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

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                          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
D
H
 I
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
w
G
H
Z
O
CO
 I
 I
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
w
D
H
en
w


H
•U
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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n
H
W
O
H
25
O
Cfl
 I
 I
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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w
o
o
w
 I
 I
M


H
oo
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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§
o
w
M
O
M
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cn
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 I
H3


s
W
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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n
w
w
D
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z
o
en
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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§

8
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ro
to
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

-------
8
n
w
M
D
H
a
o
o>
 I
 I
hd

s
W
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

-------
  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

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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

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                                              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

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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

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      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

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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

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      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

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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

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       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

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                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

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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.,
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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).
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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).
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     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.

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(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.

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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

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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

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                                          300
                                          AGO
Fig. 5
100            200            300
  Irradiation Time    (min)
                                                        400
                                            PROCEEDINGS—PAGE 79

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                                     200
                            300
400
         Fig. 6
PROCEEDINGS—PAGE 80
100            200
 Irradiation  Time   (min)
                                                  300
400

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  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

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  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
                                                   '

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                                       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
                                                         PROCEEDINGS—PAGE  121

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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

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           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

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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

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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
-

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.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%


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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

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            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

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  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
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   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

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     ^ 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

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          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

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          -
        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

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                 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

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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

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              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

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   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

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                    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

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               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

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                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

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                      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

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                                             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

-------
              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

-------
       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

-------
               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

-------
             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

-------
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

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                                     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

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         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

-------