluted nitric acid gas of a certain
concentration. At the same time, it measured the concentration
of nitric acid vapor using a chemiluminescent NOX analyzer.
Nitric acid of low-concentration diluted by air was generated
by blending of diluted gas with a high flow rate and dry air
or nitrogen with a low flow rate which is flowing over the
surface of concentrated nitric acid forming azeotrope at about
66 wt% (36 mol%) , while maintaining the vapor-liquid equilibrium.
This method enables the steady generation of diluted nitric
acid gas with a fixed concentration for a long time when the
flow rates and liquid temperature are constant. The following
experiments were carried out in order to determine whether the
diluted nitric acid gas generated by the above method can be
PROCEEDINGS — PAGE 133
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measured quantitatively with a chemiluminescent NOX analyzer
utilizing a molybudenum carbide converter which was recently
developed in Japan.
The experiment has shown that conversion efficiency of
the converter increases as the temperature rises up to
approximately 230°C and exhibits plateau at higher tempera-
tures (Figure 5). The measured values obtained with the NOX
analyzer and wet chemical analysis correspond in 1:1 ratio
within the range of those with wet chemical analysis(Figure 6) .
As the result, it was concluded that nitric acid vapor can be
quantitatively measured with a chemiluminescent NOX analyzer
when the teirtperature is over 230°C. Concentration changes of
nitric acid vapor according to variation in flow rates are
shown in Figure 7.
Nitric acid vapor in the ambient air can be measured by
obtaining differences in the readings of the chemiluminescent
NOx analyzer between sample gas which has passed through filter
of pclyaziide such as nylon, known to selectively adsorb nitric
acid vapor, and that which has not passed through the filter.
For tha application, it is considered'that adsorption
characteristics of pollutants which respond to the chemilumi-
nescenc NOX analyzer to polyaraide filters should be clarified
from the aspect of interference.
5. Suspended Particulate Matters
The environmental standard in Japan for suspended particu-
late matters in the ambient air is provided by hourly values
and a daily average of these values. Since hourly values were
difficult to measure using the commonly-used filter collection
method, it was considered appropriate to employ a relative
concentration measurement method which showed values correspond-
ing linearly to the mass concentration obtained by the filter
collection method. A light scattering dust meter was employed
to satisfy the above conditions (June, 1972). Because it is
troublesome to convert relative concentration into mass concen-
tration, studies concerning the piezo balance method and 6-ray
absorption method have been carried out. However, they have
not yet been concluded.
Recently in Japan, there has been growing interest in
particulate matters as an atmospheric pollutant, and various
PROCEEDINGS—PAGE 134
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studies concerning measurement methods related to the above
have been actively conducted. This paper will describe thin
metal-film type instrument for acidic particle concentration,
thought to provide a unique measurement method, instead of
going into any individual studies.
^Development of the above-mentioned instrument was initi-
ated because it was observed that particulate matters in the
ambient air erode and damage the metal films such as silver,
copper, and iron when photochemical smog is occurred.
In addition, acidic particles such as sulfuric acid mist were
assumed to be a major cause. The instrument has an advantage
that the amount of erosion resulting from collection of acidic
particles onto the iron film is quantitative. The iron film
is made by vacuum evaporation of iron of more than 99.99%
purity on a long polyester tape and the thickness is 500±30JU
The sample air was collected hourly using an impactor, and
the amount of erosion, caused to the iron film by acidic parti-
cles contained in the collected particulate matters was measured
by the increase in light transmittance. Concentration of
acidic particles was determined with sulfuric acid equivalent.
The schematic diagram of the instrument is shown in Figure 8.
Figure 9 indicates the calibration curve obtained using sulfuric
mist generated through a standard aerosol generating device.
The measurement sensitivity was 0.5 yg/m3. Concentrations of
acidic particles in the urban ambient air measured with the
above-mentioned instrument are shown in Table 2. Study has
been conducted concerning elemental composition of a very small
amount of particulate matters ^collected on the 2 mmc}) circular
thin iron film using energy-dispersive x-ray analysis.
The results for the same samples used for Table 2 are shown
in Figure 10.
PROCEEDINGS—PAGE 135
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REFERENCES
1) "The Expert Committee Report on Criteria for Nitrogen
Dioxide", by Expert Committee for Criteria of Nitrogen
Dioxide, Air Quality Sub-committee of the Central Council
for Environmental Pollution Control. March 20,1978,-
Journal of Japan Society of Air Pollution, 13, 118 (1978)
2) "Report on Guideline of Hydrocarbon Concentration in
Atmosphere for the Prevention of Photochemical Oxidant",
by the Expert Committee for Environmental Quality Standard
concerning Hydrocarbon, Air Quality Sub-committee of the
Central Council for Environmental Pollution, Reference
Material, July 30, 1977, ibid., 12_, 261 (1977)
3) "Study on Accuracy and Precision of Air Monitoring Instru-
ment (Comprehensive Analysis of Automated Analyzers for
Nonmethane Hydrocarbons", March 1979, Report on Work
Commissioned to the Environment Agency for FY 1978, Tokyo
Metropolitan Government.
4) "Dynamic Calibration Manual of Automated Oxidant Analyzer",
by Planning Division of Air Quality Bureau, Environment
Agency, July 1977, Journal of Japan Society of Air Pollution,
13, 370 (1973)
5) H. Akinoto et. al., ibid., 12, 266 (1978)
6) I. Iwanoto et. al., "Measurement of Gaseous Nitric Acid in
the Arnbient Air Generation of Low-concentration Gaseous
Nitric Acid for Calibration", 20th Conference Abstracts of
Japan Boc?.-.t^ of Air Pollution, p.461, Nov. 1979.
7) K. Honma , "Report on Measuring Method for Ambient Air Pollutants"
J.P.H.A, 60 (1976)
PROCEEDINGS—PAGE 136
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Table 1. Characteristics and Performance of the Saltzman Analyzer and Chemllumlneacent Analyzer
8
n
w
w
D
H
2
a
en
i
I
H3
s
U)
— — ^_
Item
Method
Required time for measurement
0 *
•H
to
^0 cr
•H J3
,, 1 1 J
cd a)
(1) Span/Mid-point
(2) Zero
**
Detection limit
(hourly value)
Variation coeffi-
cient obtained
from the measure-
ment of ambient
air by the plural
analyzers
Average time of
the measured
value
one hour
2A hours
Saltzman coefficient
Interferences
Oxidation efficiency in the
oxidation bottle
Saltzman Analyzer (batch type)
Intermit tent (one
minutes)
hour
or thirty
Static calibration by equivalent
NaN02 solution, or dynamic
calibration by standard gas
Zero adjustment by absorption
solution or zero gas
~^~- ^^^^ N0/N02
By the Environment
Agency (1978)
NO
11 ppb
N02
10 ppb
The limit for N02 was lOppb in the
continuous- type (the U.S. Environ-
mental Protection Agency, 1.975).
Number
of
analy-
zers
6
6
Nutnbel
of
con-
due Uer
days
10
10
NO
AVP-
rage
value
(ppm)
0.03'J
D.037
Varia-
tion
r.oc rr i-
cien t
U)
16
.1.1.
M02
Avc- Varia-
ragc : Lion
value ! :op.ffi-
(ppm) icicnl:
0.049
0.049
1L
9
0.86+0.03 including collection
efficiency (>98%)
Oa normally
S02normally
no effect
no effect
70% (60 - 80%)
Chemiluminescent Analyzer
Continuous
(within one
Dynamic calibration by
Zero
minute)
standard gas
gas or stopping ozone generation
Study^
By tt
j Ag_en_c
By tl
mentf
Af'/HK
Numlip.t
of
analy-
5
5
N0/N02
^— _
le Environment
.y (1*78)
le U.S. Environ-
il Protection
:y (1975)
Number
of
con-
ductec
days
JO
10
NO
Ave-
rage
va 1 uc
0.032
0.02R
-
Varia-
tion
coef f i
c ien t
15
8
NO
5 ppb
NO 2
8 ppb
12 ppb
N02
Ave-
rage
-value
(ppm)
0.036
0.036
Varia
tion
coeffi-
cient
11
12
C02 normally no effect
1I20 -5% ~ -18% of NO concentration under
a saturated condition at 25°C
-
-------
.EEDINGS — PAGE 138
NOz reduced in the NOz absorption
bottle
Performance of the reduction
converter
8% (7 - 10%)
N02 reduction efficiency
NHj conversion efficiency
PAN conversion efficienty
f Static calibration is presently used in both span and zero calibration for the Saltzraan analyzer.
** The figures were obtained as the lowest measurable values with the variation coefficient under 50%
according to the results obtained by the plural analyzers.
>95%
<5% at 10 ppm
-100%
-------
Table 2. Concentration of Acidic Particles
(Tama Area, Oct. 23, 1976)
Difference in - H2SO.» concen-
transmittance collected tration
6
7
8
9
10
11
12
13
14
15
Time
- 7
- 8
- 9
- 10
- 11
- 12
- 13
- 14
- 15
-' 16
(AC/M)
2
2
3
3
4
5
3
2
2
2
.4
.1
.6
.7
.7
.6
.7
.6
.4
.5
X
X
X
X
X
X
X
X
X
X
10"3
"*" 3
10"3
10~3
10~3
— 2
lO"3
•" Q
10~3
^ o
(mg)
0
0
1
1
1
1
1
0
0
0
.8
.7
.2
.2
.6
.9
.2
.9
.8
.9
(mg/ra3)
1
1
2
2
3
3
2
1
1
1
.6
.4
.4
.4
.2
.8
.4
.8
.6
.8
* Air sampling volume: 10Ł/min x 50min=500Ł
PROCEEDINGS—PAGE 139
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Trap
NO oxidation bottle
Particula
: filter
Sample air
absorption
bottle(Impinger)
XO absorption
bottle(Irapinger)
Optical filtef
Light ca
Flow control
valve
r-i
" Farticulate
tf t
I>7) Suction pump
Level detector
/
/ Optical filter
V
y
'Light detector
Flow of solution
"low of gas
Elec.tric circuit
Yi~W Solenoid valve
Figure I. An Example of Schematic. Diagram of Batch-type
Automated Saltzman Analyzer
PROCEEDINGS—PAGE 140
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1. Primary Standard (High-Purity Gas)
2. National Research Institutes(Determination of Purity)
3. Guidance and supervision by the Government
4. Secondary Standard (High-Purity Gas)
5. Public Inspection and Testing Institutes (Determination of Purity)
6. Guidance and supervision by the Government (Gravimetric Blending Method)
7. Confirmation of purity by public inspection and testing Institute.'!
8. Preparation, and determination of concentration and composition by
public inspection and Tea ting Institutes
9. Primary Standard Gases (Blended Gas)
10. Checks of coordination
11. Guidance and supervision by the Government
12. Standard preparing Device for Calibration Gar,
(Dynamic Blending Method)
13. Public inspection and testing institutes
14. Confirmation of performance by public inspection and testing institutes
15. Instrument Makers or Users 13
16. Preparing Devices for Calibration Gas
17. Confirmation of Concentration by Public Inspection and
Testing Institutes ,,-
18. Standard Gases (Blended Gas, Zero Gas)>
19. Standard Gases (Blended Gas; High Grade, General Grade)
20. Standard Gases (Pure Gas)
21. Gas companies or users
22 Calibration of concentration meter or scale adjustment
23. Users
§
o
w
w
D
H
2
Q
Cfi
1
I
11
21
23
Figure 2. Schematic Diagram of Inspection and Testing System concerning
Standard Gas and Preparing Devices for Calibration Gas
w
H
tt^.
-------
° Sample
{><] o Standard gas
O Hydrogen.
HC trap
Ł<[] o Ni
Nitrogen
PCtPrecolumn • EC : Empty column B : Pressure regulation
DC : Dunnny column MS : Molecular sieve valve
MC : dain column R : Restrictor SV: Solenoid valve
C C : Choke column
Figure 3. An Example of Nornnethane Hydrocarbon Analyzer
based on Direct Method
PROCEEDINGS—PAGE 142
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iverage of
'parent error"
md the standard 1C
Wation
Iverage of
insured values
"Apparent error" = measured valu
by each analyzer at a certain
time(X) - "nominal reference
value"(Y)
"Nominal reference value"(Y) =
Average of hourly values
obtained by three analyzers at
the same time as the above X.
Coticencrstion levels of "nominal reference value"(Y)
Figure 4. Relations of Average of "Apparent Error" and the Standard
Deviation with Concentration Levels of Nonmethane
Hydrocarbons
PROCEEDINGS—PAGE 143
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I
04
ffl
m
a
o
a.
03
0)
U
c
0)
o
0)
0)
0.28
0.26
0.24
0.22
0.20
175 200 225 250 275 300
Converter temperature-{"C")
Figure 5 Effect of tessperature on the efficiency of
converter for HNO, to NO
a
cu
a
m
c
o
a
01
o
Pi
0)
o
c
0)
U
CD
o
c
-H
3
rH
U
1.0
0.8
0.6
0.4
0.2
0.2
0.4
0.6
0.8
1.0
Chemical analysis Response (ppra)
Figure 6 Chemiluminescence Response vs. Chemical analysis
Response
PROCEEDINGS—PAGE 144
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Pi
0
n
o
Pi
n
o
o
u
0
o
m
ffl
0)
jc
U
0.8
0.6
0.4
0.2
0.5
1.0
1.5
2.0
2.5
Dilution Ratio x 10
3.0
3.5
Figure 7 Cheroiluminescence Response vs. Dilution Ratio
PROCEEDINGS—PAGE 145
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1. Light source
2. Lens
3. ND filter
4. Position of a sampling head
at the time of measuring
plank and transaittance
5. Lens
6. Photomultiplier tube
7. High-voltage source
8. Integration circuit for
photoelectric current
9. , Wave reform circuit
10. Operational circuit
11. Printer
12. Timer
13. Automatic-feed device
14. LAMP circuit
15. Flowmeter
16. Suction pump
Figure 8. Schematic Diagram of Instrument for Concentration
Measurement of Acidic Particles Using the
Thin Metal-Film Method
PROCEEDINGS—PAGE 146
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OJ
U
Y=3.0 x 10~3 X
r: 0.993
(yg)
Figure 9. Calibration Curve obtained by Sulfuric Acid Mist
PROCEEDINGS—PAGE 147
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0 s
A Cl
• Aerosol
IShr.
Figure 10. S and Cl Components in Particulate Matters
PROCEEDINGS—PAGE 148
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RESEARCH ON SULFATE, NITRATE AND
NITRIC ACID IN KANTO AREA
presented by T. Okita
Study Group of the Mechanism of the Formation of
Acid Precipitation, Air Quality Bureau
Environment Agency
PROCEEDINGS—PAGE 149
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I. Horizontal and Vertical Distributions of SO. , HNO-., NO., and
Other Pollutants as Measured in 1977-1978
2- -
I.I. Horizontal distribution of SO. , HNO3, NO^ and other
pollutants in urban plume
In June and July of 1975 through 1978 three dimensional study*
of trace constituents in the atmospheric boundary layer was made
in the Kanto area. The constituents involve gaseous components
such as SO-, NO, N00, HNO_, NH,, HCHO and oxidants, and aerosols
1 « 4-
and their components such as S04 , NO-, Cl and NH..
In Fig. 1 the horizontal distributions of the constituents
when major wind direction was south to south-east, i.e. their
aean concentrations at 15 ground stations together with two
Mountain sites on June 28, 1977 and June 30, July 3, 4, 6 and 7
in 1978 are shown. The sampling of the constituents was done
between 10 a.. M. and 4 ?. M. and the air trajectories are shown
in Fig. 2.
The figures show that at the downwind area -of the Tokyo-Yokohama
large urban area and of heavy industrial areas the concentrations
2- - +
of N0_, HNO,., HCHO, oxidants, total aerosols, SO. , NO., and NH.
are usually higher than in other areas with the exception of
ilune 28, 1977. In the map of July 4, 1978 the hatch indicated
the area in which about 1,500 complaints of eye and throat
irritation were reported and some others also complained at Nerima,
lOkyo. Noon temperature sounding on July 4 at Tokyo indicated
shallow mixing layer of 450 m in thickness in comparison with
the thickness of 1450 and 800 rtt on July 6 and 7 respectively.
From the data of June 28 of 1977, June 30, July 3, 4, and 5
of 1978 in Fig. 1 the variations of the concentrations of the
constituents along the air trajectories passing through Kawasaki,
Chiyoda, Urawa, Kumagaya and Maebashi are constructed in Fig. 2.
The patterns of the concentration variation have the similar
characteristics as follows.
NO: Usually NO concentration had a peak at Kawasaki and
then decreased except June 28, 1977.
NO-: The peak of NO2 concentration usually occurred at Chiyoda.
HNO-.-and oxidants: Peak HNO-, and oxidant concentrations
were usually seen at Urawa or Kumagaya. But on June 30
and July 6, 1978 peak HNO.. concentration was observed
PROCEEDINGS—PAGE 151
-------
at Kawasaki.
NO -. Aerosol NO~ concentration had no specific peak sites.
HCHO: HCHO concentration rapidly increased between
Kawasaki and Chiyoda and later on it was somewhat fluctyi-
ated.
NH3 an(* NBf : NH3 and M^ concentration increased along the trajectory. -
304 concentration had two patterns, i.e., in one case there was not
much difference of the concentration along the trajectory on days when
relatively high SO'4 concentration was observed over wide area
(June 30, July 3 and 4, 1978) and in another SO ~ con-
centration gradually increased at downwind sites.
Total aerosol: There was not much variation of total
aerosol concentration.
SO^: SO- concentration was high at Kawasaki and Maebashi
probably due to local sources.
1.2. Relations between, the concentrations of HNO,, N0_ and
oxidants taken from the data of 1977
In 1976 it v;as found that at Ohira HNO-> concentration was
closely associated with those of NO~ and oxidants.(1) In 1877
HNO3 concentration was also measured at 15 stations in Kanto
area.
The relations between the concentrations of the three
gases shown in Fig. 4 indicate that HNO, concentration was more
closely associated with oxidant* concentration than that of NO,,
and that different station had different relations between the
concentrations of the three gases. One attempt to elucidate
the relation between HNO.,, N02 and oxidant concentrations is as
shown in Fig. 5 indicating the relation between the mean con-
centrations of NO_ and oxidant when HNO- concentration of
3.0-4.9 ppb was observed. Data are taken from the results
obtained in 1978 as well as in 1977. It is found that in the
urban and incustrial areas (for example, Chiyoda, Kawasaki and
Hiratsuka) relatively high HNO3 concentration occurred with
lower oxidant but higher NO2 concentration. On the other hand,
at rural area (for example, Urawa, Tochigi and Keisen) the same
PROCEEDINGS—PAGE 152
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level of HNO occurred with higher oxidant but lower
concentration.
1.3. Vertical distribution of trace constituents in the"
boundary layer. The measurements of trace constituents
in the boundary layer of the height between 500 and 1500 .m
were made on board a helicopter on July 4 through 7 in.
1978. The route of the helicopter was as shown in Fig.6.
Fig. 7 shows the vertical distributions of NO , NHO.,, NH ,
2— - +
oxidants, SO. , NO, and NH. composed from the helicopter measure-
ment and ground level measurement at Urawa, Kumagaya, Tatebayashi
and Tochigi. Besides oxidants the concentrations of the con-
stituents usually decreased with increasing height. Although
the measurements in 1976 and 1977 revealed uniform distribu-
tion or peak concentration at several hundred meters above the
T_ _ +
ground with HNO.,, S07 , NO., and NH., in 1978 no such distri-
bution usually occurred.
(1) T. Okita and S. Ohta (1979): Measurements of
nitrogenous and other compounds in the atmosphere
and in cloud water: A study of the mechanism of
formation of acid precipitation. 'Nitrogenous Air
Pollutants, Chemical and Biological Implications.
ed. by D. Grosjean, Ann Arbor Sci. Publ. Co..
PROCEEDINGS—PAGE 153
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II. Methods of Measurement of SO^~~, HNC>3 and NO3 in 1977 —
1978
2— —
II. 1. Methods of measurement of particulate SO. and NO^
on the ground
At ground level stations particulates were collected on
Palleflex quartz fiber filter 2500 QAST of 8X10 (inch)2 using
a high volume air samplers between 10 A. M. and 4 P. M.. .
After the sampling one fourth of the filter was cut into
pieces and put into a 200 mL flask. After adding 100 mL of
water the flask was vigorously shaken for 10 min. Then the
sample solution was filtered through a Millipore filter of pore
size of 0.3 jum. The 60 mL of filtrate was served for sample
solution.
Sulfate was determined by the glycerine-alcohol method.
Glycerine-alcohol method
(1) Reagent..
a. Powdered BaCl2 ( 20—30 meshes) .
b. 1:2 (v/v) mixture of glycerine and 95 % ethanol.
c. 5N EC1.
2-
d. Stadard SO,, solution prepared by dissolving dried K~SOA
** 2—
into water. 1 mL of the standard solution= 100 ug SO. .
(2) Procedure.
10 mL each of sample water and standard solution was put
into test tube, 1 mL of 5N HCl, 2 mL of glycerine-alcohol mixture
and about 0.1 g of Bad- powder were added and the tube v/as
shaken until all the powder wa$ dissolved. After standing for
20 min the absorbance was measured at 500 nm. With this
2-
method 1-8 pg of SO. per mL may be determined.
Nitrate was determined by sodium salicylate method.
Sodium salicylate method.
(1) Reagent.
a. Sodium salicylate solution.
1 g of sodium salicylate v/as dissolved into 0.01 N NaOH
to make up volume of 100 mL.
b. uO~ standard solution.
The standard solution was prepared by dissolving dried
into water. 1 mL of the standard solution^ 20 ^ig NOT.
PROCEEDINGS—PAGE 154
-------
c. 0.2 % aqueous solution of NaCl.
d. 0.1 % aqueous solution of ammonium sulfamate.
(2) Procedure.
2-10 mL of sample solution and 2 mL of water were successi-
vely put into 100 mL beaker, 1 mL of sodium salicylate solution,;.
1 mL of 0.2 % NaCl solution and 1 mL of 0.1 % ammonium sulfa-
mate solution were added. Then the solution v;as evaporated to
dryness on a water bath. After cooling the beaker 2 mL of
^concentrated &2SQ4 was a
-------
maintain suction flow of SOL min
The materials collected on the impregnated filters were
extracted from the filters and colorimetrically determined by
the methods shown in Table I. The particulate materials were
Table I. Methods of Filter Impregnation and Analysis for the Determination of
S02, HN03, NH3 and HC1
Gas
so2
HNO,
Filter Washing
Solution
Water- (60° C)
Water (60aC)
Washing
Time
2
2
Aqueous Solution
for Impregnation
2.5% K2C03-2%
glycerine
5% NaCl
Analytical
Method
West-Gaeke
Reaction with Griess—
NH3 IX HC1
Water (60 'C)
HC1 0.5N EX03
Water (60°C)
1% oxalic acid
2%
Romijn reagent after
being reduced by
hydrazine
Indophenol
Mercuric thiocyanate
2_
ultrasonically extracted from the Teflon filter. SO. was
NO, was determined
determined by barium Chloranilate method.
by the same method as HN03. Prior to sampling the Teflon
filter was ultrasonically washed for 10 minutes. The lowest
measurable concentrations of the materials in two-hour
samples are as follows :SO2:0.5, S0^~:1.0, NO~:0.1,NH*:1.0,
and Cl~:1.0 ug m~ .
PROCEEDINGS—PAGE 156
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2-
III. Airborne Measurements of SO4 , NO., and HN03 on July 3-5,
1979
During the period of July 3 to 5 in 1979, airborne measure-
ments were made on board a helicopter (Fuji-Bell 204 B). The
flight routes are as shown in Fig. 9 along with wind direction
and speed near the ground and at height of 300 m. O., was measured
by a Dasibi UV photometer. NO and N02 were measured using a
Monitor Lab. chemiluminescent analyzer. The method of sampling
of particulate S04~ and N0~, and gaseous SO2 and HNO., is presented
in another paper provided that the sampling was conducted
successively at the interval of 15-20 min using a combination
of a timer and sequential valves (Fig. ]_QJ The methods of
determination of SO,, and HNO-, are also given in another paper.
2- -J
The particulate SO,, and NO, were determined by an ion-chromato-
graph.
For the collection of particles teflon filters (Sumitomo
Denko FP065) of 5 cm. in diameter were used. The filters were
ultrasonically washed with 20 mL of very pure acetone for 10
min. Then they were also ultrasonically washed in twice-distilled
deionized. water. Further the filters were stored in silica
2- -
gel desiccator before use. After the sampling SO. and NO3
were ultrasonically extracted into 20 mL of warm water for
15 min and 5 ir.L of the extract was injected into the Diomex
Model 10 ion chrornatograph attached with a concentration column.
The peak area of the record was measured by the Shimazu Chromato-
pack C-RlA integrator.
Tab1» TT shows thp rriRan concentrations of aaseous and
particulate components and the flight routes. It is found that
for the flight routes of II, VI, VIII and X HNO3 concentration
increased along downwind direction and only in one case of XII it
decreased. Higher HNO-, concentration was usually associated with
2-
higher O, concentration. In one case of VIII SO. concentration
increased with downwind distance whereas in three cases of II,
VI and X it decreased. In the five cases of I, V, VII, XI and
2-
XII there was no appreciable difference of the SO. concentration
along the routes. In two cases of CI and CII NO, concentration
slightly decreased whereas there was no appreciable change of NO,
concentration in the two cases of V and XI.
PROCEEDINGS—PAGE 157
-------
N01
1
2015
10
2
1020
'•1
If 23
A
15km
2.012
'3
0
3032
003
6
2QK
1
2
104
June 28,1977'10-16
Fig.1-1 Distribution of various atmospheric
trace constituents near the ground.
June 28,1977
PROCEEDINGS—PAGE 158
-------
^ PP b
29
2039
109
ppb0x.
Ppb
17
9034
125
29
9010
95
57
15km
26
9031
104
2^3
8©!2
50
38
1AQ25
104
5
506
34
Tokyo
June 28.1977
PROCEEDINGS—PAGE 159
-------
1 06
144
28,
1 04
150
87
19
1©3
119
\
15 km
145
174
97
loO
78
100
94
June 23,1977
PROCEEDINGS—PAGE 160
-------
-
N03
0
4020
!
15km
0
15010
4
8015
•10020
8
•26035
c
0
206
2 OA6
1
10
3018
3
6
20^54
6
2010
3
June 30, 1978 10-16
Fig.1-2 Distribution of various atmospheric
trace constituents near the ground.
June 30,1978
PROCEEDINGS—PAGE 161
-------
HCHO
SO, ppt>
25
40
17017
70 M
\Jf.
40.
15014
90
15©22
113Ku
12^10
54
17Q16
105U
15
906
Tokyo 2520018
10
7012
60
20 C
( Tokyo
83oi6 Bay
sis
12
June 30,1973
PROCEEDINGS—PAGE 162
-------
O
NH3 F
O
135
ITA.
195
20
1 ^5
142
109
27
1?6
1 05
127
240
10
1 °8
214
6
1 02
105
June 30, 1978
PROCEEDINGS—PAGE 163
-------
0
16010
3
0
21020
A
22026
6
L
8024 15km
1
17021
10Q9
A OA9
•1
5
17031
-J
23035
6
July 3, I97B 10K-16H
Fig.1-3 Distribution of various atmospheric
trace constituents near the ground.
July 3,1978
PROCEEDINGS—PAGE 164
-------
HCHO
70 M
20
30
1670
11017
95 Ku
16
12016
53
25
8015
82
56
28
16020
127U
47
Tokyo
5013
70
Tokyo
9 020 Bay
20
3016
30
a
9012 Yokohama
57
July 3, 1973
PROCEEDINGS—PAGE 165
-------
Cl~
16
IO
157
27
1^
215
,3o°8
184
192
,2o2,0
196
22o59
245-
156
9
1 06
197
249
003
96
July 3,1978
PROCEEDINGS—PAGE 166
-------
NOP?b
NOj
T. ,. ,
7038 15km
1
10020
2
Q015
6
5031
rags
0
12010
7
1
^
5
July
4 1973 I0-I6
0^7
3013
1
Fig.1-4 Distribution of various atmospheric
trace constituents near the ground.
July 4,1978
PROCEEDINGS—PAGE 167
-------
HCHO o
Ox
12I26
40
3«3
80 M
20
11030
67
31
40
200C4
90
17034
124 Ku
30
9018 0
79
75
7
7020
44
r-
24026
100
Tokyo 25034
30C'
( Tokyo
42\ „_..
12033
So20 Yokohama
July 4, 1978
PROCEEDINGS—PAGE 168
-------
24
lo?
231
NH, N*
28
log
178
35
229
26
1 91
244
237
35
0011 5
182
32
1 o
173
28
1 06
177
I
JuIY 4, 1973
PROCEEDINGS—PAGE 169
-------
0
;5oio
A 028
15km
2§12
0
7
5^22
-2
•5021
A
202
2 OA6
0
A 020
309
July 6, 1978 I0h-16h
Fig.1-5 Distribution of various atmospheric
trace constituents near the ground.
July 6,197R
PROCEEDINGS—PAGE 170
-------
HCHO©SOr/3/w'
•^ Ox.
50
16 023
70M
AO
22
»1
83 Ku
30
9 915
V
17
9013
33
ie
53
3'flO
20
101 U
11
9012
41
20
12 o 15
80
10016 Yokohama
59
Tokyo
11\
Hois Bay
PROCEEDINGS—PAGE 171
-------
Cr
21
1 08
160
16
1°
115
02o°4
120
26
1 ©5
141
132
35
1 93
115
142
20
1 03
151
20
1 02
129
PROCEEDINGS—PAGE 172
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N03
0
8010
9025 '15km
7i,6
9§20
7
5^23
5
3016
6
0
707
A OA10
2
5|l9
5
5027
O
July 7,1978
Distribution of various atmospheric
trace constituents near the ground.
July 7,1978
PROCEEDINGS—PAGE 173
-------
SO*
HCHO
p?b Ox.
50
23026
SOM
40
19^23
20 8°
12^25
96 Ku
1^
67
28
29
78
2
A17
92
11019
39u
20
IOKy° 16 ©19,
10 I0c
3019 ( Tokyo
J50 73o°2\ Bay ,25
2- /30 Ka
10°13 Yokohama
53
*- *j
020
0
2015
20
July 1, 1973
PROCEEDINGS—PAGE 174
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NH3
Cf © NI-U
20
1 09
209
n
1 09
175
12o39
176
2?
Oo7
163
i 9
219
15o?9
176
166
165
10,
1 oA
177
July 7, 1973
PROCEEDINGS—PAGE 175
-------
Pacific
Ocean
9AM. June 28,1977
Fia.2-1 Air trajectory.
June 28,1977
PROCEEDINGS—PAGE 176
-------
12AM,June 23, 1977
3 P.M. June 28,1977
PROCEEDINGS—PAGE 177
-------
J2AM June 30,1978
Fig.2-2 Air trajectory
June 30,1978
PROCEEDINGS—PAGE 178
-------
3PM June 30, 1978
PROCEEDINGS—PAGE 179
-------
3, 1978
Fig . 2-3 Air trajectory
July 3,1978
PROCEEDINGS—PAGE 180
-------
3PM JulyS, 1978
PROCEEDINGS—PAGE 181
-------
12AM July 4,1978
Fig.2-4 Air trajectory
July 4,1973
PROCEEDINGS—PAGE 182
-------
SJ3PM July 4,1978
PROCEEDINGS — PAGE 183
-------
12AM July 6, 1978
Fig.2-5 Air trajectory.
July 6,1978
PROCEEDINGS—PAGE 184
-------
3PM July 6, 1978
PROCEEDINGS—PAGE 185
-------
Fig.2-6 Air trajectory
July 7,1978
PROCEEDINGS—PAGE 186
-------
3PM July?, 1978
PROCEEDINGS—PAGE 187
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HCHO
NO
NOz HN05
100 20
V:NO(ppb) +:N02(ppb)
X:HN03(ppb) • :NO~(ppb)
o:HCHO(ppb) A;0xidants(ppb)
. - NO;
-.200 40
c
o
2
c
C
o
o
50 TOL
0
-100 20
M
0
20km
Fig.3-1 Variation of the concentration of various
trace constituents along the air trajectories
Kawasaki-Chiyoda-Urav/a-Kumagaya-Maebashi.
Ka:Kawasaki, C:Chiyoda, U:Urawa, Ku:Kumagaya,
M:Maebashi.
June 28,1977
PROCEEDINGS—PAGE 188
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NH3
Oxid. SOT
200 40r 4-
f 1:S02(ppb)
V:NH3(ppb)
X'Total aerosol(T.A.
A'Oxidantsfppb)
June 28, 1977
>4 (,ug/m3)
c
g
"a
o
C
o
u
100 20-
0
IA. NHt
20
-200 10
M
0 0
20km
PROCEEDINGS—PAGE 189
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HCHO
NO
NOZ HN03
100 20-
c
o
0)
o
c
o
o
50
0 0
v:MO(ppb)
X:HN03(ppb)
otHCHO(ppb)
+ :NO2 (ppb)
© :NO-. (ppb)
/.:0xidants (ppb)
-100 20
M
0 0
20 km •
Fig.3-2 Variation of the concentration of various
trace constituents along the air trajectories
Kawasakl-Chiyoda-Urawa-Kumagaya-Maebashi.
Ka:Kawasaki, C:Chiyoda, UrUrav/a, Ku:Kumagaya,
MrMaebashi.
June 30,1978
PROCEEDINGS—PAGE 190
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NH3
50*
Oxid. SO
200 40
c
o
I
~c
r;
O
100 20
0 0
f:S02(ppb)
(,ug/m)
X:Total aerosol (T. A.) (pg/m3)
^. :Oxidants (ppb)
June 30, 1978
_i 1_
Ko C U
20 km
Ku
TA.
400 20
200 10
M
0 0
PROCEEDINGS—PAGE 191
-------
NOZ HN03
100 20h
c
o
o
c
o
o
50 1C
0 0
Fig.3-3
Kd C
v :MO(ppb)
X:HN03 (ppb)
o:HCHO(ppb)
July 3, 197B
+:NO2(ppb)
o:NO~(ppb)
A:Oxidants(ppb)
Oxfd.
1200
100 20
U
Ku
M
0
0
20 km
Variation of the concentration of various
trace constituents along the air trajectories
Kawasaki-Chiyoda-Urawa-Kumagaya-llaebashi.
Ka:Kawasaki, CiChiyoda, U:Urawa, Ku:Kumagaya,
M:Maebashi.
July 3, 1978
PROCEEDINGS—PAGE 192
-------
NH,
SOr
Oxid. SCC
200 40
c
o
c
-------
HCHO
NO
N02 HNQ3
v :NO(ppb)
y.:HN03(ppb)
o:HCHO(ppb)
+:NO 2(Ppb)
o:NO~(ppb)
&:Oxidants(ppb)
Oxid.
100 20-
c
o
u
C
o
CJ
50 101-
0
-200 40
-100 20
Ka C U Ku
Fig.3-4 Variation of the concentration of various
trace constituents along the air trajectories
Kawasaki-Chiyoda-Urawa-Kumagaya-Maebashi.
Ka:Kawasaki, C:Chiyoda, U:Urawa, KuiKumagaya,
MrMaebashi.
July 4, 1978
0 0
PROCEEDINGS—PAGE 194
-------
2
Oxid.
200 40
c
o
"5
i_
"c
o
u
o
o
100 20
o o
Ka
»-
C
20km
-)- :SO2 (ppb) 0:SO
V:NH3(ppb) o.-NH
X:Total aerosol(T.A.)(pg/m3)
/I :Oxidants (ppb)
July 4, 1978
U
Ku
20
200 10
M
0
0
PROCEEDINGS—PAGE 195
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HCHO
NO
NO, HN03
100 20r
c
o
c
OJ
o
o
o
50
0
V :NO(ppb)
X:HN03(ppb)
o:HCHO(ppb)
+:NO2(ppb)
o:NO~(ppb)
A:Oxidants(ppb)
July 6, 1978
Oxid. NO;'
-i200 AO
-100 20
M
0
20km
Fig.3-5 Variation of the concentration of various
trace constituents along the air trajectories
Kawasaki-Chiyoda-Urawa-Kumagaya-Ilaebashi.
Ka:Kawasaki, CrChiyoda, U:Urav/a, Ku:Kumagaya,
MrMaebashi.
July 6, 1978
PROCEEDINGS—PAGE 196
-------
f:S02(ppb)
y:NH3(ppb)
(,ug/rn)
* (,ug/m3)
X:Total aerosol (T. A. ) (pg/m )
:Oxidants (ppb)
Oxid. SOl"
200 40
c
o
c
o
O
CJ
100 20
0
0
July 6, 1978
1T.A.
Ka c
20km'
U
Ku
400 20
200 10
M
0
0
PROCEEDINGS—PAGE 197
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PPR;
6
4
N02
2
a
5
N02
4
+>
n o rvAYYADAm UK,n nnu.
JflNWa rr''-'
x <0.9
o 1.0 -2.9 ^
• 3.0-4.9
+ 5.0-6.9
* 7.0 -8.9
^9.0-10.9
. o 2
o
0 0
oo + + N02
• "*"
• -f.
00 • +
o
% 1 T 1 f
URAWA f
4-
o o
0 0
• o
0 00 » »
o
1 1 1 »
> S 10 ^2 6 10
Ox pphm Ox
x HIRAT5UKA
- x 4
V
N02
5E O \/ f-
0
Jiii n
ICHIHARA
x
X
00
x o
XX xo
XXX OX
X
1 y 1 >
? 6 10 °2 4 " 6 8
Ox Ox
Fig.4 Relationship between the concentrations of
HNO-., NO2 and oxidants.
PROCEEDINGS—PAGE 198
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pphrn
2
x <0.9
• TOCHIGI .3.0-4.9 UT5UNOMIYA
x -i- 5.0 -6.9 x
x x ^ 7.0-8.9 oL . * °
N02
1
n
vg.0-10.9 *[ A 0°
HN03
>Po
X 0
x ° °o
x
> 1 ( •
U0 4 8
Ox
2
N02
1
0,
2
IM02
n
KUMAGAYA
o
0 +
X' 0 0
X
o DO
-
o °
X i i
2468
Ox
TATE5AYASHI
x o
x o
X
XXX
x x
xx x
X
X 0
XX
X
1111
°2 6 10
Ox
ppb x o
_ _
N02 x
X X
X
1 • °
o
X
1
12
pphm
n * ' * i
2 6 10
Ox
MAEBASHI
^ " x
X
M^ X X X "
N02 x x ~
x x x
2 - x x x
x
X X
X
X
n ' ' • ' '
6 Ox 10
TOGANE
2- o
N02
1 • xx x
x x
n
0 2 nn I 6
Ox
PROCEEDINGS—PAGE 199
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Q.
D.
C
.2 A
c
(U
o
C
o
u 2
0
0
•Ka
"Mi
•Tt
xKa
•Ku
>Ma
•Tm
*ut
•Ke
2468
Oxia'ant Concentiration pohm
•Ur
xTo
10
Fig.5 Relation between mean concentrations of NO_
and oxidant vjhen HNO, concentration of 3.0
-4 . 9 ppb was obser\4ed.
x:data in 1977, «>:data in 1978
CrChiyoda, KetKeisen, KatKawasaki, Irlchihara,
TmrTama, Mi:Mito, S:Shimodate, R:Ryugasaki,
Ur:Urav/a, Ku:Kumagaya, Ma:Maebashi, Tt:Tatebayashi,
TorTochigi, Ut:Utsunomiya H : Hiratsuka
PROCEEDINGS—PAGE 200
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35km
Tochigi
eTateboyashi
QKumagaya,
eUrawa
Fia.6 Route of helicopter in 1978
PROCEEDINGS—PAGE 201
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-V :July 4, 13h-l6h
X :July 6, 10h-13h
•« 'July 6, 13h-l6h
-A :July 7, I0h-l6h
1500f
• /•> rx\
*&
I
I
I
\
\
\
\
\
O)
"
-------
0 :July 5, 12h-l?h
X :July 6, 10h-13hi
fc :July 6, 13h-l6h|
1500
1000
500
i
o
If
\
\
\
/A .ouj.j /-, j.un— ion '
X !
\
\
\
\
" O €r
«\
/\
i \
/ \
* t
x' h,
/
i •
\ j
-4ftte
\ \ x
V \ x
0\ \
\\\ x
\ \ \
\ \ \
\V v<
!- • , \ \ \\ ,
i « \ H ~ i J
i \ * * i ^'
!_' Q '- 1
0 5 .ib
HN05 Concentration ppb
Fig.7-2 Vertical distribution of trace constituents
(HNO3) in the boundary layer in 1978.
PROCEEDINGS—PAGE 203
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O :July 5, 12h-l?h
X :July 6, 10h-13h
® :July 6, 13h-l6h
A :July %, 10h-l6h
1500r
1000-
D)
"
-------
+ :July *t, 13h-l6h j
O :July 5, 12h-17h j
X :July 6, 10h-13h
© :July 6, 13h-l6h
A :July 7, 10h-l6h j
1500
1000
(b
500
0
0
-f
50 100 150
Oxidant Concentration ppb
Fig.7-4 Vertical distribution of trace constituents
(Oxidant) in the boundary layer in 1978.
PROCEEDINGS—PAGE 205
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.-July 5, I0h-17h
:July 6, I0h-l6h
:July 7, 10h-l6h
1500
lOOOr
CT
X
SCO-
ID , 20 30
Concentration jjg/m3
Fig.7-5 Vertical distribution of trace constituents
2—
(SO, ) in the boundary layer in 1978.
PROCEEDINGS—PAGE 206
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O :July 5, 10h-17h i
X :July 6, 10h-l6h !
A :July 7, 10h-l6h i
1500
1000
en
"CD
500
NH4 Concentration pg/m2
Fig.7-6 Vertical distribution of trace constituents
) in the boundary layer in 1978.
PROCEEDINGS—PAGE 207
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O -'July 5, ioh-17h
X 'July 6, lQh-l6h
A :July 7, 10h-l6h
1500r
1000
.c
.E?
"(b
X
500-
4 6 8
Concentration pg/m3
Fig.7-7 VERtical distribution of trace constituents
(NO.,) in the boundary layer in 1978.
PROCEEDINGS—PAGE 208
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,--.
\ t >--—•;
-•^__- \r~ >
a /Jind near the ground v/ith speed Im/sec
& Wind at heigat of 300m v/ith speed 3m/sec
Fig.9-1 Flight routes on July 3,1979,1145-1322 JST
PROCEEDINGS—PAGE 209
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r
V;
I
V -1
*——->--'
o ___ i •'"•-•^i
CJ Wind near the ground with speed Ira/sec
X r.\ind at height of 300m with speed 3m/sec
Fig.9-2 Flight routes on July 3,1979,1529-1710 JST
PROCEEDINGS—PAGE 210
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3
July 4 (1979) 1028-1208 JST
'
X ^ _>
C3 Wind near the ground with speed Im/sec
ŁŁ V;ind at height of 300m v/ith speed 3ra/sec
Fig.9-3 Flight routes on July 4,1979,1028-1208 JST
PROCEEDINGS—PAGE 211
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15km
July 4 (1979). 1427-1614 JST
Wind near the ground with speed lir./sec
Wind at height of 300m v/ith speed 3m/sec
Fig.9-4 Flight routes on July 4,1979,1427-1614
PROCEEDINGS—PAGE 212
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July 5
•v^-vr^-
^
s
(1979) 1018-1205 J5T
°A
.-/
IX
I
3
\
x-'>.,
X N
» "»
1 >
i ; <;~
\
\
0 1
,—K •
Wind near the ground with speed Int/sec
VJind at height of 300m with speed 3rn/sec
Fig.9-5 Flight routes on July 5,1979,1018-1205
PROCEEDINGS—PAGE 213
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, -i July 5 , (1979) 1409-1556 J5T
15 km °N •
*
r3 i-Tind near the ground with speed Im/sec
Wind at height of 300m with speed 3m/sec
Fig.9-6 Flight routes on July 5,1979,1409-1556
PROCEEDINGS—PAGE 214
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Splitter
Rotameter
Pump
Fig.10 Automatic sampling system on board a helicopter
PROCEEDINGS—PAGE 215
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Table II
Dace
July 3
uly 4
July 5
Flight
number
I
II
III
.TV
V
VI
VII
VIII
IX
X
XI
XII
Time
1145-1202
1202-1220
1220-1239
1239-1258
1258-1316
1316-1322
1529-1549
1549-1605
1605-1621
1621-1639
1639-1656
1656-1710
1026-1043
1043-1100
1100-1116
1116-1133
1133-1150
1150-1207
1426-1441
1441-1455
1455-1510
1510-1525
1525-1539
1539-1555
1535-1610
1016-1033
1033-1048
1043-1102
1102-1119
1119-1136
1136-1150
1150-1205
1409-1425
1425-1440
1440-1456
1456-1511
1511-1526
1526-1540
1540-1556
Concentration of gases ppb
S02 HN03 -NO N02 03
0.13 40
ND 40
37
37
0.72 33
0.43 49
ND 6.4 6.4 55
0.83 9.4 26.4 61
0.12 7.9 18.1 75
0.39 6.0 18.6 77
0.05 8.3 26.2 47
0.64 5.1 6.3 42
6.8 11.6 29.5 21
4.8 6.7 18.2 42
3.1 4.7 12.0 53
1.57 3.8 12.1 47
1.41 4.9 17.2 50
1.34 7.4 27.0 45
3.6 5.4 26.4 76
3.8 3.1 22.7 94
5.4 3.1 25.6 117
2.7 2.3 22.1 118
2.4 2.9 28.1
0.29 2.9 22.9 84
0.81 3.5 24.4 66
2.3 2.9 12.3 71
2.0 2.7 8.8 82
2.2 1.9 7.2 90
2.3 2.0 8.7 82
1.43 1.7 10.2 87
1.00 1.7 9.6 83
0.13 1.6 12.0 118
2 6 2.5 30.2 138
0.65 1-9 10.4 102
1 i 1.9 9.4 99
2.1 1.5 6.9 65
0.94 1.5 9.4 101
3.6 1.5 14.0 139
3.0 2.3 24.4 109
Concentration
s°r N°3
4.9,., ND
2.1 «
6.2 9.4
8.9 ND
5.1 i.
21.8 27.6
3.1 ND
14.0 11.0
12.3 10.0
9.4 8.1
5.8
8.7 10.6
12.4 9.4
10.4 6.0
14.4 9.8
9.7 8.8
10.1 8.8
12.2 10.1
13.3 10.7
14.0 11.5
14.4 8.9
12.5 8.9
9.0 ND
5.6
4.7
4.9 ND
6.5
2.5
5.1
5.1
7.0 "
7.1 »
16.2 7.8
13.8 8.9
15.4 8.3
1.0 7.0
7.8 ND
13.4
10.0
PROCEEDINGS—PAGE 216
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USE OF AEROMETRIC DATA TO EVALUATE
THE EKMA MODEL
presented by B. Dimitriades
Environmental Protection Agency
United States
PROCEEDINGS—PAGE 217
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Use of Aerometric Data to Evaluate
the EKMA Model
B. Dimitriades
February 5, 1980
Following is a discussion of the current development status of the EKMA
model, and USEPA's on-going and planned efforts to evaluate this model.
First, it should be pointed out that the presently available EKMA model
uses a reaction mechanism that was developed 4-5 years ago. Since then,
there have been new studies which identified new mechanistic steps and
resulted in new values for some rate constants. To incorporate these
new findings into the EKMA model entails considerable work which has not
been done yet. To illustrate such deficiencies, the current EKMA model
does not include aromatic hydrocarbon chemistry, neither does it include
PAN chemistry (PAN ^ N02 +• RCCL); therefore, it cannot be used to
predict PAN. Also, it does not have temperature-dependence steps.
Another point that should be made is that although EKMA does not use the
latest mechanism, this does not necessarily mean that EKMA predicts 03
less accurately than other models which do use the latest mechanistic
schemes. This is because, unlike all other models, the EKMA model was
"tuned" to predict well (L in smog chamber irradiated auto exhaust
mixtures. The question which remains unanswered is how well EKMA —
even with the new mechanistic findings incorporated — predicts 03
concentrations in the real atmosphere. It is well established that
there are some important differences between smog chamber atmosphere and
real atmosphere; e.g., surface reactions (N205 + HgO ^ HN03) should
PROCEEDINGS—PAGE 219
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have a much greater role in the chamber than in the real atmosphere;
also, real atmosphere is much more inhomogeneous than the chamber atmosphere.
These differences raise questions that cannot be answered reliably
except by directly testing the model with real atmosphere data. Foe
these reasons, it is now felt within USEPA that it is equally or more
important to direct efforts to evaluating the EKMA model with real
atmosphere data than to further refining the model's chemical mechanism.
The remainder of this discussion will deal with the subject of evaluation
of the EKMA model with real atmosphere data.
There are two general ways of evaluating the EKMA model:
(a) Evaluate EKMA's accuracy in predicting relative air quality
levels
(b) Evaluate EKMA's accuracy in predicting absolute air quality
1 eve!s
In the first case USEPA has already conducted an evaluation effort. We
used a trends analysis method to evaluate EKMA with respect to its
accuracy in predicting air quality changes from emission changes.
Specifically, we established emission trends in the Los Angeles basin
during the past 12 years, and used EKMA to convert the emission changes
during that period into ambient air quality changes. We then compared
these EKMA-predicted 03 trends with those actually observed. This work
(published some 2 years ago) showed the EKMA model to be directionally
PROCEEDINGS—PAGE 220
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accurate, but the data were not sufficiently definitive to give a quantitative
evaluation of the method. Two problems that caused much of the inconclusiveness
were (1) the observed air quality trends reflected to a large degree the
meteorology changes from year-to-year rather than the emission changes,
i.e., the impact of emission change was obscured by the impact of meteorological
changes; (2) the measured NMHC/NO values ranged widely, which was
confusing because the prediction-vs-observation agreement depends strongly
on NMHC/NOx- The plans are to repeat this study using the additional
data obtained in the last 3 years, and applying some method refinements.
Another method of evaluating EKMA's relative air quality predictions is
through comparison with a properly validated AQSM. This evaluation will
be conducted as soon as AQSM's become available, in approximately one
year.
The method and effort that I wish to discuss in more detail here and for
which we are requesting assistance from Japan is the "upper limit"
method for evaluating EKMA's predictions of absolute air quality. The
method has been applied by Dr. Martinez of SRI using air quality data
taken in Houston. Although the method is described in some detail in a
report (attached), I would like to briefly discuss the method and explore
the possibility of applying this method using Tokyo air quality data.
The method calls for use of data on 6-9-am NMHC and NO. and on max 0?
J\ O
concentration in an urban area. The 6-9-am NMHC and N0x data are used
to calculate peak 03 concentrations using the EKMA isopleths, and these
PROCEEDINGS—PAGE 221
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model-predicted peak 03 values are then compared to the observed peak 03
values. In doing this comparison, however, we must keep in mind that
the EKMA predictions are based on the assumption that the sunlight
Intensity and temperature conditions are typical of smoggy days, and
that the CL formed is not destroyed by fresh emissions (NO). Therefore,
for e.g., cloudy or cold days, when peak (L is low, the data will be
Inappropriate for use in this model test; appropriate data are only
those for days when the conditions were similar to those assumed in the
EKMA model. Alternatively, the method should be evaluated based not on
indiscriminate comparison of predictions and observations; rather, the
evaluation should be based on comparison of predictions against the
maximum observed peak 03 values. A 1:1 comparison indicates that the
model is valid.
USEPA is now in the process of initiating an effort to apply this evaluation
method using data from several urban areas in the US. We are also
refining somewhat the method, e.g., adjust the observed NMHC values to
insure consistency with model requirements. Also, we will make an
effort to document the quality and appropriateness of the NMHC, NO , and
A
0- data to be used.
Next, I wish to bring up and discuss a proposal of USEPA for a joint
Japan-US effort to evaluate EKMA. We wish to propose specifically the
following:
PROCEEDINGS—PAGE 222
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1. Japan would conduct an effort to gather, archive, and quality-
characterize the air quality data available for an urban area
in Japan. The urban area of the study shall be selected to be
one with the highest density and highest quality of aerometric
measurements. Such measurements shall include at minimum
NMHC, NOX, peak-03, upwind Og, and, preferably, radiation, T,
wind, HC , also.
2. US would include Japanese data in the data base to be used by
US to evaluate EKMA. (Japan may wish to conduct independent
evaluation of EKMA using the Japanese data.)
3. Results and reports from US and Japanese efforts would be made
available to the two countries.
4. In view of the urgent need for EKMA evaluation evidence in the
US, the Japanese data would become available to US as soon as
possible.
PROCEEDINGS—PAGE 223
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Preliminary Study on EKMA
in Japan
Air Quality Bureau
Environment Agency
PROCEEDINGS—PAGE 225
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1. Introduction
The US EPA states views on the EKMA model as follows in the Federal Register:
" The US EPA recently developed a method that utilizes a set of simulated
03 curves to determine the sensitivity of the one-hour afternoon 03 maximum
to cheng'es in 6-9 a.m. HC and NOx under meteorological conditions conducive
to 03 formation. This method is based on a chemical kinetic model and smog
chamber experiments. Advantages of EKMA are that it is easier to apply than
simulation models and that, unlike rollback, it considers both HC and NOx.
The method also allows for consideration of background levels and, in a
limited sense, for differing meteorology between cities and for transport.
Disadvantages include lack of verification snd difficulties in interpreting
HC measurements. "
An attempt was made by Air Quality Bureau, Environment Agency to apply
EKMA to Tokyo Bay Area where heavy photochemical air pollution has been
observed. Prior to the full scale study for the applicability of EKMA to this
area, we practiced the preliminary study for the accuracy of EKMA.
Because of very complicated emission sources in Tokyo Bay Area, we thought
we should, in the first place, investigste EKMA model from the viewpoints
of ability to reflect those complicated situation of photochemical air
pollution in Tokyo Bay Area.
As a result of this preliminary study, the following matters are found
to be examined in greater detail.
. Hypothetical column
. Identification of K-| value
. Dilution rate
. Post 9 a.m. emissions
This paper presents tentative views of Air Quality Bureau,Environment
Agency on the above matters.
PROCEEDINGS—PAGE 227
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2. Views of the US EPA on the Inherent Assumptions in EKMA
The US EPA states views on the inherent assumptions in EKMA as follows:
( quotation from " User's Manual for Kinetic Model and Ozone Isopleth
Plotting Package " )
The physical model underlying the kinetic model in OZIPP is similar
in concept to a trajectory-type photochemical model. In the kinetics model,
a column of air transported along assumed trajectory is modeled. The column
is assumed to extend from the earth's surface to the base of a temperature
inversion. The horizontal dimensions of this column are such that the
concentration gradients are small. This makes it unnecessary to consider
horizontal exchange of air between the column and its surroundings. The air
within the column is assumed to be uniformly mixed at all times.
At the beginning of a simulation, the column is assumed to contain some
specified initial concentrations of NMHC and NO due tc prior emissions. The
J\
column may also contain fJMHC and NO that were transported with the column
^\
from areas upwind of the city being considered. Thass pollutants, sometimes
called background, are in this report termed pollutants "transported in the
surface layer.:1 As the column moves along the assumed trajectory, the height
of the column can change because of temporal and spati-1 variations in mixing
height. The heignt of the column is assumed to change exponentially with time
during a user selected period, arid to be constant before and after that period.
As the height of the column increases, its volume increases, and air above the
inversion layer is mixed in. Pollutants in the inversion layer are described
as "transported above the surface layer" or "transported aloft" in this report.
Any ozone or ozone precursors from the inversion layer that are mixed into the
column as it expands are assumed to be immediately mixed uniformly throughout
the column.
The kinetics model in OZIPP can also .consider emissions of NMHC and NO
X
into the column as it moves along its trajectory. The concentrations of the
species within the column are physically decreased by dilution due to the
inversion rise, and physically increased by entrainment of pollutants trans-
ported aloft and by fresh emissions. All .species react chemically according
to the kinetic mechanism shown in Appendix A. Certain photolysis rates within
that mechanism are functions of the intensity and spectral distribution of
sunlight, and they vary diurnally according to time of year and location.
PROCEEDINGS—PAGE 228
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The assumptions and specifications that describe the kinetics model are:
' The air mass of interest is an imaginary air parcel (column) of
fixed horizontal area at a constant temperature, within which
pollutants are well mixed.
' There is sufficient homogeneity that horizontal diffusion does
not affect pollutant concentrations within the column.
' The height of the column varies exponentially with time during a
specified period and is constant at other times (an exponential
variation is equivalent to a constant percentage dilution per
unit time).
' The column contains specified initial concentrations of NMHC and
NO due to emissions prior to the simulation starting time within
the urban area of interest. (These concentrations are shown on
the NMHC and NO scales of the resulting ozone isopleth diagram).
The NMHC is assumed to be 25 percent propylene and 75 percent
n-butane, unless changed by the user. Five percent of the initial
NMHC concentration is added as aldehydes, unless changed by the user.
' Pollutants transported within the surface layer from outside
the urban area of interest (sometimes called background) may
be present in the column at the start of each simulation
(0800 LOT). The pollutant concentrations due to transport in
the surface layer are normally assumed to be zero, but the user
may specify other values for the NMHC, NO and ozone concentra-
tions transported within this layer. ThexNMHC transported within
the surface kuer is assumed to be 10 percent propylene and 90
percent butane (as carbon). The NO transported in the surface
layer is assumed to be 100 percent NO-.
' The initial concentrations in the column are thus the sum of the
contributions from emissions occurring prior to 0800 LOT plus
concentrations transported in the surface layer from upwind loca-
tions. Emitted species include propylene, n-butane, NO, NO-,
acetaldehyde and formaldehyde. Transported species include
propylene, n-butane, NO^ and ozone.
' The changes in pollutant concentrations within the column are
calculated, by computer simulation, from 0800 to 1800 LOT. The
chemical reactions involving these pollutants are listed in
Appendix A.
' Entrainment of pollutants transported aloft is possible during
the rise of the inversion layer. OZIPP only permits entrain-
ment of constant concentrations of NMHC, NO and ozone. NMHC in
pollutants transported aloft is assumed to.Be 10 percent propylene
and 90 percent n-butane (as carbon). No acetaldehyde or formalde-
hyde is added. NO transported aloft is assumed to be 100 percent N0~.
A t-
PROCEEDINGS—PAGE 229
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Pollutants emitted into the column after 0800 LOT can be represented
by specifying additions of NMHC and NO each hour. The assumptions
about the propylene/n-butane and the afdehyde additions are the
same as for the initial, condition assumptions. The fraction of NO
that is NOp, however, is 10 percent for post-0800 emissions.
The rate constants of all chemical, reactions in the kinetic
mechanism are as shown in Appendix A, except for the photolysis
reactions. Photolytic rate constants vary according to the time of
day, date and location being simulated. (Default photolysis rate
constants are intended to represent the period from 0800 to 1800 PDT
on the summer solstice in Los Angeles).
Zero cloud cover is assumed.
PROCEEDINGS—PAGE 230
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APPENDIX A
KINETIC MECHANISM USED IN OZIPP
Number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
Reaction
N02 + hv -» NO + 0(3P)
0(3P) + 02 + M * 03 + M
0 + NO -> NO + 0
3 22
N0_ + 0, -»• NO, + 0_,
2 o-3 2
...
NO + 0(°P)->NO + 0
NO* NO -* 2NO-
3 2
N0_ + N0_ -+ N_0,_
2 j 25
N_0, -*• N0? + NO-
N-0.. * H.,0 -* 2HNO_
252 o
NO + NO- -v H_0 -* -2HONO
2 2
2I10NO -> NO + N0_ + H_0
2 2
HONO * hv ^-- OH + NO
OH * N02 ^ R\T03
OH + NO -V HONO
HO., + NO - NO + OH
HO •* K00 -* HOOH -> 09
HOOH + hv -* 2 OH
0, + hv " 0( D)
0, + hv ^ 0(3P)
O^D) + M -* 0(3P) + M
0(^5 + H^O -»• 20H
*
Rate Constant
vary
-5 -2 -1
2.0 X 10 ppm min
25.0
0.045
4
1.3 X 10
1.3 X 104
3
5.6 X 10
^.Onin'1
-6
2.5 X 10
-9 -2 -1
1.0 X 10 ppm nin
1.0 X lO"^
vary
. 3
8.0 X 10
3.0 X 10J
1.2 X 1Q-5
8.4 X 10°
k
vary
k
vary
k
vary
5.7 X 104
5.1 X ID3
PROCEEDINGS—PAGE 231
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Number
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
Reaction
DH * 0 -*-HO? + 0_
°3 * H°2 "*" °H * 2°2
PROP * OH * ADD
ADD + NO -«. X * N02
ADD + ADD -*- 2X
ADD + He02 -* X + MeO
ADD + C_0_ -*- X + C,0
i i -2.
ADD + C302 -*- X * C30
X -«- HCHO + ALD2 + H02
PROP * 0_ -* OH i- H0_ + ALD2
3 2
PROP + 03 -* OH + C203 + HCHO
BUT + OH M. Sc02
BUT * OH -» C..0_
4 2
NO * C402 .* N02 + C40
NO + ScO_ t- NO, + ScO
2 2
NO * C302 -* ,\02 + C30
-NO * C202 -* X02 •+ C20
NO * He02 ^ N02 + MeO
C.O H- HCHO + C,0_
4 32
ScO -*- ALD2 + C202
CjO H- HCHO + C202
C20 -^ HCHO + Me02
C.O + 0- + ALD4 + HO.
42 2
ScO + 02 + MEK + H02
*
Rate Constant
84.0
2.4
2.5 X IO4
1.0 X IO3
1.2 X IO4
1.0 X IO3
1.0 X IO3
1.0 X IO3
1.0 X IO5 min"1
8.0 X IO"3
8.0 X IO"3
1.8 X IO3
1.8 X IO3
1.8 X IO3
1.8 X IO3
1.8 X IO3
1.8 X IO3
1.8 X IO3
7.5 X IO4 min'1
i.o x io5 min-i
8.0 X IO3 min'1
4.0 X IO3 Bin-l
0.7
1.4
PROCEEDINGS—PAGE 232
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Number
46
47
48
49
50
51
52
53
54
55
56
57
f O
58
f f\
59
^ f\
60
61
62
63
64
t -
to
66
6 —
.
6S
Reaction
c3o + o
MeO + C
HCHO +
HCHO +
HCHO +
ALD2 +
ALD2 +
ALD2 +
ALD3 +
ALD3 -*•
ALD3 +
ALD4 +
ALD4 +
ALD4 +
ADD +
ADD *
C4°3 +
c3o3 *
c_o. *
2 J
CO *
S 3
C,07 •>
3 3
C2
hv -»•
OH -»-
hv -*•
hv -*
OH -*•
hv -*•
hv -*
OH
C4°2
Sc02
NO -»
NO
NO
N02
NO
2
• N02
ALD3 + HO
ALD2 •»• H02
HCHO + H02
Stable Products
2H02
HO
2
Stable Products
Me02 * H02
C2°3
Stable Products
C2°2 + H°2
C3°3
Stable Products
CO ^. tJf\
•v v*% 4iW»
32 2
•* C 0
4 3
-*- X 1- C.O
4
-*- X + ScO
' C3°2*N°2
^ C2°3 + N°2
•*• MeO + NO
2 2
-»• PAN
-> PAN
-* PAN
Rate Constant
0.5
0.4
0.4
k
vary
k
vary
A
1.5 X 10
4.2 X 1C"6
k
vary
1.5 X 104
6.0 X 10"5
2.5 X 10"3
4.5 X 104
6.0 X 10~5
1.9 X 10"3
4.5 X 104
1.0 X 103
1.0 X 103
8.0 X 102
8.0 X 102
8.0 X 102
1.0 X 102
1.0 X 102
1.0 X 102
Din
nin
nin
nin"
min
PROCEEDINGS—PAGE 233
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Number
Reaction
^1
Rate Constant
69
70
71
72
73
74
75
76
c,o_ +
4 2
C_0_ +
3.2
Sc02 *
C2°2 +
Me02 +
C4°3*
C_0, *
3 3
C00, +
2 3
HO- H.
2
HO, H-
2
H02 -
K02*
H02-^
«.°2 *
HO- •»
2
HO. -«-
2
Stable Products
Stable Products
Stable Products
Stable Products
Stable Products
Stable Products
Stable Products
Stable Products
4.0 X IO3
4.0 X IO3
4.0 X IO3
4.0 X IO3
4.0 X IO3
4.0 X IO3
4.0 X IO3
4.0 X IO3
Units of ppra" min~ unless otherwise indicated
Source: Dodge (1977).
Symbol
Definition
vary
PROP
BUT
ADD
X
MeO
C2°2
C3°2
C4°2
Sc02
ALD2
ALD3
Diurnal 1-hour average photolytic rate constant
C3H6
CH3CH(OH)CH200
CH3°2
CH3CHO
PROCEEDINGS—PAGE 234
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Svmbol Definition
ALD4
C2°3 CH3C°3
C_03 CH3CH2C°3
C4°3 CH3CH2CH2
PROCEEDINGS—PAGE 235
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3. Comments on the Assumption Inherent in EKMA Model Based on an
Preliminary Study
As descrived in Chapter 2, there are a lot of inherent assumptions in
EKMA. Preliminary study on EKMA practiced by Air Quality Bureau, Environment
Agency, however, made us consider that the following matters might be
examined in greater detail
. Hypothetical column
. Identification of K-, value
. Dilution rate
. Post 9 a.m. emissions
3.1. Hypothetical Column
(1) Uniformity of Vertical Distribution of Precursors
Vertical distribution of precursors, especially of NOx, in the source
area, is not uniform ( Fig-1 ). As far as NOx is concerned, its concentration
tends to decrease with the hight. This tendency of vertical distribution of
NOx leads to the following major difficulties.
The first is that EKMA inevitably overestimates the concentration of
precursors if we take NOx concentration on the ground as the representative
value for the column. This means that the calculated 03 concentration may not
necessarily be compatible with the actual precursors concentration in the
source area.
The second which seems of great importance, is that the NMHC/NOx ratio
on the ground may considerably differ from that of above the ground level
such as at the hight of 500 m or 1,000 m. Since the NMHC/NOx ratio play a key
role in predicting the future trend of maximum ozone level and the reduction
rate of precursors required to attain certain level of ozone, the
non-uniformity of the ratio with respect to the hight can not be ignored
We are skeptical about verifying EKMA by using the ratio on the ground
level. If we verify the EKMA using the ratio on the ground level, the
reduction rate obtained would not be meaningful because of the deviation of
the ratio from the actual situation.
PROCEEDINGS—PAGE 236
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Question we would raise here is :
Is it possible to take into account the non-uniformity of NMHC/NOx
ratio in EKMA ?
If it is possible, what modification could be made ?
(2) Vertical Uniformity of ozone
. The vertical distribution of ozone in some places in Tokyo Bay Area shows
that the difference between the ozone concentration on the ground level and
that in the upper layer is rather greater than we expected ( Fig. 2 ).
Attention should be paid to the fact that after ten hours which is the
calculation time of EKMA, mixing depth goes up to around 1,200 m. It does not
seem that there exist uniform vertical distribution of ozone at the hight of
below 1,200 m. We are now collecting data to examine whether such non-uniform
vertical distribution of ozone is generally observed over Tokyo Bay Area or not.
Taking into consideration these characteristics, can't we say that the
oxidants ( ozone ) concentration at ground level does not represent the upper
layer concentration, nor averaged concentration of the hypothetical column.
Therefore, it is critically important to identify the areas to which the model
is applicable.
Questions we would raise here are :
(i) Is it possible to apply the EKMA to the area where the change of
ozone concentration between the upper layer and ground level is
remarkable ?
(ii) If there is linearity between the ground level ozone concentration
and upper layer ozone concentration, it may be possible to modify
EKMA using this relationship. Is this kind modification possible ?
3.2. Identification of KI Value
(1) Basic Method
In EKMA, K] value is determined automatically if the date and altitude
are designated. We are interested in the method and basic data from which EPA
has derived the relationship between K] value and the set of data for date and
altitude.
PROCEEDINGS—PAGE 237
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(2) Need to Modify Kj Value Calculated Automatically in EKMA
It is generally agreed that the air pollutants such as dust, aerosola
affect the value of K-j. Furthermore, annual variation of K-J value is rather
remarkable in Tokyo Bay Area ( Fig. 3 ). Therefore, it seems difficult to
identify unique K] value based on the EKMA. In other word, vie can not consider
the isopleth obtained by EKMA as those represent the actual situation.
If the actual KI value of high oxidant ( ozone ) day is available, it
seems more appropriate to modify the method of determining K] value.
There may be two ways of modification.
(i) to find out the .date in the EKMA which correspond to the actual
K] value of high oxidznt ( ozone ) day
(l'i) to multiply the ozone concentration of isopleth byVKi ( actual )
//R7 ( EKMA ) ( Fig. 4 )
3.3 Dilution Rate
(1) Mixing Depth
Mixing depth is a factor which represents or reflects the meteorological
conditions. Meteorological conditions associated with the photochemical air
pollution, however, comprises wind direction and velosity in upper layer and
so forth. The research recently conducted by the National Institute for
Environmental Studies suggest the fact that the non-uniformity of wind
direction in the upper layer plays as an important role as the mixing depth
in high oxidant formation.
Taking these meteorological conditions into consideration, it seems that
mixing depth is not the sole factor which accounts for the high oxidant (
ozone ) formation. Since not only the mixing depth but also other meteorological
conditions play an important role in high oxidants ( ozone ) formation, the
relation between high oxidants ( ozone ) formation and mixing depth should be
examined in greater detail.
(2) Normalization for Meteorology
As mentioned above, EKMA only deals with mixing depth as a factor of
meteorological conditions. Figure 5 shows the annual variation of mixing depth
PROCEEDINGS—PAGE 238
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at Otemachi which depicts year to year differences in mixing depth. This means
we inevitably come across difficulties if we try to predict reduction rate of
precursors required to attain certain level of ozone concentration by using
one isopleth. Because the isopleth obtained never account for the future change
of meteorological conditions.
The US EPA states views on the normalization for meteorology in the report
titled " Verification of the Isopleth Method for Relating Photochemical Oxidznt
to Precursors " .
••• It would be useful in future work to normalize the actual oxidant trends
for meteorological variance. This would provide a more appropriate test of
the isopleth method. Normalization for meteorology should also decrease the error
bounds on the actual oxidznt trends, resulting in a more finely-tuned validation
study.
3.4 Post 9 A.M. Emissions and Trajectories
A lot of examinations have been made by the relevant institutes in the US.
It seems, however, the problem of post 9 a.m. emissions has been ignored.
As far as Tokyo Bay Area where various kind of emission sources are densely
located are concerned, the contribution of emission sources to high oxidznt
formation could not be ignored. In the process of examining post 9 a.m. emission
problems, we found there existed two questions. One is the question how we
should decide the source areas. The other is the question how we should take
into account the relationship between emission rate and air pass trajectory.
(1) How to decide source area
As mentioned above, various kind of emission sources are densely located
and they spread rather wider area. Main problem is how to determine the size
of grid. Emission rate changes with the size of grid. We conducted a comparative
study for 6 Km grid and 12 Km grid.
If the source area is large, ie. 12 Km grid, it would inevitably include
both heavily polluted area and relatively non polluted sub-areas. The high
oxidant formation, however, would be highly associated with not non polluted
sub-areas but heavily polluted area.
If the source area is small, ie. 6 Km grid, EKMA isopleth can not descrive
the actual situation because of the dispersion effect. This would result in
overestimation.
PROCEEDINGS—PAGE 239
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(2) Emission Rate and Air Pass Trajectory
In regard to the emission rate, we came across difficulties in terms of
the definition of source-receptor relationships in Tokyo Bay Area. Four typical
patterns of trajectory are observed in Tokyo Bay Area ( Fig. 6 ). Main receptors
change froiji year to year, such as western part of Metropolitan Tokyo in one
year and Saitama prefecture in another year.This is due to the fact that source-
receptor relationship highly depends on the meteorological conditions. In
addition to this factor, the distribution of emission sources in Tokyo Bay Area
that is,big stationary sources located along Tokyo Bay and automotive exhaust
gas in Tokyo Metropolitan area, has great impact on the formation of oxidznt.
These situations would cause following questions.
Could we investigate the historical trend analysis of oxidznt based on one
EKMA isopleth ?
Could we investigate the effects of emission reduction rate necessary for
the attainment of certain level of oxidznt concentration based on one EKMA
isopleht ?
PROCEEDINGS—PAGE 240
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( m )
500 —i
400 —
300 —
200 —
TOO ~
Ms*
Concentration of NO and NOx ( ppb )
7/26/1972 ( 9:00 - 10:00 )
7/27/1972 ( 9:05 - 10:05 )
7/28/1972 ( 9:05 - 10:05 )
Figure 1 Vertical Distribution of MO and NOx at TAKATSU
( Conducted by Kanagawa Prefectual Air Pollution
Research Association in Yokohama, Kawasaki,
Yokosuka Industrial Area )
measurement method : absorptiometry using Saltzman reagent
( one-hour average value )
PROCEEDINGS—PAGE 241
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.
Tok/q?Metro- A
^
Figure 2-1 The Flight Courses for the Aircrafts
PROCEEDINGS—PAGE 242
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2000
(ml
1500
1000
5OO
R'JN 2
9 AUG. 1978
O 5 IOI52O255035-«45K)556065
DISTANCE """'
Figure 2-2 The Ozone Concentration Pattern for Run 2
Flight Course C 10:45 A.M. -0:30 P.M.
RUN 3
9 A'JG. 1973
03 (ppb)
^ 50 35 40 45
IX.-T1)
Figure 2-3 The Ozone Concentration Pattern for Run 3
Flight Course B 2:50 - 4:50 P.M.
PROCEEDINGS—PAGE 243
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2000r
(m)
1300
ICOO
3OO
RUN 9
12 AUG. 1973
03 (ppb)
IJOiCO
D-
5 10 ID
23 53
DISTANCE
4O 43 TO 3i
Kl 63
{km)
Figure 2-4 The Ozone Concentration Pattern for Run. 9
Flight Course B 11:20 A.M. - 1:20 P.M.
PROCEEDINGS—PAGE 244
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s
r-H
t!
c
H
I
1000-
900 -
800 •
700 -
600 -
500 -
400 '
300 '
200 -
100 -
in
«*
CN
W
ft
I
I
CO
CD
2
M
Q
W
W
U
§
I 1
i r
1 I
> I
'66 '157 '68 '69 70 71 72 '73 '74 '75 '76 '77 '78
Figure 3 Year to Year Variation of Monthly Integrated Value
of Ultra-violet
From: Weathering , Vol. 6, 1979 Suga Test Instruments
-------
0 001 OCS 0.1 OJ 03 OA O.S
k) (mm1)
Figure 4 Plot of
T\\9 abscissa is in a squar s root sca'.a.
O.SO, [NO,JO =• 0.03 ppm
PROCEEDINGS—PAGE 246
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- i
100 1
50 -
"fl
June
• • June
ED n June
June
August, 1975
August, 1976
August, 1977
August, 1978
125 ' 175^225 275 325 375 425 475 525 575 625 675 725 775 825 875 925 975 10251075 11251175
I
w
g
H
Q
...
Figure 5 Ogive of Mixing Depth ( m ) a I O'l'WlAC
-------
Figure 6-4
- Moving northward from the coast of Sagarai Bay
PROCEEDINGS—PAGE 248
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Figure 6-3
- Passing over the Metropolis and then moving to
Ibaragi Prefecture
PROCEEDINGS—PAGE 249
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* -'-'
»--"'•"
Figure 6-2
- Passing over the center of the Metropolis in the
afternoon (12:00 - 14:00) and then moving to the
eastern part of Saitaraa Prefecture
PROCEEDINGS—PAGE 250
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Figure 6-1
Trajectory and the Number of Maximum Ox Concentration
Observed
- Passing over the center of the Metropolis in the morning
(10:00 - 12:00) and then moving to the eastern part of
Saitama Prefecture
PROCEEDINGS —PAGE 251
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§
o
M
M
O
H
Z
O
en
I
I
O
+ June-August 1974
(o) June-August 1975
June-August 1976
D June-August 1977
A June-August 1978
75
70
12
Figure 7
18 ' 19 ' 20 ' 21 ' 22 ' 23
Oxidant Concentration ( pphm )
Ogive of Oxidants Concentration on Warning Days in Tokyo Bay Area
( Population is 368 days )
31
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